WO2019208800A1

WO2019208800A1 - Resin-rubber composite, tire, and production method for resin-rubber composite

Info

Publication number: WO2019208800A1
Application number: PCT/JP2019/018015
Authority: WO
Inventors: 啓之筆本; 福島　敦; 正洋本間; 雄司大久保; 和也山村
Original assignee: 株式会社ブリヂストン; 国立大学法人大阪大学
Priority date: 2018-04-26
Filing date: 2019-04-26
Publication date: 2019-10-31
Also published as: JP7269573B2; JPWO2019208800A1

Abstract

Provided is a resin-rubber composite provided with: a resin member that has a treated surface to which surface treatment using plasma treatment has been applied; and a rubber member that is in contact with the treated surface of the resin member and includes a filler having a silanol group.

Description

Resin rubber composite, tire, and method for producing resin rubber composite

The present disclosure relates to a resin rubber composite, a tire, and a method for manufacturing the resin rubber composite.

Conventionally, resin rubber composites in which a resin member and a rubber member are bonded are used in various fields. For example, in the field of tires, from the viewpoint of weight reduction, ease of molding, recycling, etc., the use of resin members has been studied, and rubber members such as rubber tire frames, treads, belt members, and the like are used. Attempts have been made to bond a resin member to the resin member.
For example, Patent Document 1 discloses a tire that is formed of at least a thermoplastic resin material and has an annular tire frame, and is wound around the outer periphery of the tire frame to form a reinforcing cord layer. There is disclosed a tire including a reinforcing cord member that includes the thermoplastic resin material including at least a polyamide-based thermoplastic elastomer.

However, it is not easy to improve the adhesiveness between the resin member and the rubber member due to the difference in material. For this reason, an adhesive (for example, an organic solvent-based adhesive) is provided between the two to enhance the adhesiveness. It is.

In addition, other methods for improving adhesiveness without using an adhesive have been tried.
For example, in Patent Document 2, the surface temperature of a molded body containing an organic polymer compound is set to a melting point of the organic polymer compound of −120 ° C. or higher, and atmospheric pressure plasma treatment is performed on the surface of the molded body to perform peroxidation. A method for producing a surface-modified molded body in which a product radical is introduced is disclosed.

[Patent Document 1] JP 2012-46030 [Patent Document 2] JP 2016-56363

As described above, when an organic solvent-based adhesive is used, it is necessary to volatilize the solvent after forming the coating film, and the drying process takes time. In addition, installation of exhaust facilities and the like may be required from the viewpoint of the work environment, and there is room for improvement in terms of simplification of manufacturing and cost reduction.
Therefore, in the resin rubber composite disposed so that the resin member and the rubber member are in contact with each other, excellent adhesion between the two can be obtained even if both are in direct contact without using an adhesive. Is desired.

On the other hand, as shown in Patent Document 2, a surface-modified molded body with improved adhesion to other members such as a rubber member by performing atmospheric pressure plasma treatment on the surface of the molded body that is a resin material. Even so, there is still room for improvement in adhesion, and further excellent adhesion is required.

In view of the above circumstances, the present disclosure provides a resin rubber composite excellent in adhesiveness between a resin member and a rubber member in direct contact with the resin member, a tire having the resin rubber composite, and manufacture of the resin rubber composite. It is an object to provide a method.

The gist of the present disclosure is as follows.
<1>
A resin member having a treated surface subjected to a surface treatment by plasma treatment;
A rubber member in contact with the treated surface of the resin member and containing a filler having a silanol group;
A resin rubber composite having:

According to the present disclosure, a resin rubber composite excellent in adhesiveness between a resin member and a rubber member in direct contact with the resin member, a tire having the resin rubber composite, and a method for manufacturing the resin rubber composite are provided. can do.

It is a tire sectional view showing the tire concerning this embodiment. It is a tire half sectional view showing one side of a cut surface which cut a tire of another mode concerning this embodiment along a tire width direction. It is a schematic diagram of the perpendicular | vertical cut surface with respect to the length direction of a bead wire which shows one form of the bead core in this embodiment. It is a schematic diagram of the perpendicular | vertical cut surface with respect to the length direction of a bead wire which shows the other form of the bead core in this embodiment.

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

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.

<Resin rubber composite>
The resin rubber composite according to the present embodiment includes a resin member and a rubber member in contact with the resin member.
The resin member has a treated surface that has been subjected to a surface treatment by plasma treatment.
The rubber member includes a filler that contacts the treated surface of the resin member and has a silanol group.

In recent years, the use of resin members in the fields of tires and the like has been studied from the viewpoints of weight reduction, ease of molding, recycling, and the like. Such a resin member may be disposed at a position in contact with the rubber member. However, an adhesive (for example, an organic solvent-based adhesive) is provided between the resin member and the rubber member due to the difference in material. By improving the property, avoidance of interfacial peeling or the like is achieved.
However, when an organic solvent-based adhesive is used, it is necessary to volatilize the solvent after forming the coating film, and the drying process takes time. In addition, installation of exhaust facilities and the like may be required from the viewpoint of the work environment, and there is room for improvement in terms of simplification of manufacturing and cost reduction.
Therefore, in the resin rubber composite disposed so that the resin member and the rubber member are in contact with each other, excellent adhesion between the two can be obtained even if both are in direct contact without using an adhesive. Is desired.

On the other hand, the present inventors perform a surface treatment by plasma treatment on the resin member and contain a filler having a silanol group in the rubber member, and the rubber member is treated with the treated surface of the resin member. It has been found that the adhesiveness between the resin member and the rubber member is improved by disposing it in contact with the resin member. This is presumed that the adhesion is improved by the interaction between the surface of the resin member activated by the surface treatment and the silanol group of the filler contained in the rubber member.

As described above, according to the resin rubber composite according to the present embodiment having the above-described configuration, excellent adhesiveness between the resin member and the rubber member can be obtained without using an adhesive.

Next, the configuration of the resin rubber composite according to this embodiment will be described in detail.

The resin rubber composite according to the present embodiment includes a resin member and a rubber member in contact with the resin member. In addition, the aspect which has the 2nd rubber member which touches this rubber member may be sufficient.

Here, the method for producing the resin rubber composite according to the present embodiment is not particularly limited, for example, a surface treatment step of performing a surface treatment by plasma treatment on at least a part of the surface of the resin member; Manufactured by a production method having a bonding step in which a rubber member containing a filler having a silanol group is in contact with a surface subjected to a surface treatment in a resin member, and the resin member and the rubber member are bonded by heating. can do.
Note that in this specification, the term “process” includes not only an independent process but also a process that can be clearly distinguished from other processes as long as the purpose is achieved. Included in this term.

(Use)
The resin rubber composite according to the present embodiment is applied to various fields in which a resin member and a rubber member are used. , Seismic isolation rubber, sealing materials, caulking materials, bicycles and other fields.

In addition, when the resin rubber composite is used for a tire, examples of the combination of the resin member and the rubber member include the following combinations.
A combination of a belt layer as a resin member and at least one member selected from a tread as a rubber member, a tire skeleton, and a rubber sheet bonded to the surface of the belt layer.
A combination of a bead member as a resin member, a tire skeleton as a rubber member, and at least one member selected from a rubber sheet bonded to the surface of the bead member.
A combination of a tire skeleton as a resin member and at least one member selected from a tread as a rubber member, a belt layer, a bead member, and a rubber sheet bonded to the surface of the tire skeleton.
A combination of a belt cord as a resin member, a cord covering layer covering the belt cord as a rubber member, and at least one member selected from a rubber sheet bonded to the surface of the belt cord (that is, a belt) The layer is a resin rubber composite).
A combination of a bead wire as a resin member, a wire coating layer covering the bead wire as a rubber member, and at least one member selected from a rubber sheet bonded to the surface of the bead wire (that is, a bead core) Is a resin rubber composite).
The above-mentioned “tire frame as a rubber member” is a member constituting a tire frame such as a carcass corresponding to a rubber member (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber). It may be replaced.

In particular, as an aspect in which the resin rubber composite has a resin member, a rubber member in contact with the resin member, and a second rubber member in contact with the rubber member, for example, the following combinations may be mentioned.
A combination of a belt layer as a resin member, a rubber sheet as a rubber member, and at least one member selected from a tread as a second rubber member, a tire skeleton, and a side rubber.
A combination of a bead member as a resin member, a rubber sheet as a rubber member, a tire skeleton as a second rubber member, and at least one member selected from side rubber.
A combination of a tire skeleton as a resin member, a rubber sheet as a rubber member, and at least one member selected from a tread, a belt layer, a bead member, and a side rubber as a second rubber member.
A combination of a belt cord as a resin member, a rubber sheet as a rubber member, and a cord covering layer as a second rubber member (that is, the belt layer is a resin rubber composite).
A combination of a bead wire as a resin member, a rubber sheet as a rubber member, and a wire coating layer as a second rubber member (that is, the bead core is a resin rubber composite).
The “tire frame as the second rubber member” is a tire frame such as a carcass corresponding to the second rubber member (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber). You may replace with the member which comprises.

The structure of the tire having the resin member, the rubber member, and the second rubber member when further provided will be described later.

Here, the resin member, the rubber member, and the second rubber member constituting the resin rubber composite according to the present embodiment will be described in detail.

(Resin member)
The resin member has a treated surface that has been subjected to a surface treatment by plasma treatment. The treated surface of the resin member is activated by being subjected to the above-described surface treatment, whereby adhesion to a rubber member containing a filler having a silanol group is improved.

-Group to be introduced In addition, it is preferable that the treated surface in a resin member introduce | transduces the active group which produces interaction with a silanol group by said surface treatment.
For example, active groups introduced by surface treatment by plasma treatment include peroxy radicals (—O—O.), Hydroperoxide groups (—O—OH), carbonyl groups (—C (═O) —), aldehyde groups Examples thereof include an oxidizing group such as (—C (═O) —H), a carboxy group (—C (═O) —OH), and a hydroxyl group (—OH).
Among these, from the viewpoint of improving adhesion, a peroxy radical (—O—O.), A hydroperoxide group (—O—OH), a carbonyl group (—C (═O) —), an aldehyde group (—C (= More preferably, at least one selected from O) —H), a carboxy group (—C (═O) —OH), and a hydroxyl group (—OH) is introduced.

-Contact angle of water The treated surface of the resin member subjected to the surface treatment preferably has a contact angle of water of 20 ° or more and 98 ° or less, and 50 ° or more and 96 from the viewpoint of improving adhesiveness. More preferably, it is 60 ° or less and more preferably 60 ° or more and 95 ° or less.

The contact angle of water on the treated surface of the resin member is such that pure water is dropped at 25 ° C. on the treated surface of the resin member after the surface treatment, and automatic minimum contact made by Kyowa Interface Science Co., Ltd. It is measured by observing the shape of the droplet using a goniometer (MCA-3).

・ Surface treatment method (plasma treatment method)
Next, a surface treatment method applied to the surface of the resin member will be described.

The conditions for performing the plasma treatment as the surface treatment on the surface of the resin member are not particularly limited as long as the surface after the treatment is activated, and can be performed by a known method. In other words, conditions capable of generating plasma can be appropriately employed.

The temperature of the environment in plasma processing (that is, the environment in which the resin member is installed and plasma is generated) is preferably 0 ° C. or higher and 240 ° C. or lower from the viewpoint of improving adhesiveness and simplifying the plasma processing. More preferably, the temperature is from 150 ° C. to 220 ° C., more preferably from 15 ° C. to 200 ° C.
Further, the atmospheric pressure in the plasma treatment is preferably 5 hPa or more and 2000 hPa or less, more preferably 10 hPa or more and 1500 hPa or less, and further preferably 10 hPa or more and 1300 hPa or less, from the viewpoint of improving adhesiveness and simplifying the plasma treatment.

For the generation of plasma, for example, it is preferable to use a high-frequency power source having an applied voltage frequency of 50 Hz to 2.45 GHz.
The output power per unit area (that is, the irradiation density) is, for example, 1 W / cm ² or more, preferably 3 W / cm ² or more, more preferably 5 W / cm ² or more, while the upper limit is not particularly limited. However, it is good to set it as 50 W / cm < ² > or less, for example.
When pulse output is used, a pulse modulation frequency of 1 kHz to 50 kHz (preferably 5 kHz to 30 kHz), a pulse duty of 5% to 99% (preferably 15% to 80%, more preferably 25). % To 70%).
The counter electrode is preferably made of a cylindrical or flat metal whose one side is coated with a dielectric. The distance between the counter electrode and the resin member is not particularly limited, but is preferably 10 mm or less, more preferably 3 mm or less, still more preferably 1.2 mm or less, and particularly preferably 1 mm or less. Although the minimum of distance is not specifically limited, For example, it is 0.5 mm or more.

The time during which the plasma treatment is performed (that is, the irradiation time) is preferably 2 seconds or longer and 30 minutes or shorter, more preferably 30 seconds or longer and 20 minutes or shorter, from the viewpoint of improving adhesiveness and simplifying the plasma processing, and more preferably 1 minute More preferably, it is 10 minutes or less.

As a gas used for generating plasma, for example, a rare gas such as helium, argon, or neon, or a reactive gas such as oxygen, nitrogen, hydrogen, or ammonia can be used. That is, it is preferable to use only non-polymerizable gas as the gas used in the present embodiment. These gases may use only 1 type, or 2 or more types of noble gases, or use the mixed gas of 1 type, or 2 types or more of noble gases, and 1 type, or 2 or more types of reactive gas of appropriate amount. Also good.
The generation of the plasma may be performed under the above-described conditions in which the gas atmosphere is controlled using a chamber, or may be performed under a completely open atmosphere condition in which, for example, a rare gas is flowed to the electrode portion.

-Resin Resin is contained in the resin member in this embodiment.

The resin member preferably contains a resin as a main component. Specifically, the resin content is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 75% by mass or more with respect to the total amount of the resin members.

In the present specification, “resin” is a concept including a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, and does not include vulcanized rubber.
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.
“Thermoplastic elastomer” means a copolymer having a hard segment and a soft segment. The hard segment refers to a component that is relatively harder than the soft segment, and is preferably a molecular constraining component that serves as a crosslinking point of the crosslinked rubber that prevents plastic deformation. On the other hand, the soft segment refers to a component that is relatively softer than the hard segment, and is preferably a flexible component that exhibits rubber elasticity.
Specifically, as the thermoplastic elastomer, for example, a crystalline polymer having a high melting point hard segment or a polymer constituting a hard segment having a high cohesive force, and a polymer constituting an amorphous soft segment having a low glass transition temperature, And a copolymer having. The thermoplastic elastomer includes, for example, a polymer compound that softens and flows as the temperature rises, becomes relatively hard and strong when cooled, and has rubbery elasticity. The hard segment is, for example, a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure enabling intermolecular packing by intermolecular hydrogen bonding or π-π interaction, etc. Can be mentioned. The soft segment includes, for example, a segment having a long chain group (for example, a long chain alkylene group) in the main chain, a high degree of molecular rotation freedom, and a stretchable structure.

Examples of the thermoplastic resin contained in the resin material include polyester-based thermoplastic resins, polyamide-based thermoplastic resins, polystyrene-based thermoplastic resins, polyurethane-based thermoplastic resins, polyolefin-based thermoplastic resins, and vinyl chloride-based thermoplastic resins. Can be illustrated.

Examples of the thermoplastic elastomer contained in the resin material include polyester-based thermoplastic elastomer (TPEE), polyamide-based thermoplastic elastomer (TPA), polystyrene-based thermoplastic elastomer (TPS), and polyurethane-based thermoplastic as defined in JIS K6418. Examples include elastomers (TPU), polyolefin-based thermoplastic elastomers (TPO), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ).

Examples of the thermosetting resin contained in the resin material include phenol-based thermosetting resins, urea-based thermosetting resins, melamine-based thermosetting resins, and epoxy-based thermosetting resins.

In a resin member, you may use these individually or in combination of 2 or more types.
Among these, the resin contained in the resin material includes polyester-based thermoplastic elastomer, polyester-based thermoplastic resin, polyamide-based thermoplastic elastomer, polyamide-based thermoplastic resin, polystyrene-based thermoplastic elastomer, polystyrene-based thermoplastic resin, polyurethane. A thermoplastic thermoplastic elastomer, a polyurethane thermoplastic resin, a polyolefin thermoplastic elastomer, or a polyolefin thermoplastic resin is preferable, and a polyester thermoplastic elastomer or a polyester thermoplastic resin is more preferable.

[Thermoplastic elastomer]
-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.

As polyester which forms a hard segment, aromatic polyester can be used, for example. 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 at least one of terephthalic acid and dimethyl terephthalate and 1,4-butanediol. The aromatic polyester includes, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5 A dicarboxylic acid component such as sulfoisophthalic acid or an ester-forming derivative thereof and a diol having a molecular weight of 300 or less (for example, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc. Aliphatic diols such as: 1,4-cyclohexanedimethanol, tricyclodecane dimethylol and other alicyclic diols; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2- Bi [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′- And diol components such as aromatic diols such as dihydroxy-p-terphenyl and 4,4′-dihydroxy-p-quarterphenyl; and the like. Alternatively, it may be a copolyester in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, polyfunctional oxyacid component, polyfunctional hydroxy component and the like in a range of 5 mol% or less.
Examples of the polyester 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. .

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

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

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

-Polyamide thermoplastic elastomer-
The polyamide-based thermoplastic elastomer is a thermoplastic polymer composed only 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 a resin material 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 polyamide-based thermoplastic elastomers include amide-based thermoplastic elastomers (TPA) defined in JIS K6418: 2007, polyamide-based elastomers described in JP-A No. 2004-346273, and the like. it can.

In the polyamide-based thermoplastic elastomer, examples of the polyamide forming the hard segment include polyamides produced by 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 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 (for example, an alkylene group having 3 to 18 carbon atoms), and a hydrocarbon molecular chain having 4 to 15 carbon atoms (for example, (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 the general formula (2), R ² is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms (eg, 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.

Examples of the ω-aminocarboxylic acid 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, 12-aminododecanoic acid and the like. Examples thereof include aliphatic ω-aminocarboxylic acids. Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ε-caprolactam, udecan lactam, ω-enantolactam, and 2-pyrrolidone.
Examples of the diamine include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, 2, 4 Examples thereof include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine.
The dicarboxylic acid can be represented by HOOC- (R ³ ) _m —COOH (R ³ : a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1). For example, oxalic acid, succinic acid And aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
As the polyamide forming the hard segment, a 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. 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. 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 an integer of 1 to 20. y represents an integer of 4 to 50. ]

In 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, the combination of the hard segment and the soft segment mentioned above can be mentioned. Among these, combinations of the hard segment and the soft segment include a combination of a ring-opening polycondensate of lauryl lactam and polyethylene glycol, a combination of a ring-opening polycondensate of lauryl lactam and polypropylene glycol, and a ring opening of lauryl lactam. A combination of a polycondensate and a polytetramethylene ether glycol, or a ring-opening polycondensate of lauryl lactam and an ABA type triblock polyether is preferred, and a ring opening polycondensate of lauryl lactam and an ABA type triblock polyether The combination with is more preferable.

The number average molecular weight of the polymer forming the hard segment (that is, polyamide) is preferably 300 to 15000 from the viewpoint of melt moldability. The number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 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, and 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 UBE Kosan's “UBESTA XPA” series (for example, XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044), Daicel Eponic Co., Ltd. “Vestamide” series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) can be used.

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

As a combination of a hard segment and a soft segment, the 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 and polybutadiene or a combination of polystyrene and 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 forming the hard segment (that is, polystyrene) is preferably from 5,000 to 500,000, more preferably from 10,000 to 200,000.
Further, the number average molecular weight of the polymer forming the soft segment is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 800,000, and even more preferably from 30,000 to 500,000. Furthermore, the volume ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 5:95 to 80:20, more preferably 10:90 to 70:30, from the viewpoint of moldability.

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 copolymers [eg, SBS (polystyrene-poly (butylene) block-polystyrene), SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene)], styrene- Isoprene copolymer (polystyrene-polyisoprene block-polystyrene), styrene-propylene copolymer [eg SEP (polystyrene- (ethylene / propylene) block), SEPS (polystyrene-poly (ethylene / propylene) block-polystyrene), SEEPS (polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene), SEB (polystyrene (ethylene / butylene) block)] and the like.

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 or a long-chain aliphatic polyester. Examples of such diol compounds include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly-ε-caprolactone diol, poly (hexamethylene carbonate) having a molecular weight within the above range. Diol, ABA type triblock polyether, etc. are mentioned.
These can be used alone or in combination of two or more.

In Formula A and Formula B, R is a partial structure introduced using a diisocyanate compound containing an aliphatic hydrocarbon, 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 thereof 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 forming the hard segment (that is, polyurethane) is preferably 300 to 1500 from the viewpoint of melt moldability. 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. . The mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 15:85 to 90:10, and 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 consisting only of an aromatic diol and an aromatic diisocyanate and a soft segment consisting only of a polycarbonate ester is preferable, and more specifically, tolylene Isocyanate (TDI) / polyester polyol copolymer, TDI / polyether polyol copolymer, TDI / caprolactone polyol copolymer, TDI / polycarbonate polyol copolymer, 4,4′-diphenylmethane diisocyanate (MDI) / Polyester polyol copolymer, MDI / polyether polyol copolymer, MDI / caprolactone polyol copolymer, MDI / polycarbonate polyol copolymer, and MDI + hydroquinone / polyhe At least one selected from Sa methylene carbonate copolymer. Among them, TDI / polyester polyol copolymer, TDI / polyether polyol copolymer, MDI / polyester polyol copolymer, MDI / polyether polyol copolymer, and MDI + hydroquinone / polyhexamethylene carbonate copolymer At least one selected from is more preferable.

Examples of commercially available polyurethane-based thermoplastic elastomers include, for example, “Elastolan” series (for example, ET680, ET880, ET690, ET890, etc.) manufactured by BASF, and “Clamiron U” series (manufactured by Kuraray Co., Ltd.). For example, 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 ) Etc. can be used.

-Polyolefin thermoplastic elastomer-
Examples of the polyolefin-based thermoplastic elastomer include, for example, a hard segment in which at least polyolefin is crystalline and having a high melting point, and other polymers (for example, other polyolefins, polyvinyl compounds, etc.) are amorphous and have a low glass transition temperature. The material which forms the segment is mentioned. Examples of the polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.

Examples of polyolefin-based thermoplastic elastomers include olefin-α-olefin random copolymers and olefin block copolymers. Specifically, 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, 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-methacrylic Methyl copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-acetic acid Examples thereof include vinyl copolymers and propylene-vinyl acetate copolymers.

Among these, polyolefin-based thermoplastic elastomers include propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, 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, Lopylene-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 polyolefin-type thermoplastic elastomer are preferable.

The number average molecular weight of the polyolefin-based thermoplastic elastomer is preferably 5,000 to 10,000,000. When the number average molecular weight of the polyolefin-based thermoplastic elastomer is 5,000 to 10,000,000, the mechanical properties of the thermoplastic resin material are sufficient, and the processability is also excellent. From the same viewpoint, the number average molecular weight of the polyolefin-based 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. The number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 95:15, and more preferably 50:50 to 90:10, from the viewpoint of moldability.
The polyolefin-based thermoplastic elastomer can be synthesized by copolymerization by a known method.

In addition, as the polyolefin-based thermoplastic elastomer, those obtained by acid-modifying a polyolefin-based thermoplastic elastomer may be used.
“A product obtained by acid-modifying a polyolefin-based thermoplastic elastomer” refers to a product obtained by bonding an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group to a polyolefin-based thermoplastic elastomer.
Examples of bonding an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group to a polyolefin-based thermoplastic elastomer include, for example, an unsaturated compound having an acidic group as a polyolefin-based thermoplastic elastomer, Examples include bonding (for example, graft polymerization) an unsaturated bonding site of an unsaturated carboxylic acid (for example, generally maleic anhydride).
As the unsaturated compound having an acidic group, an unsaturated compound having a carboxylic acid group which is a weak acid group is preferable from the viewpoint of suppressing deterioration of the polyolefin-based thermoplastic elastomer. Examples of the unsaturated compound having an acidic group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and the like.

Commercially available products of polyolefin-based thermoplastic elastomers include, for example, “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, N11 manufactured by Polychemical Co., Ltd. 8C, 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, etc. 2715AC, 3117AC, 3427AC, 3717AC, etc.), Sumitomo Chemical's "Acryt" series, "Evertate" series, etc., Tosoh Corporation's "Ultrasen" series, etc., "Prime TPO" series (Prime polymer) For example, E-2900H, F-3900H, E-2900, F-3900, J-5900, E-2910, F-3910, J-5910, E-2710 F-3710, J-5910, E-2740, F-3740, R110MP, R110E, can be used T310E, also M142E, etc.) and the like.

[Thermoplastic resin]
-Polyester thermoplastic resin-
Examples of the polyester-based thermoplastic resin include polyester that forms the hard segment of the above-described polyester-based thermoplastic elastomer.
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 thermoplastic resins include “Duranex” series (for example, 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., and “Novaduran” series (for example, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) 5010R5, 5010R3-2, etc.), “Toraycon” series (for example, 1401X06, 1401X31, etc.) manufactured by Toray Industries, Inc. can be used.

-Polyamide thermoplastic resin-
Examples of the polyamide-based thermoplastic resin include polyamides that form the hard segments of the aforementioned polyamide-based thermoplastic elastomer.
Specifically, polyamide-based thermoplastic resins include 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 {CO— (CH ₂ ) ₁₀ —NH} _n , for example. 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, for example, by the following structural formula (A-1). 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, “Leona” series (for example, 1300S, 1700S, etc.) manufactured by Asahi Kasei Corporation 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 consisting only of 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.

-Polyolefin thermoplastic resin-
Examples of the polyolefin-based thermoplastic resin include polyolefins that form the hard segment of the aforementioned polyolefin-based thermoplastic elastomer.
Specific examples of the polyolefin-based thermoplastic resin include a polyethylene-based thermoplastic resin, a polypropylene-based thermoplastic resin, and a polybutadiene-based thermoplastic resin. Among these, from the viewpoints of heat resistance and processability, a polypropylene-based thermoplastic resin is preferable as the polyolefin-based 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 thereof include α-olefins having about 3 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene.

[Other ingredients]
The resin member may contain other components such as an additive in addition to the resin as long as the effect is not impaired. Examples of other components include rubber, various fillers (for example, silica, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, color formers, weathering agents, and the like.

(Rubber member)
The rubber member includes a filler having a silanol group. The rubber member containing this filler is in contact with the treated surface of the resin member, thereby improving the adhesion between them.

-Filler which has a silanol group As a filler which has a silanol group contained in a rubber member, particles, such as silica and glass (for example, glass fiber, glass bead, etc.), are mentioned, for example.
Especially, as a filler which has a silanol group, a silica particle is preferable from a viewpoint of adhesive improvement.

Silica includes not only silicon dioxide (SiO ₂ ) in a narrow sense but also silicate compounds, and silicates such as hydrous silicate, calcium silicate, and aluminum silicate in addition to anhydrous silicate. There is no restriction | limiting in particular as said silica, What is used for a commercially available rubber composition etc. can be used. The aggregation state of the silica is not particularly limited, and includes precipitated silica, gel silica, dry silica, colloidal silica, and the like.

In the present embodiment, it is preferable to use hydrophilic silica from the viewpoint of the number of silanol groups on the surface.
Here, that the silica is “hydrophilic” means that the moisture content (that is, loss on drying) specified in JIS-K1150 (1994) is 10% by mass or less.

The content of the filler having a silanol group in the rubber member is preferably 20 phr or more and 100 phr or less, and more preferably 30 phr or more and 90 phr or less, with respect to the total amount of rubber contained, from the viewpoint of improving adhesiveness. .

The rubber member may further contain a silane coupling agent from the viewpoint of dispersibility of the filler having a silanol group. Examples of silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2- Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-isocyanatopropyltriethoxysilane, trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride Etc.
Moreover, as a silane coupling agent, it is preferable to use the polysulfide type | system | group silane coupling agent which has 2 or more sulfur from a dispersible viewpoint of the filler which has a silanol group. Examples of polysulfide silane coupling agents having two or more sulfur include bis- (3- (triethoxysilyl) propyl) -disulfide, bis- (3- (triethoxysilyl) propyl) -tetrasulfide, bis Bis- (trialkoxysilylalkyl) -polysulfides such as-(triethoxysilylpropyl) -polysulfides.
These silane coupling agents may be used alone or in combination of two or more.

-Triazine dithiol The rubber member may contain triazine dithiol from a viewpoint of an adhesive improvement, and a viewpoint of accelerating the vulcanization speed of a rubber member.
Examples of the triazine thiol include alkylaminotriazine dithiol (for example, 2-dimethylamino-4,6-dimercapto-s-triazine, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropylamino-4, 6-dimercapto-s-triazine, 2-diisopropylamino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-diisobutylamino-4,6-dimercapto-s -Triazine, 2-di-tert-butylamino-4,6-dimercapto-s-triazine, 2-dioctylamino-4,6-dimercapto-s-triazine, 2-didodecylamino-4,6-dimercapto-s -Triazine, 2-dipropenylamino-4,6-dimer P-s-triazine, 2-octadecenylamino-4,6-dimercapto-s-triazine, etc.), 2,4,6-trimercapto-s-triazine, 2-phenylamino-4,6-dimercapto-s -Triazine, 2-diphenylamino-4,6-dimercapto-s-triazine, 2-cyclohexylamino-4,6-dimercapto-s-triazine, 2-dicyclohexylamino-4,6-dimercapto-s-triazine, etc. It is done.
Among these, alkylaminotriazine dithiol is preferable.

The content of triazine dithiol in the rubber member is preferably 0.01 phr or more and 10 phr or less with respect to the total amount of rubber, from the viewpoint of improving adhesiveness and increasing the vulcanization speed of the rubber member. It is more preferably 05 phr or more and 5 phr or less, and further preferably 0.1 phr or more and 3 phr or less.

-Rubber The rubber member in the present embodiment includes rubber.

The content of the rubber relative to the total amount of the rubber member is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. On the other hand, as an upper limit, 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is further more preferable.

The rubber contained in the rubber member is not particularly limited, and natural rubber and various synthetic rubbers conventionally used for blending rubber can be used alone or in combination of two or more. For example, a rubber as shown below or a blend of two or more of these can be used.
The natural rubber may be a sheet rubber or a block rubber, and all of RSS # 1 to # 5 can be used.
As the synthetic rubber, various diene synthetic rubbers, diene copolymer rubbers, special rubbers, modified rubbers, and the like can be used. Specifically, for example, a butadiene polymer such as polybutadiene (BR), a copolymer of butadiene and an aromatic vinyl compound (eg, SBR, NBR, etc.), a copolymer of butadiene and another diene compound, and the like; Isoprene polymers such as polyisoprene (IR), copolymers of isoprene and aromatic vinyl compounds, copolymers of isoprene and other diene compounds; chloroprene rubber (CR), butyl rubber (IIR), halogenated Examples thereof include butyl rubber (X-IIR); ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), and any blend thereof.

Moreover, in a rubber member, you may add other components, such as an additive, according to the objective.
Examples of additives include reinforcing materials such as carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, anti-aging agents, and the like. can do.

It should be noted that the rubber member is in an unvulcanized state, and is preferably a vulcanized rubber that is molded into a required shape and crosslinked by heating.

(Second rubber member)
The resin rubber composite according to the present embodiment may have a second rubber member in contact with the rubber member.
The second rubber member includes rubber. Examples of the rubber used include those listed as the rubber contained in the rubber member.
In addition, other components such as additives may be added to the second rubber member depending on the purpose. Examples of this additive include those listed as the additives contained in the rubber member described above. It is mentioned in.

<Tire>
The tire according to this embodiment has the resin rubber composite according to the above-described embodiment.

In addition, when a resin rubber composite is used for a tire, the following combinations are mentioned as a combination of a resin member and a rubber member.
When the resin member is a “belt layer”, examples of the rubber member include at least one member selected from “tread, tire frame, and rubber sheet bonded to the surface of the belt layer”.
When the resin member is a “bead member”, examples of the rubber member include at least one member selected from “a tire frame body and a rubber sheet bonded to the surface of the bead member”.
When the resin member is a “tire frame”, the rubber member includes at least one member selected from “tread, belt layer, bead member, and rubber sheet bonded to the surface of the tire frame”. It is done.
When the resin member is a “belt cord”, the rubber member includes at least one member selected from “a cord covering layer covering the belt cord and a rubber sheet bonded to the surface of the belt cord”. .
When the resin member is “bead wire”, the rubber member includes at least one member selected from “a wire coating layer covering the bead wire and a rubber sheet bonded to the surface of the bead wire”. .
The “tire frame” as the rubber member is a member that forms a tire frame such as a carcass corresponding to the rubber member (for example, a carcass made of only a carcass ply in which a plurality of wires are covered with rubber). It may be replaced.

Moreover, the following combinations are mentioned when the resin rubber composite is an aspect having a resin member, a rubber member in contact with the resin member, and a second rubber member in contact with the rubber member.
When the resin member is a “belt layer”, the rubber member includes “rubber sheet”, and the second rubber member includes at least one member selected from “tread, tire frame body, and side rubber”. Can be mentioned.
When the resin member is a “bead member”, the rubber member includes “rubber sheet”, and the second rubber member includes at least one member selected from “tire frame and side rubber”. .
When the resin member is a “tire frame”, the rubber member includes “rubber sheet”, and the second rubber member is at least one selected from “tread, belt layer, bead member, and side rubber” These members are mentioned.
When the resin member is “belt cord”, the rubber member includes “rubber sheet”, and the second rubber member includes “cord coating layer”.
When the resin member is “bead wire”, the rubber member includes “rubber sheet”, and the second rubber member includes “wire coating layer”.
The “tire skeleton body” as the second rubber member is a skeleton of a tire such as a carcass (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber) corresponding to the second rubber member. You may replace with the member which comprises.

Here, the configuration of the tire according to the present embodiment will be described using specific examples and drawings. In addition, the magnitude | size of the member in each figure is notional, The relative relationship of the magnitude | size between members is not limited to this. Moreover, the same code | symbol is attached | subjected to the member which has the substantially same function through all the drawings, and the overlapping description may be abbreviate | omitted.

First, as a first embodiment, a tire skeleton body and a belt layer will be described by taking a tire corresponding to a resin member as an example.

[First Embodiment]
FIG. 1 is a cross-sectional view along the tire width direction of the tire of the first embodiment.
In the tire of the first embodiment, the tire case 17 (an example of a tire skeleton) corresponds to a resin member. In the first embodiment, as illustrated in FIG. 1, the tire 200 includes a belt layer in which a belt in which a belt cord 26 </ b> A is covered with a coating resin 26 </ b> B is wound in the circumferential direction on the outer peripheral surface of a crown portion 16 of a tire case 17. 26 is formed, and this belt layer 26 also corresponds to a resin member. The belt layer 26 constitutes the outer peripheral portion of the tire case 17 and reinforces the circumferential rigidity of the crown portion 16.
Note that the tire case 17 and the belt layer 26 corresponding to the resin member are treated surfaces in which at least the surface in contact with the cushion rubber 28 is treated by the above-described surface treatment.

In the tire case 17 which is a resin member, the melting point of the resin is, for example, about 100 ° C. to 350 ° C., and from the viewpoint of tire durability and productivity, about 100 ° C. to 250 ° C. is preferable, and 120 ° C. to 250 ° C. is more preferable.

The tensile modulus of elasticity defined in JIS K7113: 1995 of the tire frame body (for example, the tire case 17) 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 modulus is 50 MPa to 1000 MPa, the rim can be assembled efficiently while maintaining the shape of the tire frame.

The tensile strength specified in JIS K7113 (1995) of the tire frame body (for example, the tire case 17) 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 tire frame body (for example, the tire case 17) 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 is 5 MPa or more, it is possible to withstand deformation against a load applied to the tire during traveling or the like.

The tensile yield elongation defined by JIS K7113 (1995) of the tire frame body (for example, the tire case 17) itself is preferably 10% or more, more preferably 10% to 70%, and particularly preferably 15% to 60%. When the tensile yield elongation is 10% or more, the elastic region is large, and the rim assembly property can be improved.

The tensile elongation at break stipulated in JIS K7113 (1995) of the tire frame (for example, the tire case 17) itself is preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, most preferably 200% or more. preferable. When the tensile elongation at break is 50% or more, the rim assemblability is good and it is difficult to break against collision.

The load deflection temperature (at 0.45 MPa load) specified in ISO 75-2 or ASTM D648 of the tire frame body (for example, the tire case 17) itself is preferably 50 ° C. or more, more preferably 50 ° C. to 150 ° C., 50 C. to 130.degree. C. is particularly preferable. When the deflection temperature under load is 50 ° C. or higher, deformation of the tire skeleton can be suppressed even when vulcanization is performed in the manufacture of the tire.

The belt layer 26 is formed by coating a belt cord 26A having higher rigidity than the resin forming the tire case 17 with a coating resin 26B separate from the resin forming the tire case 17. In addition, the belt layer 26 is joined to the belt layer 26 and the tire case 17 at the contact portion with the crown portion 16 (for example, bonded by welding or an adhesive).

Further, a cushion rubber 28 is joined so as to contact a region of the outer peripheral surface of the belt layer 26 and the outer peripheral surface of the tire case 17 that is not covered with the belt layer 26, and rubber is further applied on the outer peripheral surface of the cushion rubber 28. The tread layer 30 including it is joined. The cushion rubber 28 and the tread layer 30 form a rubber tread, and the cushion rubber 28 corresponds to a rubber member. The tread layer 30 is formed with a tread pattern (not shown) including a plurality of grooves on the ground contact surface with the road surface.

Next, a method for manufacturing a tire according to the first embodiment including a tire case 17 and a belt layer 26 corresponding to a resin member will be described.

-Tire case shaping | molding process First, a tire case half body (namely, one half of the tire case which has the shape where the tire case was cut | disconnected by the center part of the tire width direction) is formed by methods, such as extrusion molding, for example. Next, the tire case halves are joined to each other by a method such that the tire case halves face each other and are pressed at a melting point or higher of the resin material constituting the tire case.

Belt layer winding step As a method of forming the belt layer 26 on the crown portion 16 of the tire case 17, for example, a belt wound around a reel while rotating the tire case 17 (that is, the belt cord 26A is applied to the coating resin 26B). The belt member 26 is unwound and this belt is wound around the crown portion 16 a predetermined number of times to form the belt layer 26. The coating resin 26B may be welded to the tire case 17 by heating and pressurizing.

Surface treatment step It should be noted that at least the above-described method is applied to the outer peripheral surface of the belt layer 26 in contact with the cushion rubber 28 and the region of the outer peripheral surface of the tire case 17 that is not covered with the belt layer 26 and in contact with the cushion rubber 28 Surface treatment is performed by However, the timing for performing the surface treatment is not particularly limited. For example, the tire case 17 and the belt layer 26 may be collectively treated after the belt layer 26 is formed. Further, the tire case 17 may be first processed before the belt layer 26 is formed, and then the belt layer 26 may be processed again after the belt layer 26 is formed.

-Lamination process and vulcanization process Next, the cushion rubber 28 in an unvulcanized state is provided for one round so as to come into contact with the outer peripheral surface of the belt layer 26 and the outer peripheral surface of the tire case 17 not covered with the belt layer 26. Wrap. The cushion rubber 28 corresponding to the rubber member contains a filler having a silanol group. Thereafter, the vulcanized, semi-vulcanized or unvulcanized tread layer 30 is wound on the cushion rubber 28 for one turn. Thereafter, the tire of the first embodiment is obtained by vulcanization.

The bead portion 12 of the tire case 17 may be provided with a seal layer 24 that is softer than the resin material used for the tire case 17 using an adhesive or the like.

In the tire 200 of the first embodiment, the cushion rubber 28 corresponding to the rubber member contains a filler having a silanol group, and the tire case 17 corresponding to the resin member and the region in contact with the cushion rubber 28 of the belt layer 26 are described above. Surface treatment by the method of is performed. Therefore, the tire case 17 and the belt layer 26 and the cushion rubber 28 constituting the tread are excellent without using an adhesive between the tire case 17 and the cushion rubber 28 and between the belt layer 26 and the cushion rubber 28. Adhesiveness can be obtained.

(Modification)
In the tire 200 of the first embodiment shown in FIG. 1, the tread is formed on the outer peripheral surface of the tire case 17 by laminating the cushion rubber 28 and the tread layer 30, but the present invention is not limited thereto, and the cushion rubber 28 is not disposed. It is good also as a structure. In this case, the tread layer 30 constituting the tread corresponds to a rubber member, and the tread layer 30 contains a filler having a silanol group.

In the tire 200 according to the first embodiment shown in FIG. 1, the cushion rubber 28 is in direct contact with the tire case 17 and the belt layer 26. However, the present invention is not limited thereto, and the cushion rubber 28, the tire case 17, and the belt are not limited thereto. A rubber sheet corresponding to a rubber member may be interposed between the layer 26 and the layer 26. In this case, the rubber sheet corresponds to a rubber member, and the rubber sheet contains a filler having a silanol group. The cushion rubber 28 corresponds to the second rubber member, and the cushion rubber 28 may not contain a filler having a silanol group.

When a rubber sheet corresponding to the rubber member is interposed between the tire case 17 and belt layer 26 corresponding to the resin member and the cushion rubber 28 corresponding to the second rubber member, the thickness of the rubber sheet is as follows. Is preferably 0.1 μm or more and 100 mm or less, and more preferably 1 μm or more and 2 mm or less.

Next, as a second embodiment, a bead member, a belt cord, and a bead wire will be described as an example of a tire corresponding to a resin member.

[Second Embodiment]
FIG. 2 is a tire half sectional view showing one side of a cut surface cut along the tire width direction of the tire 110 of the second embodiment. In the figure, an arrow TW indicates the width direction of the tire 110 (tire width direction), and an arrow TR indicates the radial direction of the tire 110 (tire radial direction).

As shown in FIG. 2, the tire 110 includes a pair of left and right bead portions 112 (only one bead portion 112 is shown in FIG. 2), and a pair of tires extending from the pair of bead portions 112 outward in the tire radial direction. A side portion 114 and a tread portion 116 extending from one tire side portion 114 to the other tire side portion 114 are provided.

A tire 110 shown in FIG. 2 includes a tire case 140 corresponding to a tire skeleton. The tire case 140 corresponds to a rubber member, and is formed using rubber and contains a filler having a silanol group. The tire case 140 includes a bead portion 112, a tire side portion 114, and a tread portion 116.
In FIG. 2, a tire case 140 corresponding to a rubber member is a member constituting a tire skeleton such as a carcass corresponding to a rubber member (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber). It may be replaced.

A protective layer 122 is provided on the tire side portion 114 and the bead portion 112 in the tire width direction outer side, the bead portion 112 in the tire radial direction inner side, and the bead portion 112 on the tire width direction inner side. In the tire case 140, the bead portion 112, the tire side portion 114, and the tread portion 116 may be integrally formed in the same process, or may be a combination of members formed in different processes. However, it is preferably formed integrally from the viewpoint of production efficiency.

Further, a bead filler 120 extending along the protective layer 122 from the bead core 118 to the outer side in the tire radial direction is embedded in the bead portion 112. The bead filler 120 corresponds to a resin member, and the surface in contact with the tire case 140 is a treated surface treated by the surface treatment described above.

The bead portion 112 is a part that contacts a rim (not shown), and an annular bead core 118 extending along the tire circumferential direction is embedded. The forms that the bead core 118 can take will be described later.

The protective layer 122 is provided for the purpose of increasing the airtightness between the tire case 140 and the rim, and is made of a material such as rubber that is softer and weatherproof than the tire case 140. , May be omitted.

The tread portion 116 is a portion corresponding to the ground contact surface of the tire 110, and is provided with a belt layer 124A. Further, a tread layer 130 is provided on the belt layer 124A via a cushion rubber 124B. The forms that the belt layer 124A can take will be described later.

-Manufacture of tire The manufacturing method of the tire case 140 is not particularly limited. For example, the tire case halves in a state where the tire case 140 is divided by the equator plane (the surface indicated by CL in FIG. 2) are respectively produced by an extrusion molding method (for example, an injection molding method) or the like, You may produce by joining in an equatorial plane. Further, when the tire case 140 corresponding to the rubber member is replaced with a carcass, a carcass produced by a conventionally known method may be used.
As a method of forming the belt layer 124A on the tread portion 116 of the tire case 140, for example, a belt wound around a reel while the tire case 140 is rotated (the belt cord 1 shown in FIG. 3A is coated on the cord covering layer 3). The belt layer 124A is formed by winding the belt around the crown portion 16 a predetermined number of times. The cord covering layer 3 may be welded to the tire case 140 by heating and pressurizing.
As a method for forming the bead filler 120 and the bead core 118 in the bead portion 112 of the tire case 140, for example, a preformed bead filler 120 and an annular member for the bead core 118 are embedded in the bead portion 112 by a known method. May be formed.

In the tire 110 of the second embodiment, a tire case 140 corresponding to a rubber member contains a filler having a silanol group, and a bead filler 120 (an example of a bead member) corresponding to a resin member is in contact with the tire case 140. Is subjected to surface treatment by the above-described method. Therefore, excellent adhesion between the tire case 140 and the bead filler 120 (an example of a bead member) can be obtained without using an adhesive between the tire case 140 and the bead filler 120.

(Modification)
In the tire 110 according to the second embodiment illustrated in FIG. 2, the tire case 140 is shown in a form in which the tire case 140 is in direct contact with the bead filler 120. However, the present invention is not limited thereto, and the rubber member is interposed between the tire case 140 and the bead filler 120. A corresponding rubber sheet may be interposed. In this case, the rubber sheet corresponds to a rubber member, and the rubber sheet contains a filler having a silanol group. The tire case 140 corresponds to the second rubber member, and the tire case 140 may not contain a filler having a silanol group.

When a rubber sheet corresponding to the rubber member is interposed between the bead filler 120 corresponding to the resin member and the tire case 140 corresponding to the second rubber member, the thickness of the rubber sheet is, for example, 0. 1 μm or more and 100 mm or less is preferable, and 1 μm or more and 2 mm or less is more preferable.

(Bead core form)
Next, the forms that the bead core 118 shown in FIG. 2 can take will be described with a plurality of examples.
FIG. 3A is a diagram schematically illustrating a cross section when a part of the bead core 118 is cut perpendicularly to the length direction of the bead wire 1. In FIG. 3A, the wire coating layer 3 is provided so as to be in direct contact with the three bead wires 1. In the embodiment shown in FIG. 3A, the bead wire 1 corresponds to a resin member, and the surface in contact with the wire coating layer 3 is a treated surface treated by the surface treatment described above. Moreover, the wire coating layer 3 corresponds to a rubber member, and is formed using rubber and contains a filler having a silanol group. Therefore, excellent adhesiveness between the bead wire 1 and the wire coating layer 3 can be obtained without using an adhesive between the bead wire 1 and the wire coating layer 3.
In addition, you may produce by carrying out the horizontal and vertical stepping of the one bead wire 1 while heat-welding.

Further, the bead core 118 may have the rubber sheet 2 disposed between the bead wire 1 and the wire covering layer 3. A part of the bead core 118 shown in FIG. 3B is provided with the rubber sheet 2 bonded to the surface of each of the three bead wires 1, and the wire coating layer 3 is further provided on the surface. The rubber sheet 2 corresponds to a rubber member, and the rubber sheet 2 contains a filler having a silanol group. Moreover, the wire coating layer 3 corresponds to a second rubber member, and the wire coating layer 3 may not contain a filler having a silanol group. Thereby, even if it does not interpose an adhesive agent between bead wire 1 and rubber sheet 2, the superior adhesiveness of bead wire 1 and rubber sheet 2 is obtained.

3A and 3B show an embodiment in which three bead wires 1 are arranged in parallel, the number may be two or less, or four or more.
Further, the bead core 118 shown in FIG. 2 is formed by laminating three layers of the three bead wires 1 and the wire covering layer 3 shown in any of FIG. 3A and FIG. 3B (and the rubber sheet 2 in FIG. 3B). It has a form. However, the bead core 118 may be used as a single layer or may be used as a laminate of two or more layers. In that case, it is preferable to weld the wire coating layers.
In addition, although the form which the bead core 118 can take was demonstrated referring FIG. 3A and FIG. 3B, it is not limited to this structure.

The method for producing the bead core 118 is not particularly limited. For example, in the case of producing the bead core 118 shown in FIG. 3B, the rubber material for forming the rubber sheet 2 after the above-described surface treatment is performed on the bead wire 1 which is a resin member (the rubber material is silanol) Containing a filler having a group) and a rubber material for forming the wire coating layer 3 can be produced by an extrusion molding method.

(Belt layer form)
Next, modes that the belt layer 124A shown in FIG. 2 can take will be described.
For example, a configuration similar to that of the bead core 118 illustrated in FIG. 3A can be given, that is, a configuration in which a cord covering layer is provided so as to be in direct contact with three belt cords. In this case, the belt cord corresponds to a resin member, and the surface in contact with the cord covering layer is the treated surface treated by the surface treatment described above. The cord covering layer corresponds to a rubber member, and contains a filler that is formed using rubber and has a silanol group. Therefore, excellent adhesiveness between the belt cord and the cord covering layer can be obtained without using an adhesive between the belt cord and the cord covering layer.

Further, the belt layer 124A may have a rubber sheet disposed between the belt cord and the cord covering layer. As this form, the same configuration as the bead core 118 shown in FIG. 3B can be mentioned, that is, a rubber sheet is adhered to each surface of the three belt cords, and a cord covering layer is further provided on the surface. A configuration is mentioned. In this case, the rubber sheet corresponds to a rubber member, and the rubber sheet contains a filler having a silanol group. The cord coating layer corresponds to the second rubber member, and the cord coating layer may not contain a filler having a silanol group. As a result, excellent adhesion between the belt cord and the rubber sheet can be obtained without using an adhesive between the belt cord and the rubber sheet.

The number of belt cords may be two or less, or four or more, as well as a mode in which three belt cords are arranged in parallel.
Further, the belt layer 124A shown in FIG. 2 has a configuration in which three belt cords and a cord covering layer (and, if necessary, a rubber sheet) are laminated. However, the belt layer 124A may be used by stacking two or more layers. In this case, it is preferable to weld the cord coating layers.
In addition, although the form which 124A can take was demonstrated as mentioned above, it is not limited to this structure.

As mentioned above, although the structure of the tire which concerns on this embodiment was demonstrated giving 1st and 2nd embodiment, these embodiment is an example, In this embodiment, in the range which does not deviate from the summary, various changes are carried out. Can be added. It goes without saying that the scope of rights of the present disclosure is not limited to these embodiments.

As described above, according to the present disclosure, the following resin rubber composite, tire, and method for producing the resin rubber composite are provided.
<1> According to the first aspect of the present disclosure,
A resin member having a treated surface subjected to a surface treatment by plasma treatment;
A rubber member in contact with the treated surface of the resin member and containing a filler having a silanol group;
There is provided a resin rubber composite having
<2> According to the second aspect of the present disclosure,
The treated surface of the resin member is treated with a peroxy radical (—O—O.), A hydroperoxide group (—O—OH), a carbonyl group (—C (═O) —), an aldehyde group (— The resin rubber according to the first aspect, which is a surface into which at least one selected from C (═O) —H), a carboxy group (—C (═O) —OH), and a hydroxyl group (—OH) is introduced. A complex is provided.
<3> According to the third aspect of the present disclosure,
The resin rubber composite according to the first or second aspect, in which a contact angle of water on the treated surface of the resin member is 20 ° or more and 98 ° or less, is provided.
<4> According to the fourth aspect of the present disclosure,
There is provided a resin rubber composite according to any one of the first to third aspects, wherein the filler having a silanol group is silica.
<5> According to the fifth aspect of the present disclosure,
The resin rubber composite according to the fourth aspect, in which the silica is hydrophilic silica, is provided.
<6> According to the sixth aspect of the present disclosure,
The resin rubber composite according to any one of the first to fifth aspects is provided, wherein the rubber member further contains a polysulfide-based silane coupling agent having two or more sulfur.
<7> According to the seventh aspect of the present disclosure,
Furthermore, the resin rubber composite according to any one of the first to sixth aspects is provided, which has a second rubber member in contact with the rubber member.
<8> According to the eighth aspect of the present disclosure,
The resin rubber composite according to any one of the first to seventh aspects is provided, wherein the rubber member further contains triazinedithiol.
<9> According to the ninth aspect of the present disclosure,
The rubber member includes the resin rubber composite according to the eighth aspect, in which the triazinedithiol is contained in an amount of 0.01 phr to 10 phr with respect to the rubber contained therein.
<10> According to the tenth aspect of the present disclosure,
The resin member is polyester-based thermoplastic elastomer, polyester-based thermoplastic resin, polyamide-based thermoplastic elastomer, polyamide-based thermoplastic resin, polystyrene-based thermoplastic elastomer, polystyrene-based thermoplastic resin, polyurethane-based thermoplastic elastomer, polyurethane-based heat A resin rubber composite according to any one of the first to ninth aspects is provided, which contains at least one resin selected from a plastic resin, a polyolefin-based thermoplastic elastomer, and a polyolefin-based thermoplastic resin.
<11> According to the eleventh aspect of the present disclosure,
The resin rubber composite according to the tenth aspect is provided, wherein the resin member contains at least one resin selected from a polyester-based thermoplastic elastomer and a polyester-based thermoplastic resin.
<12> According to the twelfth aspect of the present disclosure,
A tire having a resin rubber composite according to any one of the first to eleventh aspects is provided.
<13> According to the thirteenth aspect of the present disclosure,
A belt layer as the resin member; and at least one member selected from a tread as the rubber member, a tire skeleton, and a rubber sheet bonded to the surface of the belt layer. A tire according to the aspect is provided.
<14> According to the fourteenth aspect of the present disclosure,
According to the twelfth aspect, including a bead member as the resin member, a tire skeleton as the rubber member, and at least one member selected from a rubber sheet bonded to a surface of the bead member. Tires are provided.
<15> According to the fifteenth aspect of the present disclosure,
A tire skeleton as the resin member, and at least one member selected from a tread, a belt layer, a bead member, and a rubber sheet bonded to the surface of the tire skeleton as the rubber member. A tire according to the twelfth aspect is provided.
<16> According to the sixteenth aspect of the present disclosure,
The resin rubber composite is at least one selected from a belt cord as the resin member, a cord covering layer covering the belt cord as the rubber member, and a rubber sheet bonded to the surface of the belt cord. The tire according to the twelfth aspect is provided.
<17> According to the seventeenth aspect of the present disclosure,
The resin rubber composite is at least one selected from a bead wire as the resin member, a wire coating layer covering the bead wire as the rubber member, and a rubber sheet bonded to the surface of the bead wire. There is provided a tire according to the twelfth aspect of the present invention.
<18> According to the eighteenth aspect of the present disclosure,
A surface treatment step of applying a surface treatment by plasma treatment to at least a part of the surface of the resin member;
A bonding step of placing the rubber member containing a filler having a silanol group in contact with the surface of the resin member that has been subjected to the surface treatment, and heating and bonding the resin member and the rubber member;
A method for producing a resin rubber composite having the following is provided.

Hereinafter, the present disclosure will be specifically described by way of examples. However, the present disclosure is not limited to these descriptions.

[Example 1]
<Preparation of test piece>
1. Resin member As a resin composition, Hytrel 4767N manufactured by Toray DuPont was used as a commercially available polyester-based thermoplastic elastomer to obtain a resin square plate having a thickness of 0.6 mm.

2. Rubber member As the rubber member, the rubber and various compounding agents shown in Table 1 were mixed and stirred at 110 ° C. for 3 minutes with a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a rubber sheet having a thickness of 2.5 mm was obtained with a roll It was.

3. Surface treatment A plasma generator (product name: K2X02L023, manufactured by Myeongchang Kiko Co., Ltd.) was used as the plasma irradiation apparatus for performing the surface treatment on the resin member. As a high frequency power source for the plasma generator, an applied voltage having a frequency of 13.56 MHz is used. As an electrode, a copper tube having an inner diameter of 1.8 mm, an outer diameter of 3 mm, and a length of 165 mm is outer diameter of 5 mm, thickness of 1 mm, and length. The thing of the structure coat | covered with the 100 mm-thick alumina tube was used. A resin member was placed on the upper surface of the sample holder, and the distance between the resin member surface and the electrode was set to 1.0 mm.
The chamber was sealed, and the pressure was reduced to 10 Pa or less with a rotary pump, and then helium gas was introduced until atmospheric pressure (that is, 1013 hPa). Thereafter, the high frequency power source was set so that the output power density (that is, the irradiation density) was 5.7 W / cm ^2, and the moving speed of the scanning stage was set to 2 mm / second.
Thereafter, the surface of the resin member (that is, the square plate) was irradiated with plasma in a helium atmosphere while moving the scanning stage, and the scanning stage was reciprocated twice to perform surface treatment.
The contact angle of water on the treated surface that has been subjected to the surface treatment is shown in Table 1 below. However, the contact angle of water shown in Table 1 is based on the simulation based on the contact angle of water of the resin member obtained by surface treatment using a plasma generator having a specification different from that of the above plasma generator. This is the predicted value obtained.

4). Adhesion A rubber member (that is, a sheet) was bonded to a resin member (that is, a square plate) subjected to plasma treatment, and vulcanized at a vulcanization temperature of 150 ° C. and a pressure of 2 MPa for 30 minutes to obtain a test piece.
After vulcanization, the following peel test was performed on the test piece. The results are shown in Table 1.

[Examples 2 to 10, Comparative Examples 1 to 4]
A test piece was prepared in the same manner as in Example 1 except that a rubber member (that is, a sheet) was prepared according to the formulation shown in Table 1, and a peel test was performed. However, in Example 10, the vulcanization temperature was 145 ° C.

<Measurement of adhesive strength>
Using the test piece obtained in each example, the rubber member and the resin member were peeled off at room temperature (that is, 25 ° C.) at a tensile rate of 100 mm / min with a tensile tester (RTF-1210, manufactured by A & D). A test was conducted, and the adhesive strength [N / 10 mm] was determined from the maximum strength.

Details of each component shown in Table 1 are as follows.
・ Rubber (SBR) / styrene butadiene rubber, JSR Corporation, JSR1502
・ Rubber (NR) / Natural rubber, RSS # 3
・ Carbon Black / Asahi Carbon Co., Ltd., Asahi # 51
・ Silica / Tosoh ・ Silica Co., Ltd., Product name: Nip seal
・ Silane coupling agent / manufactured by Shin-Etsu Chemical Co., Ltd., product name: bis- (triethoxysilylpropyl) -polysulfide ・ accelerator (DPG) / diphenylguanidine, manufactured by Ouchi Shinsei Chemical Industry, Noxeller D
・ Accelerator (CZ) / N-cyclohexylbenzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry, Noxeller CZ
・ Accelerator (DM) / di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Industry, Noxeller DM
Accelerator (NS) / Nt-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry, Noxeller NS-P
・ TADT / 2-dibutylamino-4,6-dimercapto-s-triazine, manufactured by Tokyo Chemical Industry Co., Ltd.

DESCRIPTION OF SYMBOLS 1 Bead wire 2 Rubber sheet 3 Wire coating layer 12 Bead part 16 Crown part 17 Tire case (an example of a tire frame)
18 Bead core 26 Belt layer

26A Belt cord

26B Coating resin 28 Cushion rubber 30 Tread layer 110 Tire 112 Bead portion 114 Tire side portion 116 Tread portion 118 Bead core 122 Protective layer

124A Belt layer

124B Cushion rubber 130 Tread layer 140 Tire case (tire frame) Example)
200 Tire CL Tire Equatorial Plane Q Midpoint

Claims

A resin member having a treated surface subjected to a surface treatment by plasma treatment;
A rubber member in contact with the treated surface of the resin member and containing a filler having a silanol group;
A resin rubber composite having:
The treated surface of the resin member is treated with a peroxy radical (—O—O.), A hydroperoxide group (—O—OH), a carbonyl group (—C (═O) —), an aldehyde group (— 2. The resin rubber composite according to claim 1, which is a surface into which at least one selected from C (═O) —H), a carboxy group (—C (═O) —OH), and a hydroxyl group (—OH) is introduced. body.
The resin rubber composite according to claim 1 or 2, wherein a contact angle of water on the treated surface of the resin member is 20 ° or more and 98 ° or less.
The resin rubber composite according to any one of claims 1 to 3, wherein the filler having a silanol group is silica.
The resin rubber composite according to claim 4, wherein the silica is hydrophilic silica.
The resin rubber composite according to any one of claims 1 to 5, wherein the rubber member further contains a polysulfide-based silane coupling agent having two or more sulfur.
The resin rubber composite according to any one of claims 1 to 6, further comprising a second rubber member in contact with the rubber member.
The resin rubber composite according to any one of claims 1 to 7, wherein the rubber member further contains triazine dithiol.
The resin rubber composite according to claim 8, wherein the rubber member contains 0.01 phr or more and 10 phr or less of the triazine dithiol with respect to the contained rubber.
The resin member is polyester-based thermoplastic elastomer, polyester-based thermoplastic resin, polyamide-based thermoplastic elastomer, polyamide-based thermoplastic resin, polystyrene-based thermoplastic elastomer, polystyrene-based thermoplastic resin, polyurethane-based thermoplastic elastomer, polyurethane-based heat The resin rubber composite according to any one of claims 1 to 9, comprising at least one resin selected from a plastic resin, a polyolefin-based thermoplastic elastomer, and a polyolefin-based thermoplastic resin.
The resin rubber composite according to claim 10, wherein the resin member contains at least one resin selected from a polyester-based thermoplastic elastomer and a polyester-based thermoplastic resin.
A tire having the resin rubber composite according to any one of claims 1 to 11.
The belt layer as the resin member, and at least one member selected from a tread as the rubber member, a tire skeleton, and a rubber sheet bonded to the surface of the belt layer. Tires.
The tire according to claim 12, comprising a bead member as the resin member, a tire skeleton as the rubber member, and at least one member selected from a rubber sheet bonded to a surface of the bead member. .
A tire skeleton as the resin member, and at least one member selected from a tread, a belt layer, a bead member, and a rubber sheet bonded to the surface of the tire skeleton as the rubber member. Item 13. The tire according to Item 12.
The resin rubber composite is at least one selected from a belt cord as the resin member, a cord covering layer covering the belt cord as the rubber member, and a rubber sheet bonded to the surface of the belt cord. The tire according to claim 12, wherein the tire layer is a belt layer.
The resin rubber composite is at least one selected from a bead wire as the resin member, a wire coating layer covering the bead wire as the rubber member, and a rubber sheet bonded to the surface of the bead wire. The tire according to claim 12, wherein the tire is a bead core.
A surface treatment step of applying a surface treatment by plasma treatment to at least a part of the surface of the resin member;
A bonding step of placing the rubber member containing a filler having a silanol group in contact with the surface of the resin member that has been subjected to the surface treatment, and heating and bonding the resin member and the rubber member;
The manufacturing method of the resin rubber composite which has this.