JPWO2019208800A1 - Resin-rubber composite, tire, and method for manufacturing resin-rubber composite - Google Patents

Abstract

A resin-rubber composite comprising a resin member having a treated surface that has been surface-treated by plasma treatment, and a rubber member that is in contact with the treated surface of the resin member and contains a filler having a silanol group.

Description

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

Conventionally, a resin-rubber composite in which a resin member and a rubber member are bonded has been used in various fields. For example, in the field of tires, the use of resin members is being considered from the viewpoints of weight reduction, ease of molding, recycling, etc., and rubber members such as rubber tire skeletons, treads, and belt members. It has been tried to use it by adhering it to a resin member.
For example, Patent Document 1 describes, at least, a tire formed of a thermoplastic resin material and having an annular tire skeleton, which is wound around the outer peripheral portion of the tire skeleton in the circumferential direction to form a reinforcing cord layer. A tire having a reinforcing cord member and the thermoplastic resin material containing at least a polyamide-based thermoplastic elastomer is disclosed.

However, it is not easy to improve the adhesiveness between the resin member and the rubber member due to the difference in materials. Therefore, an adhesive (for example, an organic solvent-based adhesive) is provided between the resin member and the rubber member to improve the adhesiveness. It has been.

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 product containing an organic polymer compound is set to −120 ° C. or higher, which is the melting point of the organic polymer compound, and the surface of the molded product is subjected to atmospheric pressure plasma treatment to peroxidize. A method for producing a surface-modified molded product into which a substance radical is introduced is disclosed.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2012-46030 [Patent Document 2] Japanese Unexamined Patent Publication No. 2016-56363

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

On the other hand, as shown in Patent Document 2, a surface-modified molded body having improved adhesiveness to other members such as a rubber member by performing atmospheric pressure plasma treatment on the surface of the molded body which is a resin material. Even if there is, there is still room for improvement in adhesiveness, and even better adhesiveness is required.

In view of the above circumstances, the present disclosure describes the production of a resin-rubber composite having excellent adhesiveness between a resin member and a rubber member in direct contact with the resin member, a tire having the resin-rubber composite, and the resin-rubber composite. The challenge is to provide a method.

The gist of this disclosure is as follows.
<1>
A resin member having a treated surface that has been surface-treated by plasma treatment,
A rubber member that is in contact with the treated surface of the resin member and contains a filler having a silanol group,
Resin rubber complex having.

According to the present disclosure, there is provided a resin rubber composite having excellent 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 producing the resin rubber composite. can do.

It is a tire sectional view which shows the tire which concerns on this embodiment. It is a tire semi-cross-sectional view which shows one side of the cut surface which cut the tire of another aspect which concerns on this embodiment along the tire width direction. It is a schematic diagram of the cut plane perpendicular to the length direction of the bead wire which shows one form of the bead core in this embodiment. It is a schematic diagram of the cut plane perpendicular to the length direction of the 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 may be carried out with appropriate modifications within the scope of the purpose of the present disclosure.

The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

<Resin rubber complex>
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 surface-treated by plasma treatment.
The rubber member contains a filler that is in contact with the treated surface of the resin member and has a silanol group.

In recent years, the use of resin members has been studied in the fields of tires and the like from the viewpoints of weight reduction, ease of molding, recycling and the like. In addition, such a resin member may be arranged at a position where it comes into contact with a rubber member, but due to the difference in materials, an adhesive (for example, an organic solvent-based adhesive) is provided between the resin member and the rubber member to bond them. By improving the properties, interfacial peeling and the like are avoided.
However, when an organic solvent-based adhesive is used, it is necessary to volatilize the solvent after the coating film is formed, and the drying process takes time. In addition, the installation of exhaust equipment and the like may be required from the viewpoint of work environment, and there is room for improvement from the viewpoint of simplification of manufacturing and cost reduction.
Therefore, in the resin-rubber composite arranged so that the resin member and the rubber member are in contact with each other, excellent adhesiveness between the two can be obtained even when the resin member and the rubber member are in direct contact with each other without using an adhesive. Is desired.

On the other hand, the present inventors apply a surface treatment by plasma treatment to the resin member, and the rubber member contains a filler having a silanol group, and the rubber member is subjected to 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 arranging the resin member in contact with the rubber member. It is presumed that this is because the adhesiveness was 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-mentioned 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 the present 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 embodiment may further have a second rubber member in contact with the rubber member.

Here, the method for producing the resin-rubber composite according to the present embodiment is not particularly limited, and for example, a surface treatment step of applying a surface treatment by plasma treatment to at least a part of the surface of the resin member and the like. Manufactured by a manufacturing method including a bonding step in which a rubber member containing a filler having a silanol group is placed in contact with the surface-treated surface of the resin member and heated to bond the resin member and the rubber member. can do.
In the present specification, the term "process" is used not only for an independent process but also for a process as long as the purpose is achieved even if the process cannot be clearly distinguished from other processes. Included in this term.

(Use)
The resin-rubber composite according to the present embodiment is applied to various fields in which the resin member and the rubber member are used, for example, a tire, a vibration-proof rubber, a rubber hose, a rubber-resin composite hose, a belt, a rubber crawler, a golf ball, and a bellows. , Seismic isolation rubber, sealing material, coking material, bicycle, etc.

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 adhered 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 adhered 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, a belt layer, a bead member as a rubber member, and a rubber sheet adhered to the surface of the tire skeleton.
-A combination of a belt cord as a resin member, a cord coating layer covering the belt cord as a rubber member, and at least one member selected from a rubber sheet adhered 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 adhered to the surface of the bead wire (that is, a bead core). Is a resin-rubber composite).
The above-mentioned "tire skeleton body as a rubber member" is a member forming a tire skeleton such as a carcass corresponding to a rubber member (for example, a carcass composed of only a carcass ply whose circumference of a plurality of wires is covered with rubber). You may replace it.

In particular, examples of the embodiment 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 include the following combinations.
-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 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 rubbers.
-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 coating 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 above-mentioned "tire skeleton body as the second rubber member" is a tire skeleton such as a carcass corresponding to the second rubber member (for example, a carcass composed of only a carcass ply whose circumference of a plurality of wires is covered with rubber). It may be replaced with a member forming the above.

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

Here, each of 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 surface-treated by plasma treatment. The treated surface of the resin member is activated by the surface treatment, which improves the adhesiveness to the rubber member containing the filler having a silanol group.

-Groups to be introduced It is preferable that an active group that causes an interaction with a silanol group is introduced into the treated surface of the resin member by the above surface treatment.
For example, the active group introduced by the surface treatment by plasma treatment includes a peroxy radical (-O-O.), A hydroperoxide group (-O-OH), a carbonyl group (-C (= O)-), and an aldehyde group. 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, peroxy radical (-O-O.), Hydroperoxide group (-O-OH), carbonyl group (-C (= O)-), 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.

-Water contact angle The treated surface of the surface-treated resin member preferably has a water contact angle of 20 ° or more and 98 ° or less, and 50 ° or more and 96 ° or more, from the viewpoint of improving adhesiveness. It is more preferably ° or less, and even 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 on the treated surface of the resin member after the surface treatment at 25 ° C, and automatic minimum contact manufactured by Kyowa Interface Science Co., Ltd. The measurement is performed by observing the shape of the droplet using an angle meter (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 applying the plasma treatment as the surface treatment to 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. That is, conditions that can generate plasma can be appropriately adopted.

The temperature of the environment in the plasma treatment (that is, the environment in which the resin member is installed and the plasma is generated) is preferably 0 ° C. or higher and 240 ° C. or lower from the viewpoint of improving the adhesiveness and simplifying the plasma treatment. The temperature is more preferably ℃ or more and 220 ℃ or less, and more preferably 15 ℃ or more and 200 ℃ or less.
Further, the atmospheric pressure in the environment 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 the adhesiveness and simplifying the plasma treatment.

For the generation of plasma, for example, it is preferable to use a high frequency power supply having an applied voltage frequency of 50 Hz or more and 2.45 GHz or less.
The output power per unit area (that is, 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, for example, it may be ^{50 W / cm 2 or less.}
When a pulse output is used, a pulse modulation frequency of 1 kHz or more and 50 kHz or less (preferably 5 kHz or more and 30 kHz or less), a pulse duty of 5% or more and 99% or less (preferably 15% or more and 80% or less, more preferably 25). % Or more and 70% or less).
For the counter electrode, it is preferable to use a cylindrical or flat metal having one side 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. The lower limit of the distance is not particularly limited, but is, for example, 0.5 mm or more.

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

As the gas used to generate the 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 a non-polymerizable gas as the gas used in this embodiment. As these gases, only one or more rare gases may be used, or a mixed gas of one or two or more rare gases and an appropriate amount of one or two or more reactive gases may be used. May be good.
The plasma may be generated under the condition that the above-mentioned gas atmosphere is controlled by using a chamber, or may be performed under the condition of complete open to the atmosphere in the form of flowing a rare gas to the electrode portion, for example.

-Resin The resin member in the present embodiment contains a resin.

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

In addition, in this specification, "resin" is a concept including a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, and does not include vulcanized rubber.
The "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 rubber-like 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 restraint component that serves as a cross-linking point of the cross-linked 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 polymer constituting a hard segment having a high crystallinity and a high melting point or a hard segment having a high cohesive force, and a polymer constituting an amorphous soft segment having a low glass transition temperature. Examples thereof include copolymers having. Examples of the thermoplastic elastomer include polymer compounds that soften and flow as the temperature rises, become relatively hard and strong when cooled, and have rubber-like elasticity. The hard segment has, for example, a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure that enables intermolecular packing by intermolecular hydrogen bonds or π-π interactions. Segments can be mentioned. Further, the soft segment includes, for example, a segment having a structure having a long chain group (for example, a long chain alkylene group) in the main chain, a high degree of freedom of molecular rotation, and elasticity.

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

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

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

In the resin member, these may be used alone or in combination of two or more.
Among these, the resins contained in the resin material include polyester-based thermoplastic elastomers, polyester-based thermoplastic resins, polyamide-based thermoplastic elastomers, polyamide-based thermoplastic resins, polystyrene-based thermoplastic elastomers, polystyrene-based thermoplastic resins, and polyurethanes. A based thermoplastic elastomer, a polyurethane-based thermoplastic resin, a polyolefin-based thermoplastic elastomer, or a polyolefin-based thermoplastic resin is preferable, and a polyester-based thermoplastic elastomer or a polyester-based thermoplastic resin is more preferable.

[Thermoplastic elastomer]
-Polyester-based thermoplastic elastomer-
As the polyester-based thermoplastic elastomer, for example, at least polyester forms a hard segment having a high crystallinity and a high melting point, and another polymer (for example, polyester or polyether) is amorphous and has a low glass transition temperature. Examples include the forming material.

As the polyester forming the hard segment, for example, aromatic polyester can be used. The aromatic polyester can be formed from, for example, 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 polyesters include, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyetanedicarboxylic acid, 5 -Dicarboxylic acid components such as sulfoisophthalic acid or ester-forming derivatives thereof and diols having a molecular weight of 300 or less (for example, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.) Alibo diols; 1,4-cyclohexanedimethanol, alicyclic diols such as tricyclodecanedimethylol; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2- Bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4'- It may be a polyester derived from a diol component of an aromatic diol such as dihydroxy-p-terphenyl, 4,4'-dihydroxy-p-quarterphenyl; etc.). Alternatively, it may be a copolymerized polyester 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 functional polyfunctional carboxylic acid component, a polyfunctional oxyic acid component, a 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.

Examples of the polymer forming the soft segment include aliphatic polyesters and aliphatic polyethers.
Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide). ) Ethylene oxide addition polymer of glycol, copolymer of ethylene oxide and tetrahydrofuran, etc. can be mentioned.
Examples of the aliphatic polyester include poly (ε-caprolactone), polyenant lactone, polycaprilolactone, polybutylene adipate, polyethylene adipate and the like.
Among these aliphatic polyethers and aliphatic polyesters, poly (tetramethylene oxide) glycol and poly (propylene oxide) glycol are examples of polymers that form soft segments from the viewpoint of the elastic properties of the obtained polyester block copolymer. Ethylene oxide adduct, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate and the like are preferable.

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. Further, the mass ratio (x: y) of 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 above-mentioned hard segment and the soft segment include the respective combinations of the above-mentioned hard segment and the soft segment. Among these, as the combination of the above-mentioned hard segment and soft segment, a combination in which the hard segment is polybutylene terephthalate and the soft segment is an aliphatic polyether is preferable, and the hard segment is polybutylene terephthalate and the soft segment. More preferably, the combination is poly (ethylene oxide) glycol.

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

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

-Polyamide-based thermoplastic elastomer-
The polyamide-based thermoplastic elastomer is a thermoplastic composed of only a copolymer having a polymer that forms a hard segment that is crystalline and has a high melting point and a polymer that forms a soft segment that is amorphous and has 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 polyamide forms a hard segment having a high crystallinity and a high melting point, and other polymers (for example, polyester, polyether, etc.) are amorphous and have a low glass transition temperature. Examples include the forming material. Further, the polyamide-based thermoplastic elastomer may be formed by using a chain length extender such as a dicarboxylic acid in addition to the hard segment and the soft segment.
Specific examples of the polyamide-based thermoplastic elastomer include the amide-based thermoplastic elastomer (TPA) defined in JIS K6418: 2007, the polyamide-based elastomer described in JP-A-2004-346273, and the like. it can.

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

一般式（１）
［一般式（１）中、Ｒ^１は、炭素数２〜２０の炭化水素の分子鎖（例えば炭素数２〜２０のアルキレン基）を表す。］

General formula (1)
[In the 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). ]

一般式（２）
［一般式（２）中、Ｒ^２は、炭素数３〜２０の炭化水素の分子鎖（例えば炭素数３〜２０のアルキレン基）を表す。］

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

In the general formula (1), the ^{R 1,} preferably a molecular chain of a hydrocarbon of 3 to 18 carbon atoms (e.g., an alkylene group having 3 to 18 carbon atoms), the molecular chain of a hydrocarbon of 4 to 15 carbon atoms (e.g. 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.
Further, in the general formula (2), the ^{R 2,} the molecular chains of hydrocarbon having 3 to 18 carbon atoms (e.g., an alkylene group having 3 to 18 carbon atoms) are preferable, the molecular chain of a hydrocarbon of 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 and lactam. Examples of the polyamide forming the hard segment include polycondensates of these ω-aminocarboxylic acids or lactams, and copolymers of diamines and dicarboxylic acids.

Examples of the ω-aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like having 5 to 20 carbon atoms. An aliphatic ω-aminocarboxylic acid and the like can be mentioned. Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ε-caprolactam, udecan lactam, ω-enantractam, and 2-pyrrolidone.
Examples of the diamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 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 metaxylene diamine.
Further, the dicarboxylic acid can be represented by HOOC- (R ³ ) _m- COOH (R ³ : molecular chain of hydrocarbon having 3 to 20 carbon atoms, m: 0 or 1), for example, oxalic acid, succinic acid. , Glutaric acid, adipic acid, pimelic acid, oxalic acid, azelaic acid, succinic acid, dodecanedioic acid and other aliphatic dicarboxylic acids having 2 to 20 carbon atoms can be mentioned.
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.

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

一般式（３）
［一般式（３）中、ｘ及びｚは、１〜２０の整数を表す。ｙは、４〜５０の整数を表す。］

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

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

Examples of the combination of the hard segment and the soft segment include the respective combinations of the hard segment and the soft segment mentioned above. Among these, the combination of the hard segment and the soft segment includes a combination of a ring-opened polycondensate of lauryllactam and polyethylene glycol, a combination of a ring-opened polycondensate of lauryllactam and polypropylene glycol, and a ring-opened lauryllactam. A combination of a polycondensate and polytetramethylene ether glycol or a ring-opened polycondensate of lauryl lactam and an ABA-type triblock polyether is preferable, and a ring-opened polycondensate of lauryl lactam and an ABA-type triblock polyether are preferable. The combination with is more preferable.

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

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 Industries, Ltd.'s "UBESTA XPA" series (for example, XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.), Daicel Eponic. The "bestamide" series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) can be used.

-Polystyrene-based thermoplastic elastomers As polystyrene-based thermoplastic elastomers, 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 forming soft segments that are crystalline and have a low glass transition temperature. As the polystyrene forming the hard segment, for example, polystyrene obtained by a known radical polymerization method, ionic polymerization method or the like is preferably used, and specific examples thereof include polystyrene having anionic living polymerization. Examples of the polymer forming the soft segment include polybutadiene, polyisoprene, and poly (2,3-dimethyl-butadiene).

Examples of the combination of the hard segment and the soft segment include the respective combinations of the hard segment and the soft segment mentioned above. Among these, as the combination of the hard segment and the soft segment, a combination of polystyrene and polybutadiene or a combination of polystyrene and polyisoprene is preferable. Further, in order to suppress an unintended cross-linking reaction of the thermoplastic elastomer, it is preferable that the soft segment is hydrogenated.

The number average molecular weight of the polymer (that is, polystyrene) forming the hard segment is preferably 5000 to 500000, more preferably 1000 to 20000.
The number average molecular weight of the polymer forming the soft segment is preferably 5000 to 1,000,000, more preferably 1000 to 8,000,000, and even more preferably 30,000 to 500000. Further, 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.

Polystyrene-based thermoplastic elastomers can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
Examples of polystyrene-based thermoplastic elastomers include styrene-butadiene-based copolymers [for example, SBS (polystyrene-poly (butylene) block-polystyrene), SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene)], styrene-. Isoprene copolymers (polystyrene-polystyrene block-polystyrene), styrene-propylene copolymers [eg SEP (polystyrene- (ethylene / propylene) block), SEPS (polystyrene-poly (ethylene / propylene) block-polystyrene), SEEPS (polystyrene-poly (polystyrene-ethylene / propylene) block-polystyrene), SEB (polystyrene (ethylene / butylene) block)] and the like can be mentioned.

Commercially available polystyrene-based thermoplastic elastomers include, for example, the "Tough Tech" series manufactured by Asahi Kasei Corporation (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.). The "SEBS" series (8007, 8076, etc.) and "SEPS" series (2002, 2063, etc.) manufactured by Kuraray Co., Ltd. can be used.

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

［式中、Ｐは、長鎖脂肪族ポリエーテル又は長鎖脂肪族ポリエステルを表す。Ｒは、脂肪族炭化水素、脂環族炭化水素、又は芳香族炭化水素を表す。Ｐ’は、短鎖脂肪族炭化水素、脂環族炭化水素、又は芳香族炭化水素を表す。］

[In the formula, P represents a long-chain aliphatic polyether or a long-chain aliphatic polyester. R represents an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. P'represents a short-chain aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. ]

As the long-chain aliphatic polyether or the long-chain aliphatic polyester represented by P in the formula A, 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 a diol compound include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly-ε-caprolactone diol, and poly (hexamethylene carbonate) having a molecular weight within the above range. Examples thereof include diols and ABA-type triblock polyethers.
These can be used alone or in combination of two or more.

In formulas A and B, R is a partial structure introduced using a diisocyanate compound containing an aliphatic hydrocarbon represented by R, an alicyclic hydrocarbon, or an aromatic hydrocarbon. Examples of the aliphatic diisocyanate compound containing an aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, and 1,6-hexamethylene diisocyanate. Can be mentioned.
Examples of the diisocyanate compound containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexanediisocyanate and 4,4-cyclohexanediisocyanate. Further, 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 represented by P', the alicyclic hydrocarbon, or the aromatic hydrocarbon, for example, those having a molecular weight of less than 500 can be used. Further, P'is derived from a diol compound containing a short-chain aliphatic hydrocarbon represented by P', an alicyclic hydrocarbon, or an aromatic hydrocarbon. Examples of the aliphatic diol compound containing a short-chain aliphatic hydrocarbon represented by P'include glycols and polyalkylene glycols, and 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- Examples thereof include decanediol.
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, and the like. Cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like can be mentioned.
Further, 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'-dihydroxydiphenylsulfide, 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-dihydroxynaphthalin, and 2,6-dihydroxynaphthalin.
These can be used alone or in combination of two or more.

The number average molecular weight of the polymer (that is, polyurethane) forming the hard segment 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 viewpoint 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, 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, the thermoplastic polyurethane described in JP-A-5-331256 can be used.

As the polyurethane-based thermoplastic elastomer, specifically, a combination of a hard segment composed of only an aromatic diol and an aromatic diisocyanate and a soft segment composed of only a polycarbon ester is preferable, and more specifically, a tolylene. Isocyanate (TDI) / polyester-based polyol copolymer, TDI / polyether-based polyol copolymer, TDI / caprolactone-based polyol copolymer, TDI / polycarbonate-based polyol copolymer, 4,4'-diphenylmethane diisocyanate (MDI) / Polyol-based polyol copolymer, MDI / polyether-based polyol copolymer, MDI / caprolactone-based polyol copolymer, MDI / polycarbonate-based polyol copolymer, and MDI + hydroquinone / polyhexamethylene carbonate copolymer. At least one is preferable. Among them, TDI / polyester-based polyol copolymer, TDI / polyether-based polyol copolymer, MDI / polyester polyol copolymer, MDI / polyether-based polyol copolymer, and MDI + hydroquinone / polyhexamethylene carbonate copolymer. At least one selected from the above is more preferable.

Commercially available products of polyurethane-based thermoplastic elastomers include, for example, the "Elastran" series manufactured by BASF (for example, ET680, ET880, ET690, ET890, etc.) and the "Chramiron U" series manufactured by Kuraray Co., Ltd. For example, 2000 series, 3000 series, 8000 series, 9000 series, etc.), "Milactran" series manufactured by Nippon Miractran Co., Ltd. (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc. ) Etc. can be used.

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

Examples of the polyolefin-based thermoplastic elastomer include olefin-α-olefin random copolymers and olefin block copolymers. Specifically, propylene block copolymer, ethylene-propylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1pentene 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- Methacrylate 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-methacrylate copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, Examples thereof include a propylene-ethyl acrylate copolymer, a propylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, and a propylene-vinyl acetate copolymer.

Among these, as the polyolefin-based thermoplastic elastomer, a propylene block copolymer, an ethylene-propylene copolymer, a propylene-1-hexene copolymer, a propylene-4-methyl-1pentene copolymer, and a 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-methacrylate copolymer , Propropylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer At least one selected from coalescence, ethylene-vinyl acetate copolymer, and propylene-vinyl acetate copolymer is preferable, and ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-1-butene copolymer are weighted. At least one selected from coalescing, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer is more preferable.
Further, two or more kinds of olefin resins such as ethylene and propylene may be used in combination. The content of the olefin resin in the polyolefin-based thermoplastic elastomer is preferably 50% by mass or more and 100% by mass or less.

The number average molecular weight of the polyolefin-based thermoplastic elastomer is preferably 5000 to 10000000. When the number average molecular weight of the polyolefin-based thermoplastic elastomer is 5000 to 1000000, 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 1,000 to 1,000,000. Thereby, the mechanical physical characteristics and workability 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, more preferably 50:50 to 90:10, from the viewpoint of moldability.
The polyolefin-based thermoplastic elastomer can be synthesized by copolymerizing by a known method.

Further, as the polyolefin-based thermoplastic elastomer, one obtained by acid-modifying the polyolefin-based thermoplastic elastomer may be used.
The "polyolefin-based thermoplastic elastomer acid-modified" refers to a polyolefin-based thermoplastic elastomer to which an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfate group, or a phosphoric acid group is bonded.
To bond 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, for example, as an unsaturated compound having an acidic group to a polyolefin-based thermoplastic elastomer. It is possible to bond (for example, graft polymerization) an unsaturated bond 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 unsaturated compounds 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, the "Toughmer" series manufactured by Mitsui Chemicals, Inc. (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010. , XM-7070, XM-7080, BL4000, BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-0180, P-0280, P-0480, P-0680, etc.), Mitsui Dupont "Nucrel" series manufactured by Polychemical Co., Ltd. (for example, AN4214C, AN4225C, AN42115C, N0903HC, N0908C, AN42012C, N410, N1050H, N1108C, N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN42 N035C), etc., "Elvalois AC" series (for example, 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715AC, 3117AC, 3427AC, 3717AC, etc.), Sumitomo Chemical Co., Ltd. "Aklift" series , "Evertate" series, etc., "Ultrasen" series manufactured by Tosoh Corporation, etc., "Prime TPO" series made of 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, T310E, M142E, etc.) can also be used.

[Thermoplastic resin]
-Polyester-based thermoplastic resin-
Examples of the polyester-based thermoplastic resin include polyesters that form the hard segments of the polyester-based thermoplastic elastomer described above.
Specific examples of the polyester-based thermoplastic resin include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly (ε-caprolactone), polyenant lactone, polycapryrolactone, and polybutylene. Examples thereof include aliphatic polyesters such as adipate and polyethylene adipate, aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene naphthalate. Among these, polybutylene terephthalate is preferable as the polyester-based thermoplastic resin from the viewpoint of heat resistance and processability.

Commercially available polyester-based thermoplastic resins include, for example, the "Juranex" series manufactured by Polyplastics Co., Ltd. (for example, 2000, 2002, etc.) and the "Novaduran" series manufactured by Mitsubishi Engineering Plastics Co., Ltd. (for example,). 5010R5, 5010R3-2, etc.), "Trecon" series manufactured by Toray Industries, Inc. (for example, 1401X06, 1401X31, etc.) and the like can be used.

-Polyamide-based thermoplastic resin-
Examples of the polyamide-based thermoplastic resin include polyamides that form hard segments of the above-mentioned polyamide-based thermoplastic elastomers.
Specific examples of the polyamide-based thermoplastic resin include a polyamide obtained by ring-opening polycondensation of ε-caprolactam (amide 6), a polyamide obtained by ring-opening polycondensation of undecanlactam (amide 11), and a ring-opening polycondensation of lauryl lactam. Examples thereof include polyamide (amide 12), polyamide (amide 66) obtained by polycondensing diamine and dibasic acid, and polyamide (amide MX) having metaxylene diamine as a constituent unit.

The amide 6 can be represented by, for example, {CO- (CH ₂ ) _5- NH} _n. The amide 11 can be represented by, for example, {CO- (CH ₂ ) _10- NH} _n. The amide 12 can be represented by, for example, {CO- (CH ₂ ) _11- NH} _n. The amide 66 can be represented by, for example, {CO (CH ₂ ) ₄ CONH (CH ₂ ) ₆ NH} _n . The amide MX can be represented by, for example, the following structural formula (A-1). Here, n represents the number of repeating units.

As a commercially available product of amide 6, for example, the "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, the "Rilsan B" series manufactured by Arkema Co., Ltd. can be used. As a commercially available product of amide 12, for example, the "UBE nylon" series manufactured by Ube Industries, Ltd. (for example, 3024U, 3020U, 3014U, etc.) can be used. As a commercially available product of amide 66, for example, the "Leona" series manufactured by Asahi Kasei Corporation (for example, 1300S, 1700S, etc.) can be used. As a commercially available product of amide MX, for example, "MX nylon" series manufactured by Mitsubishi Gas Chemical Company, Inc. (for example, S6001, S6021, S6011, etc.) can be used.

The polyamide-based thermoplastic resin may be a homopolymer composed of only the above-mentioned structural units, or may be a copolymer of the above-mentioned structural units and other monomers. In the case of a copolymer, the content of the structural unit in each polyamide-based thermoplastic resin is preferably 40% by mass or more.

-Polyolefin-based thermoplastic resin-
Examples of the polyolefin-based thermoplastic resin include polyolefins that form hard segments of the above-mentioned polyolefin-based thermoplastic elastomer.
Specific examples of the polyolefin-based thermoplastic resin include polyethylene-based thermoplastic resins, polypropylene-based thermoplastic resins, and polybutadiene-based thermoplastic resins. Among these, polypropylene-based thermoplastic resin is preferable as the polyolefin-based thermoplastic resin from the viewpoint of heat resistance and processability.
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, and the like. 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-eicosen.

[Other ingredients]
In addition to the resin, the resin member may contain other components such as additives as long as the effect is not impaired. Examples of other components include rubber, various fillers (for example, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weather resistant agents, and the like.

(Rubber member)
The rubber member contains a filler having a silanol group. When the rubber member containing the filler comes into contact with the treated surface of the resin member, the adhesiveness between the two is improved.

-Filler having a silanol group Examples of the filler having a silanol group contained in the rubber member include particles such as silica and glass (for example, glass fiber, glass beads, etc.).
Among them, as the filler having a silanol group, silica particles are preferable from the viewpoint of improving the adhesiveness.

Silica contains not only silicon dioxide (SiO ₂ ) in a narrow sense but also silicic acid-based compounds, and in addition to silicic anhydride, contains silicates such as hydrous silicic acid, calcium silicate, and aluminum silicate. The silica is not particularly limited, and those used in commercially available rubber compositions and the like can be used. The aggregated state of the silica is not particularly limited, and includes precipitation method silica, gel method silica, dry silica, colloidal silica and the like.

In this embodiment, it is preferable to use hydrophilic silica from the viewpoint of the number of silanol groups on the surface.
Here, the fact that silica is "hydrophilic" means that the water content (that is, weight loss by drying) defined in JIS-K1150 (1994) is 10% by mass or less.

From the viewpoint of improving adhesiveness, 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. ..

The rubber member may further contain a silane coupling agent from the viewpoint of dispersibility of the filler having a silanol group. Examples of the silane coupling agent 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-isocyanoxidetriethoxysilane, trimethoxysilylpropyl succinate anhydride, triethoxysilylpropyl succinate anhydride And so on.
Further, as the silane coupling agent, it is preferable to use a polysulfide-based silane coupling agent having two or more sulfurs from the viewpoint of dispersibility of the filler having a silanol group. Examples of the polysulfide-based silane coupling agent having two or more sulfurs include bis- (3- (triethoxysilyl) propyl) -disulfide, bis- (3- (triethoxysilyl) propyl) -tetrasulfide, and bis. Examples thereof include bis- (trialkoxysilylalkyl) -polysulfide such as − (triethoxysilylpropyl) -polysulfide.
These silane coupling agents may be used alone or in combination of two or more.

-Triazinedithiol The rubber member may contain triazinedithiol from the viewpoint of improving the adhesiveness and increasing the vulcanization rate of the rubber member.
Examples of triazinethiol include alkylaminotriazinedithiol (eg, 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-dimercapto-s-triazine, 2-octadekenylamino-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 Examples thereof include -4,6-dimercapto-s-triazine.
Of these, alkylaminotriazinedithiol is preferred.

The content of triazinedithiol in the rubber member is preferably 0.01 phr or more and 10 phr or less with respect to the total amount of rubber contained, from the viewpoint of improving the adhesiveness and accelerating the vulcanization rate 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 rubber with respect 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 the upper limit value, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is further preferable.

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

Further, in the rubber member, other components such as additives may be added depending on the purpose.
Examples of the additive include a reinforcing material such as carbon black, a filler, a vulcanizing agent, a vulcanization accelerator, a fatty acid or a salt thereof, a metal oxide, a process oil, an antiaging agent, and the like, and these are appropriately blended. can do.

The rubber member is in an unvulcanized state, and it is preferable that the unvulcanized rubber is a vulcanized rubber that is formed into a desired shape and crosslinked by heating.

(2nd 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 above-mentioned rubber member as well.
Further, other components such as additives may be added to the second rubber member depending on the purpose, and examples of the additives include those listed as the additives contained in the rubber member described above. Listed in.

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

When the resin-rubber composite is used for the tire, the following combinations can be mentioned as the combination of the resin member and the rubber member.
When the resin member is a "belt layer", the rubber member includes at least one member selected from "a tread, a tire skeleton, and a rubber sheet adhered to the surface of the belt layer".
When the resin member is a "bead member", the rubber member includes at least one member selected from "a tire skeleton body and a rubber sheet adhered to the surface of the bead member".
-When the resin member is a "tire skeleton body", the rubber member includes at least one member selected from "tread, belt layer, bead member, and rubber sheet adhered to the surface of the tire skeleton body". Be done.
-When the resin member is a "belt cord", the rubber member includes at least one member selected from "a cord coating layer covering the belt cord and a rubber sheet adhered to the surface of the belt cord". ..
-When the resin member is a "bead wire", the rubber member includes at least one member selected from "a wire coating layer covering the bead wire and a rubber sheet adhered to the surface of the bead wire". ..
The "tire skeleton" as the rubber member is a member forming the skeleton of a tire such as a carcass corresponding to the rubber member (for example, a carcass composed of only a carcass ply whose circumference of a plurality of wires is covered with rubber). You may replace it.

Further, when 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, the following combinations can be mentioned.
-When the resin member is a "belt layer", the rubber member includes a "rubber sheet", and the second rubber member is at least one member selected from "tread, tire skeleton, and side rubber". Can be mentioned.
-When the resin member is a "bead member", the rubber member includes a "rubber sheet", and the second rubber member includes at least one member selected from "tire skeleton and side rubber". ..
-When the resin member is a "tire skeleton", the rubber member includes a "rubber sheet", and the second rubber member is at least one selected from "tread, belt layer, bead member, and side rubber". Members can be mentioned.
-When the resin member is a "belt cord", the rubber member includes a "rubber sheet" and the second rubber member includes a "cord coating layer".
-When the resin member is a "bead wire", the rubber member includes a "rubber sheet" and the second rubber member includes a "wire coating layer".
The "tire skeleton" as the second rubber member is a tire skeleton such as a carcass corresponding to the second rubber member (for example, a carcass composed of only a carcass ply whose circumference of a plurality of wires is covered with rubber). It may be replaced with a member forming the above.

Here, the configuration of the tire according to the present embodiment will be described with reference to specific examples and drawings. The size of the members in each figure is conceptual, and the relative relationship between the members is not limited to this. In addition, members having substantially the same function may be designated by the same reference numerals throughout the drawings, and duplicate description may be omitted.

First, as the first embodiment, a tire in which the tire skeleton body and the belt layer correspond to the resin member will be described as an example.

[First Embodiment]
FIG. 1 is a cross-sectional view of the tire of the first embodiment along the tire width direction.
In the tire of the first embodiment, the tire case 17 (an example of a tire skeleton body) corresponds to a resin member. In the first embodiment, as shown in FIG. 1, in the tire 200, a belt in which the belt cord 26A is covered with the coating resin 26B is wound around the outer peripheral surface of the crown portion 16 of the tire case 17 in the circumferential direction to form a belt layer. 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.
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-mentioned 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, it is preferably about 100 ° C. to 250 ° C., preferably about 120 ° C. to 120 ° C. 250 ° C. is more preferable.

The tensile elastic modulus of the tire skeleton (for example, the tire case 17) itself as defined in JIS K7113: 1995 is preferably 50 MPa to 1000 MPa, more preferably 50 MPa to 800 MPa, and particularly preferably 50 MPa to 700 MPa. When the tensile elastic modulus is 50 MPa to 1000 MPa, the rim assembly can be efficiently performed while maintaining the shape of the tire skeleton.

The tensile strength of the tire skeleton (for example, the tire case 17) itself as defined in JIS K7113 (1995) is usually about 15 MPa to 70 MPa, preferably 17 MPa to 60 MPa, and even more preferably 20 MPa to 55 MPa.

The tensile yield strength specified in JIS K7113 (1995) of the tire skeleton 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 can withstand deformation due to a load applied to the tire during running or the like.

The tensile yield elongation specified in JIS K7113 (1995) of the tire skeleton 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 specified in JIS K7113 (1995) of the tire skeleton body (for example, the tire case 17) itself is preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, and most preferably 200% or more. preferable. When the tensile elongation at break is 50% or more, the rim assembly property is good and it is possible to make it difficult to break due to a collision.

The deflection temperature under load (at 0.45 MPa load) specified in ISO 75-2 or ASTM D648 of the tire skeleton (for example, tire case 17) itself is preferably 50 ° C. or higher, more preferably 50 ° C. to 150 ° C., and 50 ° C. ° C to 130 ° 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, which has a higher rigidity than the resin forming the tire case 17, with a coating resin 26B different from the resin forming the tire case 17. Further, in the belt layer 26, the belt layer 26 and the tire case 17 are joined (for example, welded or adhered with an adhesive) at a contact portion with the crown portion 16.

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

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

-Tire case molding process First, a tire case half body (that is, one half of a tire case having a shape in which the tire case is cut at the center in the tire width direction) is formed by, for example, a resin material by a method such as extrusion molding. Next, the tire case 17 is formed by joining the tire case halves to each other by facing each other and pressing the tire case halves at a temperature equal to or higher than the melting point 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, the belt wound on the reel while rotating the tire case 17 (that is, the belt cord 26A is attached to the coating resin 26B). The coated member) is unwound and the 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 In addition, at least the above-mentioned method is applied to the outer peripheral surface of the belt layer 26 in contact with the cushion rubber 28 and the outer peripheral surface of the tire case 17 which is not covered by the belt layer 26 and is in contact with the cushion rubber 28. Surface treatment is applied. However, the timing of applying the surface treatment is not particularly limited, and 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 treated first before the belt layer 26 is formed, and then the belt layer 26 may be treated again after the belt layer 26 is formed.

Laminating step and vulcanization step Next, one round of unvulcanized cushion rubber 28 is applied so as to be in contact with the outer peripheral surface of the belt layer 26 and the outer peripheral surface of the tire case 17 that are not covered by the belt layer 26. Wrap it around. The cushion rubber 28 corresponding to the rubber member contains a filler having a silanol group. Then, the vulcanized, semi-vulcanized, or unvulcanized tread layer 30 is wound around the cushion rubber 28 for one round. Then, by vulcanization, the tire of the first embodiment is obtained.

The bead portion 12 of the tire case 17 may be provided with a seal layer 24 which is softer than the resin material used for the tire case 17 by 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 region of the tire case 17 corresponding to the resin member and the belt layer 26 in contact with the cushion rubber 28 is described above. The surface is treated by the above method. Therefore, the tire case 17, 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 is obtained.

(Modification example)
In the tire 200 of the first embodiment shown in FIG. 1, a 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 tread is not limited to this, and the cushion rubber 28 is not arranged. It may be configured. In that case, the tread layer 30 constituting the tread corresponds to the rubber member, and the tread layer 30 contains a filler having a silanol group.

Further, in the tire 200 of the first embodiment shown in FIG. 1, the mode in which the cushion rubber 28 is in direct contact with the tire case 17 and the belt layer 26 is shown, but the present invention is not limited to this, and the cushion rubber 28, the tire case 17, and the belt are not limited to this. 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 the rubber member, and the rubber sheet contains a filler having a silanol group. Further, the cushion rubber 28 corresponds to the second rubber member, and the cushion rubber 28 does not have to contain a filler having a silanol group.

When a rubber sheet corresponding to the rubber member is interposed between the tire case 17 and the 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 set. 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 tire in which the bead member, the belt cord, and the bead wire correspond to the resin member will be described as an example.

[Second Embodiment]
FIG. 2 is a half cross-sectional view of a tire showing one side of a cut surface cut along the tire width direction of the tire 110 of the second embodiment. In the figure, the arrow TW indicates the width direction of the tire 110 (tire width direction), and the 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 (note that only one bead portion 112 is shown in FIG. 2) and a pair of tires extending outward in the tire radial direction from the pair of bead portions 112. It has a side portion 114 and a tread portion 116 extending from one tire side portion 114 to the other tire side portion 114.

The tire 110 shown in FIG. 2 includes a tire case 140 corresponding to a tire skeleton body. The tire case 140 corresponds to a rubber member and contains a filler formed of rubber and 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, the tire case 140 corresponding to the rubber member is a member forming the skeleton of a tire such as a carcass corresponding to the rubber member (for example, a carcass composed of only a carcass ply whose circumference of a plurality of wires is covered with rubber). You may replace it.

Further, a protective layer 122 is provided on a part of the tire side portion 114 and the bead portion 112 on the outside in the tire width direction, the bead portion 112 on the inside in the tire radial direction, and the bead portion 112 on the inside in the tire width direction. The tire case 140 may have a bead portion 112, a tire side portion 114, and a tread portion 116 integrally formed in the same process, or may be a combination of members formed in different processes. However, from the viewpoint of production efficiency, it is preferable that the tires are integrally formed.

Further, a bead filler 120 extending from the bead core 118 outward in the tire radial direction along the protective layer 122 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 above-mentioned surface treatment.

The bead portion 112 is a portion that comes into contact with a rim (not shown), and an annular bead core 118 extending along the tire circumferential direction is embedded in the bead portion 112. The possible forms of the bead core 118 will be described later.

The protective layer 122 is provided for the purpose of improving the airtightness between the tire case 140 and the rim, and is made of a material such as rubber that is softer and has higher weather resistance 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 the belt layer 124A is provided. Further, a tread layer 130 is provided on the belt layer 124A via a cushion rubber 124B. The possible forms of the belt layer 124A will be described later.

-Manufacture of tires The method of manufacturing 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 equatorial plane (the plane indicated by CL in FIG. 2) are manufactured by an extrusion molding method (for example, an injection molding method), and the tire case halves are separated from each other. It may be manufactured by joining at the equatorial plane. Further, when the tire case 140 corresponding to the rubber member is replaced with the carcass, the 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, the belt wound around the reel while rotating the tire case 140 (the belt cord 1 shown in FIG. 3A is covered with the cord coating layer 3). The member) is unwound and the belt is wound around the crown portion 16 a predetermined number of times to form the belt layer 124A. The cord coating layer 3 may be welded to the tire case 140 by heating and pressurizing.
As a method of 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 with.

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

(Modification example)
In the tire 110 of the second embodiment shown in FIG. 2, the mode in which the tire case 140 is in direct contact with the bead filler 120 is shown, but the present invention is not limited to this, and a rubber member is formed 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 the rubber member, and the rubber sheet contains a filler having a silanol group. Further, the tire case 140 corresponds to the second rubber member, and the tire case 140 does not have to 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.

(Form of bead core)
Next, the possible forms of the bead core 118 shown in FIG. 2 will be described with reference to a plurality of examples.
FIG. 3A is a diagram schematically showing 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 aspect 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 above-mentioned surface treatment. Further, the wire coating layer 3 corresponds to a rubber member, and contains a filler formed by using rubber and 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.
It should be noted that one bead wire 1 may be manufactured by heat-welding and stepping horizontally and vertically.

Further, the bead core 118 may have a rubber sheet 2 arranged between the bead wire 1 and the wire coating layer 3. A part of the bead core 118 shown in FIG. 3B is provided with a rubber sheet 2 adhered to the surface of each of the three bead wires 1, and a wire coating layer 3 is further provided on the surface thereof. The rubber sheet 2 corresponds to a rubber member, and the rubber sheet 2 contains a filler having a silanol group. Further, the wire coating layer 3 corresponds to the second rubber member, and the wire coating layer 3 does not have to contain a filler having a silanol group. As a result, excellent adhesiveness between the bead wire 1 and the rubber sheet 2 can be obtained without using an adhesive between the bead wire 1 and the rubber sheet 2.

Although 3A and 3B show a mode in which three bead wires 1 are arranged in parallel, the number of the bead wires 1 may be 2 or less or 4 or more.
Further, in the bead core 118 shown in FIG. 2, three bead wires 1 shown in any one of FIGS. 3A and 3B, a wire coating layer 3 (and a rubber sheet 2 in FIG. 3B) are laminated in three layers. It is in the form. However, the bead core 118 may be used as one layer or may be used by stacking two or more layers. In that case, it is preferable to weld the wire coating layers.
Although the possible forms of the bead core 118 have been described with reference to FIGS. 3A and 3B, the present invention is not limited to this configuration.

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 bead wire 1 which is a resin member is subjected to the above-mentioned surface treatment, and then a rubber material for forming the rubber sheet 2 (the rubber material is silanol). It can be produced by an extrusion molding method using (containing a filler having a group) and a rubber material for forming the wire coating layer 3.

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

Further, the belt layer 124A may have a rubber sheet arranged between the belt cord and the cord coating 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 provided by adhering to the surface of each of the three belt cords, and a cord coating layer is further provided on the surface thereof. The configuration can be mentioned. In this case, the rubber sheet corresponds to the rubber member, and the rubber sheet contains a filler having a silanol group. Further, the cord coating layer corresponds to the second rubber member, and the cord coating layer does not have to contain a filler having a silanol group. As a result, excellent adhesiveness between the belt cord and the rubber sheet can be obtained without using an adhesive between the belt cord and the rubber sheet.

Not only the three belt cords are arranged in parallel, but the number of the belt cords may be two or less or four or more.
Further, the belt layer 124A shown in FIG. 2 has a form in which three belt cords, a cord coating layer (and a rubber sheet if necessary) are laminated in one layer. However, the belt layer 124A may be used by laminating two or more layers. In that case, it is preferable to weld the cord coating layers.
Although the possible forms of the belt layer 124A have been described above, the present invention is not limited to this configuration.

The configuration of the tire according to the present embodiment has been described above with reference to the first and second embodiments, but these embodiments are examples, and in the present embodiment, various changes are made within a range that does not deviate from the gist thereof. 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, the present disclosure provides the following methods for producing a resin-rubber composite, a tire, and a resin-rubber composite.
<1> According to the first aspect of the present disclosure,
A resin member having a treated surface that has been surface-treated by plasma treatment,
A rubber member that is in contact with the treated surface of the resin member and contains a filler having a silanol group,
A resin-rubber composite having the above is provided.
<2> According to the second aspect of the present disclosure,
The treated surface of the resin member is subjected to the peroxy radical (-O-O.), Hydroperoxide group (-O-OH), carbonyl group (-C (= O)-), and aldehyde group (-O-O.) By the surface treatment. Resin rubber according to the first aspect, wherein 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,
Provided is a resin-rubber composite according to the first or second aspect, wherein the contact angle of water on the treated surface of the resin member is 20 ° or more and 98 ° or less.
<4> According to the fourth aspect of the present disclosure,
Provided is 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,
Provided is a resin-rubber composite according to the fourth aspect, wherein the silica is hydrophilic silica.
<6> According to the sixth aspect of the present disclosure,
Provided is a resin-rubber complex according to any one of the first to fifth aspects, wherein the rubber member further contains a polysulfide-based silane coupling agent having two or more sulfurs.
<7> According to the seventh aspect of the present disclosure,
Further, a resin rubber composite according to any one of the first to sixth aspects, which has a second rubber member in contact with the rubber member, is provided.
<8> According to the eighth aspect of the present disclosure,
Provided is a resin-rubber composite according to any one of the first to seventh aspects, wherein the rubber member further contains triazinedithiol.
<9> According to the ninth aspect of the present disclosure.
The rubber member is provided with a resin rubber composite according to the eighth aspect, which contains the triazinedithiol in an amount of 0.01 phr or more and 10 phr or less with respect to the contained rubber.
<10> According to the tenth aspect of the present disclosure,
The resin member is a polyester-based thermoplastic elastomer, a polyester-based thermoplastic resin, a polyamide-based thermoplastic elastomer, a polyamide-based thermoplastic resin, a polystyrene-based thermoplastic elastomer, a polystyrene-based thermoplastic resin, a polyurethane-based thermoplastic elastomer, or a polyurethane-based thermal. Provided is a resin-rubber composite according to any one of the first to ninth aspects, 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,
Provided is a resin-rubber composite according to the tenth aspect, 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 complex according to any one of the first to eleventh aspects is provided.
<13> According to the thirteenth aspect of the present disclosure,
The twelfth member having a belt layer as the resin member and at least one member selected from a tread as the rubber member, a tire skeleton body, and a rubber sheet adhered to the surface of the belt layer. Tires from the point of view are provided.
<14> According to the fourteenth aspect of the present disclosure,
According to the twelfth aspect, which comprises a bead member as the resin member, a tire skeleton as the rubber member, and at least one member selected from a rubber sheet adhered to the surface of the bead member. Tires are provided.
<15> According to the fifteenth aspect of the present disclosure,
It has a tire skeleton body as the resin member, and at least one member selected from a tread, a belt layer, a bead member as the rubber member, and a rubber sheet adhered to the surface of the tire skeleton body. A tire according to the twelfth aspect is provided.
<16> According to the 16th viewpoint of the present disclosure,
The resin rubber composite is at least one selected from a belt cord as the resin member, a cord coating layer covering the belt cord as the rubber member, and a rubber sheet adhered to the surface of the belt cord. A tire according to the twelfth aspect, which is a belt layer having the member of the above.
<17> According to the 17th viewpoint 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 adhered to the surface of the bead wire. A tire according to the twelfth aspect, which is a bead core having the member of the above.
<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, and
A bonding step in which a rubber member containing a filler having a silanol group is placed in contact with the surface-treated surface of the resin member and heated to bond the resin member and the rubber member.
A method for producing a resin-rubber complex having the above is provided.

Hereinafter, the present disclosure will be specifically described with reference to Examples, but the present disclosure is not limited to these descriptions.

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

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

3. 3. Surface treatment A plasma generator (manufactured by Meisho Kiko Co., Ltd., product name K2X02L023) was used as the plasma irradiation device for surface-treating the resin member. A high-frequency power source for the plasma generator is one with an applied voltage frequency of 13.56 MHz, and the electrodes are copper tubes with an inner diameter of 1.8 mm, an outer diameter of 3 mm, and a length of 165 mm, and an outer diameter of 5 mm, a thickness of 1 mm, and a length. A structure coated with an alumina tube having a diameter of 100 mm was used. A resin member was placed on the upper surface of the sample holder, and the distance between the surface of the resin member and the electrode was set to 1.0 mm.
The chamber was sealed, the pressure was reduced to 10 Pa or less by a rotary pump, and then helium gas was introduced until the atmospheric pressure (that is, 1013 hPa) was reached. After that, the high frequency power supply 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 / sec.
Then, while moving the scanning stage, the surface of the resin member (that is, the square plate) was irradiated with plasma in a helium atmosphere, and the scanning stage was reciprocated twice to perform surface treatment.
The contact angles of water on the treated surface that has been surface-treated are shown in Table 1 below. However, the water contact angle shown in Table 1 is based on the water contact angle of the resin member obtained by surface treatment using a plasma generator having specifications different from those of the above plasma generator, and is based on a simulation. It is the obtained predicted value.

4. A rubber member (that is, a sheet) was attached to a resin member (that is, a square plate) subjected to an adhesive 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 peeling 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 with the formulation shown in Table 1, and a peeling test was performed. However, in Example 10, the vulcanization temperature was set to 145 ° C.

<Measurement of adhesive strength>
Using the test pieces obtained in each example, the rubber member and the resin member were peeled off at a tensile speed of 100 mm / min at room temperature (that is, 25 ° C.) by a tensile tester (RTF-1210, manufactured by A & D Co., Ltd.). A test was carried out, 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 AQ
-Silane coupling agent / manufactured by Shin-Etsu Chemical Co., Ltd., product name: bis- (triethoxysilylpropyl) -polysulfide / accelerator (DPG) / diphenylguanidine, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., Noxeller D
・ Accelerator (CZ) / N-cyclohexylbenzothiazyl sulfenamide, manufactured by Ouchi Shinko Kagaku Kogyo, Noxeller CZ
・ Accelerator (DM) / di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinko Kagaku Kogyo, Noxeller DM
Accelerator (NS) / N-t-Butyl-2-benzothiazolyl sulphenamide, manufactured by Ouchi Shinko Kagaku Kogyo, Noxeller NS-P
-TADT / 2-dibutylamino-4,6-dimercapto-s-triazine, manufactured by Tokyo Chemical Industry Co., Ltd.

1 Bead wire 2 Rubber sheet 3 Wire coating layer 12 Bead part 16 Crown part 17 Tire case (an example of tire skeleton)
18 Bead core 26 Belt layer 26A Belt cord 26B Coating resin 28 Cushion rubber 30 Tread layer 110 Tire 112 Bead part 114 Tire side part 116 Tread part 118 Bead core 122 Protective layer 124A Belt layer 124B Cushion rubber 130 Tread layer 140 Tire case (tire skeleton) Example)
200 Tire CL Tire Equatorial Q Midpoint

Claims (18)

A resin member having a treated surface that has been surface-treated by plasma treatment,
A rubber member that is in contact with the treated surface of the resin member and contains a filler having a silanol group,
Resin rubber complex having. The treated surface of the resin member is subjected to the peroxy radical (-O-O.), Hydroperoxide group (-O-OH), carbonyl group (-C (= O)-), and aldehyde group (-O-O.) By the surface treatment. The resin-rubber composite according to claim 1, wherein 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 the 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 complex 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 sulfurs. 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 triazinedithiol. The resin-rubber composite according to claim 8, wherein the rubber member contains the triazinedithiol in an amount of 0.01 phr or more and 10 phr or less with respect to the contained rubber. The resin member is a polyester-based thermoplastic elastomer, a polyester-based thermoplastic resin, a polyamide-based thermoplastic elastomer, a polyamide-based thermoplastic resin, a polystyrene-based thermoplastic elastomer, a polystyrene-based thermoplastic resin, a polyurethane-based thermoplastic elastomer, or a polyurethane-based thermal. The resin-rubber composite according to any one of claims 1 to 9, which contains 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 complex according to any one of claims 1 to 11. The twelfth aspect of claim 12, wherein the belt layer as the resin member and at least one member selected from the tread as the rubber member, the tire skeleton, and the rubber sheet adhered to the surface of the belt layer. Tires. The tire according to claim 12, further 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 adhered to the surface of the bead member. .. A claim having a tire skeleton as the resin member and at least one member selected from a tread, a belt layer, a bead member as the rubber member, and a rubber sheet adhered to the surface of the tire skeleton. Item 12. 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 coating layer covering the belt cord as the rubber member, and a rubber sheet adhered to the surface of the belt cord. The tire according to claim 12, which is a belt layer having the member of the above. 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 adhered to the surface of the bead wire. The tire according to claim 12, which is a bead core having the member of the above. A surface treatment step of applying a surface treatment by plasma treatment to at least a part of the surface of the resin member, and
A bonding step in which a rubber member containing a filler having a silanol group is placed in contact with the surface-treated surface of the resin member and heated to bond the resin member and the rubber member.
A method for producing a resin-rubber complex having.

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