JP7312411B2 - RESIN-RUBBER COMPOSITE, TIRE, AND METHOD FOR MANUFACTURING RESIN-RUBBER COMPOSITE - Google Patents

Description

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

2. Description of the Related Art Conventionally, resin-rubber composites in which a resin member and a rubber member are bonded together have been used in various fields. For example, in the field of tires, the use of resin members has been studied from the viewpoint of weight reduction, ease of molding, recycling, etc., and rubber members such as rubber tire frame bodies, treads, belt members, and the like are being tried to be used by bonding these resin members.
For example, Patent Literature 1 discloses a tire that is formed of at least a thermoplastic resin material and has an annular tire frame, and that has a reinforcing cord member that is wound around the outer periphery of the tire frame in the circumferential direction to form a reinforcing cord layer, and the thermoplastic resin material contains at least a polyamide-based thermoplastic elastomer.

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

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

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

As described above, when an organic solvent-based adhesive is used, it is necessary to evaporate the solvent after the coating film is formed, and the drying process takes time. In addition, there is a need to install an exhaust system or the like from the standpoint of working environment, and there is room for improvement from the standpoint of simplification of manufacturing, cost reduction, and the like.
Therefore, in a resin-rubber composite in which a resin member and a rubber member are arranged so as to be in contact with each other, it is desired to obtain excellent adhesion between the two even when the two are in direct contact with each other without an adhesive.

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

In view of the above circumstances, an object of the present disclosure is to provide a resin-rubber composite having excellent adhesion 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.

The gist of the present disclosure is as follows.
<1>
A resin member having a treated surface which has been subjected to a first surface treatment by plasma treatment and further subjected to a second surface treatment with a reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group on the surface subjected to the plasma treatment;
a rubber member that is in contact with the treated surface of the resin member and contains a rubber containing a functional group exhibiting reactivity with the organic reactive group;
A resin-rubber composite having

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

It is a tire sectional view showing a tire concerning this embodiment. It is a tire half cross-sectional view which shows one side of the cut surface which cut|disconnected the tire of another aspect which concerns on this embodiment along the tire width direction. FIG. 3 is a schematic diagram of a cross section perpendicular to the length direction of the bead wire, showing one form of the bead core in the present embodiment. FIG. 4 is a schematic diagram of a cross-section perpendicular to the length direction of the bead wire, showing another form of the bead core in this embodiment.

Specific embodiments of the present disclosure will be described in detail below. However, the present disclosure is by no means limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the purpose of the present disclosure.

In this specification, the numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.

<Resin-rubber composite>
A resin-rubber composite according to the first embodiment has a resin member and a rubber member in contact with the resin member.
The resin member is subjected to a first surface treatment by plasma treatment, and further has a treated surface subjected to a second surface treatment with a reactive inorganic compound containing at least one group selected from an organic reactive group, a hydroxyl group (-OH), and an alkoxy group (-OR: R represents an alkyl group) on the surface subjected to the plasma treatment.
The rubber member is in contact with the treated surface of the resin member and includes rubber containing functional groups exhibiting reactivity with the organic reactive groups.

In recent years, the use of resin members in the field of tires and the like has been studied from the viewpoints of weight reduction, ease of molding, recycling, and the like. Such a resin member may be arranged at a position in contact with the rubber member, but due to the difference in materials between the resin member and the rubber member, an adhesive (for example, an organic solvent-based adhesive) is provided between them to increase adhesion, thereby avoiding interfacial peeling and the like.
However, if an organic solvent-based adhesive is used, it is necessary to evaporate the solvent after the coating film is formed, and the drying process takes time. In addition, there is a need to install an exhaust system or the like from the standpoint of working environment, and there is room for improvement from the standpoint of simplification of manufacturing, cost reduction, and the like.
Therefore, in a resin-rubber composite in which a resin member and a rubber member are arranged so as to be in contact with each other, it is desired to obtain excellent adhesion between the two even when the two are in direct contact with each other without an adhesive.

In response to this, the present inventors performed a first surface treatment by plasma treatment on a resin member, and then applied a second surface treatment on the plasma-treated surface with a reactive inorganic compound containing at least one group selected from an organic reactive group and a hydroxyl group (-OH) and an alkoxy group (-OR: R represents an alkyl group). It has been found that the arrangement improves the adhesion between the resin member and the rubber member.
The reason is presumed as follows.

First, a first surface treatment by plasma treatment activates the surface of the resin member to introduce active groups (for example, peroxy radicals, hydroperoxide groups, carbonyl groups, aldehyde groups, carboxy groups, hydroxyl groups, etc.) to the surface. Moreover, the active groups introduced into the surface of the resin member react with the hydroxyl groups or alkoxy groups in the reactive inorganic compound by the second surface treatment with the reactive inorganic compound. That is, the active group and the reactive inorganic compound react with each other to introduce the organic reactive group onto the surface of the resin member. Furthermore, since the rubber member that is in contact with the treated surface that has been subjected to the first surface treatment and the second surface treatment contains a functional group that exhibits reactivity with the organic reactive group, the organic reactive group and the functional group of the rubber in the rubber member are bonded. That is, in the resin-rubber composite according to the first embodiment, the treated surface of the resin member and the surface of the rubber member are bonded by the organic reactive groups, and the formation of this bond is presumed to improve the adhesiveness between the resin member and the rubber member.

A resin-rubber composite according to the second embodiment has a resin member and a rubber member in contact with the resin member.
The rubber member includes rubber containing functional groups exhibiting reactivity with organic reactive groups possessed by the reactive inorganic compound.
At the interface between the resin member and the rubber member, at least one selected from peroxy radicals, hydroperoxide groups, carbonyl groups, aldehyde groups, carboxyl groups, and hydroxyl groups reacts with a reactive inorganic compound having an organic reactive group and containing at least one selected from a hydroxyl group (—OH) and an alkoxy group (—OR: R represents an alkyl group), whereby the surface of the resin member and the surface of the rubber member are bonded by cross-linking.

The inventors have found that the configuration of the second embodiment improves the adhesiveness between the resin member and the rubber member.
The reason is presumed as follows.

On the surface of the resin member, at least one selected from a peroxy radical, a hydroperoxide group, a carbonyl group, an aldehyde group, a carboxyl group, and a hydroxyl group reacts with a hydroxyl group or an alkoxy group in the reactive inorganic compound to introduce a cross-linking group. Furthermore, the organic reactive group in this cross-linking group is bonded to the functional group contained in the rubber member, whereby the surface of the resin member and the surface of the rubber member are linked by the cross-linking group. It is presumed that the formation of this bond improves the adhesiveness between the resin member and the rubber member.

The resin-rubber composite according to the first embodiment, which has a resin member having a treated surface to which the first surface treatment and the second surface treatment have been applied, and a rubber member containing a rubber containing a functional group exhibiting reactivity with an organic reactive group, preferably further comprises the resin-rubber composite according to the second embodiment.

Next, the configurations of the resin-rubber composites according to the first embodiment and the second embodiment will be described in detail.
In addition, hereinafter, when referring to both the resin-rubber composites according to the first embodiment and the second embodiment, they are simply referred to as "the resin-rubber composite according to the present embodiment".

The resin-rubber composite according to this embodiment has a resin member and a rubber member in contact with the resin member. In addition, the aspect which has the 2nd rubber member further contact|connected with this rubber member may be sufficient.

Here, the method of manufacturing the resin-rubber composite according to the first embodiment and the second embodiment (that is, the present embodiment) is not particularly limited.
For example, a surface treatment step of subjecting at least a part of the surface of the resin member to a first surface treatment by plasma treatment, and a second surface treatment on the plasma-treated surface with a reactive inorganic compound containing at least one group selected from an organic reactive group and a hydroxyl group (-OH) and an alkoxy group (-OR: R represents an alkyl group); and a bonding step of placing the resin member and the rubber member in contact with each other and bonding the resin member and the rubber member by heating.
In the present specification, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as its purpose is achieved.

(Application)
The resin-rubber composite according to the present embodiment is applied to various fields in which resin members and rubber members are used, for example, tires, anti-vibration rubbers, rubber hoses, rubber-resin composite hoses, belts, rubber crawlers, golf balls, bellows, seismic isolation rubbers, sealing materials, caulking materials, bicycles, and the like.

When the resin-rubber composite is used for a tire, examples of combinations of resin members and rubber members 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 frame body, and a rubber sheet adhered to the surface of the belt layer.
- A combination of a bead member as a resin member and at least one member selected from a tire frame body as a rubber member and a rubber sheet adhered to the surface of the bead member.
A combination of a tire frame as a resin member and at least one member selected from a rubber member such as a tread, a belt layer, a bead member, and a rubber sheet adhered to the surface of the tire frame.
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, the belt 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, the bead core is a resin-rubber composite).
The above-mentioned "tire frame as a rubber member" may be replaced with a member forming a tire frame such as a carcass corresponding to a rubber member (for example, a carcass consisting of only a carcass ply in which a plurality of wires are coated with rubber).

In particular, examples of embodiments 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, a tire frame, and a side rubber as a second rubber member.
- A combination of a bead member as a resin member, a rubber sheet as a rubber member, and at least one member selected from a tire frame body as a second rubber member and a side rubber.
A combination of a tire frame 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 frame as the second rubber member" may be replaced with a tire frame member such as a carcass corresponding to the second rubber member (for example, a carcass consisting of only a carcass ply in which a plurality of wires are coated with rubber).

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

Here, each of the resin member, the rubber member, and the second rubber member, which constitute the resin-rubber composite according to the present embodiment, will be described in detail.

(Resin member)
The resin member according to the first embodiment is subjected to a first surface treatment by plasma treatment, and further has a treated surface subjected to a second surface treatment with a reactive inorganic compound containing at least one group selected from an organic reactive group, a hydroxyl group (-OH), and an alkoxy group (-OR: R represents an alkyl group) on the plasma-treated surface.

In the resin member according to the second embodiment, at the interface with the rubber member, the surface of the resin member and the surface of the rubber member are bonded by a cross-linking group obtained by reacting at least one selected from the group represented by the group [P] below with the reactive inorganic compound described below.
・ Group [P]
peroxy radical (-O-O), hydroperoxide group (-O-OH), carbonyl group (-C(=O)-), aldehyde group (-C(=O)-H), carboxy group (-C(=O)-OH), and hydroxyl group (-OH)
- Reactive inorganic compound A reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group (-OH) and an alkoxy group (-OR: R represents an alkyl group)

In addition, the resin member is subjected to a first surface treatment by plasma treatment to introduce at least one selected from the group represented by the group [P] to the surface of the resin member, and the plasma-treated surface is further subjected to a second surface treatment with the reactive inorganic compound, thereby forming a cross-linking group in the resin member according to the second embodiment, which is formed by reacting at least one selected from the group represented by the group [P] with the reactive inorganic compound.

-First surface treatment/plasma treatment-
Introduced Group A group capable of bonding to at least one of a hydroxyl group (--OH) and an alkoxy group (--OR: R represents an alkyl group) is introduced into the surface of the resin member by the first surface treatment using plasma treatment.
For example, the groups introduced by the first surface treatment by plasma treatment include peroxy radicals (-O-O), hydroperoxide groups (-O-OH), carbonyl groups (-C(=O)-), aldehyde groups (-C(=O)-H), carboxyl groups (-C(=O)-OH), oxidizing groups such as hydroxyl groups (-OH), and the like.
Among these, from the viewpoint of improving adhesion, it is more preferable to introduce at least one group selected from a peroxy radical (-O-O), a hydroperoxide group (-O-OH), a carbonyl group (-C(=O)-), an aldehyde group (-C(=O)-H), a carboxy group (-C(=O)-OH), and a hydroxyl group (-OH).

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

Conditions for plasma treatment as the first surface treatment on the surface of the resin member are not particularly limited as long as the surface after the treatment is activated, and the plasma treatment can be performed by a known method. In other words, conditions under which plasma can be generated can be appropriately employed.

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

For plasma generation, it is preferable to use, for example, a high-frequency power supply with an applied voltage frequency of 50 Hz or more and 2.45 GHz or less.
In addition, 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, and more preferably 5 W/cm ² or more ^.
When using a pulse output, the pulse modulation frequency is 1 kHz or more and 50 kHz or less (preferably 5 kHz or more and 30 kHz or less), and the pulse duty is 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 plate-shaped metal coated with a dielectric on one side. Although the distance between the counter electrode and the resin member is not particularly limited, it is preferably 10 mm or less, more preferably 3 mm or less, even more preferably 1.2 mm or less, and particularly preferably 1 mm or less. Although the lower limit of the distance is not particularly limited, it is, for example, 0.5 mm or more.

From the viewpoint of improving adhesiveness and simplifying the plasma treatment, the plasma treatment time (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 even more preferably 1 minute or more and 10 minutes or less.

As a gas used for generating plasma, for example, a rare gas such as helium, argon, or neon, or a reactive gas such as oxygen, nitrogen, hydrogen, or ammonia can be used. That is, it is preferable to use only non-polymerizable gas as the gas used in this embodiment. As these gases, only one or two 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.
Plasma may be generated using a chamber under conditions in which the gas atmosphere is controlled as described above, or may be performed under conditions completely open to the atmosphere in which, for example, a noble gas is allowed to flow to the electrode portion.

-Second surface treatment/treatment with reactive inorganic compound-
The surface of the resin member subjected to the first surface treatment (that is, plasma treatment) is further subjected to a second surface treatment with a reactive inorganic compound containing at least one group selected from organic reactive groups, hydroxyl groups (-OH) and alkoxy groups (-OR: R represents an alkyl group). By the second surface treatment, bonds are formed between at least one group selected from hydroxyl groups and alkoxy groups possessed by the reactive inorganic compound and the groups introduced to the surface of the resin member by the plasma treatment.

- Reactive inorganic compound The reactive inorganic compound has at least one group selected from a hydroxyl group and an alkoxy group.
Examples of the above groups include hydroxyl group (--OH), methoxy group (--OCH ₃ ), ethoxy group (--OC ₂ H ₅ ), isopropoxy group (--OC ₃ H ₇ ), t-butoxy group (--OC ₄ H ₉ ) and the like. Among them, a hydroxyl group (--OH), a methoxy group (--OCH ₃ ), or an ethoxy group (--OC ₂ H ₅ ) is preferred.

The reactive inorganic compound may have one or more of the above groups in one molecule.

The reactive inorganic compound contains an organic reactive group that exhibits reactivity with the functional group of the rubber contained in the rubber member.
Examples of organic reactive groups include polysulfide groups, vinyl groups, thiol groups, amino groups, epoxy groups, isocyanate groups, isocyanurate groups, styryl groups (that is, vinylphenyl groups), acryl groups, methacryl groups, ureido groups (—NHCONH ₂ ), hydroxyl groups, and aldehyde groups.
Among these, polysulfide groups, vinyl groups, thiol groups, amino groups, epoxy groups, and isocyanate groups are preferred, and polysulfide groups, vinyl groups, and thiol groups are more preferred, from the viewpoint of forming good bonds between the reactive inorganic compound and the rubber in the rubber member.

The reactive inorganic compound preferably has at least one or more organic reactive groups in one molecule.

A reactive inorganic compound has an inorganic element in the molecule. Examples of inorganic elements include Si atoms, among which Si atoms are preferred.
The reactive inorganic compound preferably has at least one inorganic element in one molecule.

- Specific examples of reactive inorganic compounds Examples of reactive inorganic compounds include compounds in which at least one group selected from a hydroxyl group and an alkoxy group is directly bonded to an inorganic element (preferably a Si atom), and a group having an organic reactive group is further bonded to the inorganic element.

Examples of reactive inorganic compounds include the following compounds.
(Compound with Si atom)
Polysulfide-based silane coupling agents having two or more sulfurs (bis-(trialkoxysilylalkyl)-polysulfides such as bis-(3-(triethoxysilyl)propyl)-disulfide, bis-(3-(triethoxysilyl)propyl)-tetrasulfide, and bis-(triethoxysilylpropyl)-polysulfide), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3 -aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, 11-aminoundecyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltriisoproxysilane, (isocyanatomethyl)methyldimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, triethoxysilylpropylenylcarbamate, trimethoxysilylpropylsuccinic anhydride, triethoxysilylpropylsuccinic anhydride, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisoproxysilane, vinyl-t- butoxysilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, allyltriethoxysilane, butenyltrimethoxysilane, butenyltriethoxysilane, hexenyltrimethoxysilane, hexenyltriethoxysilane, octenyltrimethoxysilane, octenyltriethoxysilane, dodecenyltrimethoxysilane, dodecenyltriethoxysilane, styrenetrimethoxysilane, (bicycloheptenyl)triethoxysilane Silane (norbornenetriethoxysilane), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, p-styrene ryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 11-mercaptoundecyltrimethoxysilane, 1 1-mercaptoundecyltriethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriisoproxysilane, 3-mercaptopropyltri-t-butoxysilane and the like.

Among them, the following compounds are preferable as the reactive inorganic compound from the viewpoint of improving adhesiveness.
Bis-(3-(triethoxysilyl)propyl)-disulfide, bis-(3-(triethoxysilyl)propyl)-tetrasulfide, bis-(triethoxysilylpropyl)-polysulfide, 3-mercaptopropyltriethoxysilane are preferred.

In the second surface treatment, one type of reactive inorganic compound may be used alone, or two or more types may be used in combination.

Method of second surface treatment The method of applying the second surface treatment using a reactive inorganic compound to the surface of the resin member that has been subjected to the first surface treatment (that is, plasma treatment) is not particularly limited as long as it is a method that forms a bond between at least one group selected from hydroxyl groups and alkoxy groups possessed by the reactive inorganic compound and a group introduced to the surface of the resin member by plasma treatment.
For example, there is a method of adding a reactive inorganic compound to a liquid to prepare a surface treatment liquid, and immersing a resin member that has undergone a plasma treatment in this surface treatment liquid.

Liquids used for the surface treatment liquid include, for example, organic solvents and aqueous solutions, and specifically water, methanol, ethanol, acetone, methyl ethyl ketone, acetonitrile, toluene, xylene and the like are preferred. Also, water and the above organic solvent may be mixed at an arbitrary ratio and used.

The liquid used for the surface treatment liquid is preferably adjusted to be acidic (e.g., pH 2 or more and 10 or less, preferably pH 3 or more and 9 or less) before adding the reactive inorganic compound, in order to suppress the condensation reaction rate between the reactive inorganic compounds and efficiently promote the reaction between the alkoxide of the reactive inorganic compound and the functional group present on the resin surface.

The concentration of the reactive inorganic compound contained in the surface treatment liquid is preferably 0.5% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, from the viewpoint of forming good bonds between the reactive inorganic compound and the groups introduced to the surface of the resin member by the plasma treatment.

The time for which the resin member subjected to the first surface treatment is immersed in the surface treatment liquid is not particularly limited, but is preferably 10 seconds or more and 3600 seconds or less, more preferably 60 seconds or more and 600 seconds or less, from the viewpoint of forming good bonds between the reactive inorganic compound and the groups introduced to the surface of the resin member by the plasma treatment.

In the second surface treatment, after the immersion treatment in the surface treatment liquid, treatment such as washing and drying may be performed as necessary.

・Water contact angle In the resin rubber composite of the first embodiment, the treated surface of the resin member that has been subjected to the first surface treatment and the second surface treatment has a water contact angle of preferably 20° or more and 98° or less, more preferably 50° or more and 96° or less, and further preferably 60° or more and 95° or less, from the viewpoint of improving adhesiveness.
Also in the resin-rubber composite of the second embodiment, the contact angle of water on the resin member-side surface at the interface between the resin member and the rubber member is preferably within the above range from the viewpoint of improving adhesiveness.

The contact angle of water on the treated surface of the resin member or on the resin member side surface at the interface between the resin member and the rubber member is measured by dropping pure water at 25° C. and observing the shape of the droplet using an automatic minimum contact angle meter (MCA-3) manufactured by Kyowa Interface Science Co., Ltd.

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

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

In this specification, the term "resin" is a concept that includes thermoplastic resins, thermoplastic elastomers, and thermosetting resins, and does not include vulcanized rubber.
By "thermoplastic resin" is meant a polymeric compound that softens and flows as the temperature rises, becomes relatively hard and strong when cooled, but does not possess rubber-like elasticity.
"Thermoplastic elastomer" means a copolymer having hard and soft segments. The hard segment refers to a component that is relatively harder than the soft segment, and is preferably a molecular constraint component that serves as a cross-linking point of cross-linked rubber to prevent 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 exhibiting rubber elasticity.
Specific examples of thermoplastic elastomers include copolymers having a polymer that constitutes a crystalline hard segment with a high melting point or a hard segment with a high cohesive strength, and a polymer that constitutes an amorphous soft segment with a low glass transition temperature. Thermoplastic elastomers include, for example, 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 includes, 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 due to intermolecular hydrogen bonding or π-π interaction. Further, the soft segment includes, for example, a segment having a structure that has a long-chain group (for example, a long-chain alkylene group) in the main chain, has a high degree of freedom of molecular rotation, and has 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.

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

Thermosetting resins contained in the resin material include, for example, phenolic thermosetting resins, urea-based thermosetting resins, melamine-based thermosetting resins, and epoxy-based thermosetting resins.

Resin members WHEREIN: You may use these individually or in combination of 2 or more types.
Among these, the resin contained in the resin material is preferably polyester-based thermoplastic elastomer, polyester-based thermoplastic resin, polyamide-based thermoplastic elastomer, polyamide-based thermoplastic resin, polystyrene-based thermoplastic elastomer, polystyrene-based thermoplastic resin, polyurethane-based thermoplastic elastomer, polyurethane-based thermoplastic resin, polyolefin-based thermoplastic elastomer, or polyolefin-based thermoplastic resin, and more preferably polyester-based thermoplastic elastomer or polyester-based thermoplastic resin.

[Thermoplastic elastomer]
－Polyester Thermoplastic Elastomer－
Examples of polyester-based thermoplastic elastomers include materials in which at least polyester forms a crystalline hard segment with a high melting point and another polymer (e.g., polyester or polyether) forms an amorphous soft segment with a low glass transition temperature.

As the polyester forming the hard segment, for example, an aromatic polyester can be used. Aromatic polyesters can be formed, for example, from aromatic dicarboxylic acids or ester-forming derivatives thereof and aliphatic diols. The aromatic polyester is preferably polybutylene terephthalate derived from at least one of terephthalic acid and dimethyl terephthalate and 1,4-butanediol. Aromatic polyesters are composed of dicarboxylic acid components such as isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and diols having a molecular weight of 300 or less (e.g., ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol). Alicyclic diols such as 1,4-cyclohexanedimethanol and 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′-dihydroxy-p-terphenyl , 4,4′-dihydroxy-p-quarterphenyl; Alternatively, it may be a copolymer polyester in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize trifunctional or higher polyfunctional carboxylic acid components, polyfunctional oxyacid components, polyfunctional hydroxy components, etc. in an amount 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, with polybutylene terephthalate being preferred.

Moreover, examples of polymers that form the soft segment include aliphatic polyesters and aliphatic polyethers.
Examples of aliphatic polyethers include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of poly(propylene oxide) glycol, copolymers of ethylene oxide and tetrahydrofuran, and the like.
Aliphatic polyesters include poly(ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, polyethylene adipate and the like.
Among these aliphatic polyethers and aliphatic polyesters, poly(tetramethylene oxide) glycol, ethylene oxide adducts of poly(propylene oxide) glycol, poly(ε-caprolactone), polybutylene adipate, polyethylene adipate and the like are preferable as the polymer forming the soft segment from the viewpoint of the elastic properties of the resulting polyester block copolymer.

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

Examples of the combination of the above-mentioned hard segment and soft segment include each combination of the above-mentioned hard segment and soft segment. Among these, as the combination of the hard segment and the soft segment, a combination in which the hard segment is polybutylene terephthalate and the soft segment is an aliphatic polyether is preferable, and a combination in which the hard segment is polybutylene terephthalate and the soft segment is poly(ethylene oxide) glycol is more preferable.

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

A 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－
A polyamide-based thermoplastic elastomer is a thermoplastic resin material composed only of a copolymer having a polymer that forms a crystalline hard segment with a high melting point and a polymer that forms an amorphous soft segment with a low glass transition temperature, and has an amide bond (-CONH-) in the main chain of the polymer that forms the hard segment.
Examples of polyamide-based thermoplastic elastomers include materials in which at least a polyamide forms a crystalline hard segment with a high melting point, and another polymer (e.g., polyester, polyether, etc.) forms an amorphous soft segment with a low glass transition temperature. Further, the polyamide-based thermoplastic elastomer may be formed using a chain extender such as dicarboxylic acid in addition to the hard segment and soft segment.
Specific examples of thermoplastic polyamide elastomers include thermoplastic amide elastomers (TPA) defined in JIS K6418:2007 and polyamide elastomers described in JP-A-2004-346273.

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

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

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

In general formula (1), R ¹ is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms (eg, an alkylene group having 3 to 18 carbon atoms), more preferably a hydrocarbon molecular chain having 4 to 15 carbon atoms (eg, an alkylene group having 4 to 15 carbon atoms), and particularly preferably a hydrocarbon molecular chain having 10 to 15 carbon atoms (eg, an alkylene group having 10 to 15 carbon atoms).
In general formula (2), R ² is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms (eg, an alkylene group having 3 to 18 carbon atoms), more preferably a hydrocarbon molecular chain having 4 to 15 carbon atoms (eg, an alkylene group having 4 to 15 carbon atoms), and particularly preferably a hydrocarbon molecular chain having 10 to 15 carbon atoms (eg, an alkylene group having 10 to 15 carbon atoms).
Monomers represented by general formula (1) or general formula (2) include ω-aminocarboxylic acids and lactams. Polycondensates of these ω-aminocarboxylic acids or lactams, cocondensates of diamines and dicarboxylic acids, and the like are examples of polyamides forming the hard segment.

Examples of ω-aminocarboxylic acids include aliphatic ω-aminocarboxylic acids having 5 to 20 carbon atoms such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Lactams include aliphatic lactams having 5 to 20 carbon atoms such as lauryllactam, ε-caprolactam, udecanelactam, ω-enantholactam and 2-pyrrolidone.
As for Jiamine, for example,, for example, ethylenium, trimethylange hyamine, tetramethylange oimin, hexamethylange oimin, heptamethylangeamine, octamethylange oimin, namethylange oimin, decamethylange aliamine, onda kamethylianiamine, dodkamethye min, 2,2,4 -. It is possible to list diamine compounds such as 2-20 carbon diamine, 2 to 20 carbon diamine, such as Remethyl Hexamethylange Amin, 2,4,4 -4 -4, Trimethyl Hexrange Aramin, 3 -methylpentamethylangeiamine, and metakic syrange.
The dicarboxylic acid can be represented by HOOC-(R ³ ) _m -COOH (R ³ : hydrocarbon molecular chain with 3 to 20 carbon atoms, m: 0 or 1), and examples thereof include aliphatic dicarboxylic acids with 2 to 20 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
Polyamides obtained by ring-opening polycondensation of lauryllactam, ε-caprolactam, or udecanelactam can be preferably used as the polyamide forming the hard segment.

Polymers forming the soft segment include, for example, polyesters and polyethers. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and ABA triblock polyether. These can be used individually or in combination of 2 or more types. In addition, polyether diamine obtained by reacting the end of polyether with ammonia or the like can also be used.
Here, "ABA-type triblock polyether" means a polyether represented by the following general formula (3).

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

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

As a combination of the hard segment and the soft segment, each combination of the hard segment and the soft segment mentioned above can be mentioned. Among these, the combination of the hard segment and the soft segment is preferably a combination of a ring-opening polycondensate of lauryllactam and polyethylene glycol, a combination of a ring-opening polycondensate of lauryllactam and polypropylene glycol, a combination of a ring-opening polycondensate of lauryllactam and polytetramethylene ether glycol, or a combination of a ring-opening polycondensate of lauryllactam and an ABA triblock polyether, and more preferably a combination of a ring-opening polycondensate of lauryllactam and an ABA triblock polyether.

The polymer (that is, polyamide) forming the hard segment preferably has a number average molecular weight of 300 to 15,000 from the viewpoint of melt moldability. Moreover, the number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low-temperature flexibility. Furthermore, the mass ratio (x:y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, more preferably 50:50 to 80:20, from the viewpoint of moldability.

A 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.

Commercially available thermoplastic polyamide elastomers include, for example, UBE Industries, Ltd.'s "UBESTA XPA" series (e.g., XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2, XPA9044, etc.), and Daicel-Eponic's "VESTAMID". Series (eg, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) and the like can be used.

- Polystyrene Thermoplastic Elastomer Polystyrene thermoplastic elastomers include, for example, materials in which at least polystyrene forms hard segments and other polymers (e.g., polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) form amorphous soft segments with a low glass transition temperature. As the polystyrene forming the hard segment, for example, those obtained by a known radical polymerization method, ionic polymerization method, or the like are preferably used, and specific examples include polystyrene having anionic living polymerization. Polymers forming the soft segment include, for example, polybutadiene, polyisoprene, poly(2,3-dimethyl-butadiene) and the like.

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

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

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

Commercially available polystyrene-based thermoplastic elastomers include, for example, Asahi Kasei Corp.'s "Tuftec" series (e.g., H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.), and Kuraray Co., Ltd.'s "SEBS" series (8007, 80). 76 etc.), "SEPS" series (2002, 2063 etc.) etc. can be used.

－Polyurethane Thermoplastic Elastomer－
Examples of polyurethane-based thermoplastic elastomers include materials in which at least polyurethane forms hard segments forming pseudo-crosslinks by physical aggregation, and other polymers form amorphous soft segments with a low glass transition temperature.
Specific examples of thermoplastic polyurethane elastomers include thermoplastic polyurethane elastomers (TPU) defined in JIS K6418:2007. The thermoplastic polyurethane elastomer can be represented as a copolymer containing a soft segment containing a unit structure represented by formula A below and a hard segment containing a unit structure represented by formula B below.

[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 long-chain aliphatic polyester represented by P in formula A, those having a molecular weight of 500 to 5,000, for example, can be used. P is derived from a diol compound containing a long-chain aliphatic polyether or long-chain aliphatic polyester represented by P. Such diol compounds include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly(butylene adipate) diol, poly-ε-caprolactone diol, poly(hexamethylene carbonate) diol, ABA type triblock polyether, etc., having a molecular weight within the above range.
These can be used individually or in combination of 2 or more types.

In formulas A and B, R is a partial structure introduced using a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by R. Examples of aliphatic diisocyanate compounds containing aliphatic hydrocarbons represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate and the like.
Examples of diisocyanate compounds containing alicyclic hydrocarbons represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate. Furthermore, examples of aromatic diisocyanate compounds containing aromatic hydrocarbons represented by R include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate.
These can be used individually or in combination of 2 or more types.

As the short-chain aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by P′ in Formula B, those having a molecular weight of less than 500 can be used, for example. Moreover, P' is derived from a diol compound containing a short-chain aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by P'. Aliphatic diol compounds containing short-chain aliphatic hydrocarbons represented by P′ include, for example, glycols and polyalkylene glycols, and specific examples include 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-decanediol, and the like. mentioned.
Examples of alicyclic diol compounds containing alicyclic hydrocarbons represented by P′ include cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol.
Furthermore, examples of aromatic diol compounds containing aromatic hydrocarbons represented by P′ include hydroquinone, resorcinol, 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, 1,1-di(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like.
These can be used individually or in combination of 2 or more types.

The polymer (that is, polyurethane) forming the hard segment preferably has a number average molecular weight of 300 to 1,500 from the viewpoint of melt moldability. The number average molecular weight of the polymer forming the soft segment is preferably 500 to 20,000, more preferably 500 to 5,000, particularly preferably 500 to 3,000, from the viewpoint of flexibility and thermal stability of the thermoplastic polyurethane elastomer. Also, 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.

A thermoplastic polyurethane 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 thermoplastic polyurethane elastomer, for example, the thermoplastic polyurethane described in JP-A-5-331256 can be used.

Specifically, a combination of a hard segment consisting only of an aromatic diol and an aromatic diisocyanate and a soft segment consisting only of a polycarbonate ester is preferable as the thermoplastic polyurethane elastomer. More specifically, tolylene diisocyanate (TDI)/polyester polyol copolymer, TDI/polyether polyol copolymer, TDI/caprolactone polyol copolymer, TDI/polycarbonate polyol copolymer, 4,4'-diphenylmethane diisocyanate (MDI)/polyester. polyol copolymer, MDI/polyether polyol copolymer, MDI/caprolactone polyol copolymer, MDI/polycarbonate polyol copolymer, and MDI+hydroquinone/polyhexamethylene carbonate copolymer. Among them, at least one selected from TDI/polyester polyol copolymer, TDI/polyether polyol copolymer, MDI/polyester polyol copolymer, MDI/polyether polyol copolymer, and MDI+hydroquinone/polyhexamethylene carbonate copolymer is more preferable.

Commercially available thermoplastic polyurethane elastomers include, for example, BASF's "Elastollan" series (e.g., ET680, ET880, ET690, ET890, etc.), Kuraray Co., Ltd.'s "Clamilon U" series (e.g., 2000s, 3000s, 8000s, 9000s, etc.), and Nippon Miractran Co., Ltd.'s "Milactran" series (e.g., XN). -2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc.) and the like can be used.

－Polyolefin Thermoplastic Elastomer－
Examples of polyolefin-based thermoplastic elastomers include materials in which at least polyolefin forms a crystalline hard segment with a high melting point, and other polymers (e.g., other polyolefins, polyvinyl compounds, etc.) form an amorphous soft segment with a low glass transition temperature. Polyolefins forming the hard segment include, for example, polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.

Polyolefin thermoplastic elastomers include, for example, olefin-α-olefin random copolymers and olefin block copolymers. Specifically, propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-pentene copolymers, ethylene-1-butene copolymers, 1-butene-1-hexene copolymers, 1-butene-4-methyl-pentene, ethylene-methacrylic acid copolymers, ethylene- Methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene -vinyl acetate copolymer, propylene-vinyl acetate copolymer and the like.

Among these, polyolefin-based thermoplastic elastomers include propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-pentene copolymers, ethylene-1-butene copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, and ethylene-ethyl methacrylate. from copolymers, ethylene-butyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, propylene-methacrylic acid copolymers, propylene-methyl methacrylate copolymers, propylene-ethyl methacrylate copolymers, propylene-butyl methacrylate copolymers, propylene-methyl acrylate copolymers, propylene-ethyl acrylate copolymers, propylene-butyl acrylate copolymers, ethylene-vinyl acetate copolymers, and propylene-vinyl acetate copolymers At least one selected is preferred, and at least one selected from ethylene-propylene copolymers, propylene-1-butene copolymers, ethylene-1-butene copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-butyl acrylate copolymers is more preferred.
Also, two or more olefin resins such as ethylene and propylene may be used in combination. Moreover, the olefin resin content in the polyolefin-based thermoplastic elastomer is preferably 50% by mass or more and 100% by mass or less.

The number average molecular weight of the thermoplastic polyolefin elastomer is preferably from 5,000 to 10,000,000. When the polyolefin thermoplastic elastomer has a number average molecular weight of 5,000 to 10,000,000, the thermoplastic resin material has sufficient mechanical properties and excellent workability. From the same point of view, the number average molecular weight of the thermoplastic polyolefin elastomer is more preferably 7,000 to 1,000,000, particularly preferably 10,000 to 1,000,000. Thereby, the mechanical properties 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 200-6000 from the viewpoint of toughness and low-temperature flexibility. Furthermore, the mass ratio (x:y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 95:15, more preferably 50:50 to 90:10, from the viewpoint of moldability.
A polyolefin-based thermoplastic elastomer can be synthesized by copolymerization by a known method.

Moreover, as the thermoplastic polyolefin elastomer, a polyolefin thermoplastic elastomer modified with an acid may be used.
The term "acid-modified thermoplastic polyolefin elastomer" refers to a thermoplastic polyolefin elastomer to which an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group is bound.
Examples of bonding an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfate group, or a phosphoric acid group to a polyolefin thermoplastic elastomer include bonding (eg, graft polymerization) an unsaturated bond site of an unsaturated carboxylic acid (eg, generally maleic anhydride) as an unsaturated compound having an acidic group to the polyolefin thermoplastic elastomer.
As the unsaturated compound having an acidic group, an unsaturated compound having a carboxylic acid group, which is a weakly acidic group, is preferable from the viewpoint of suppressing deterioration of the thermoplastic polyolefin elastomer. Examples of unsaturated compounds having an acidic group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid.

Commercially available polyolefin-based thermoplastic elastomers include, for example, Mitsui Chemicals, Inc. "Tafmer" series (e.g., A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010, XM-707 0, XM-7080, BL4000, BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-0180, P-0280, P-0480, P-0680, etc.), Dupont Mitsui Polychemical Co., Ltd. "Nucrel" series (e.g., AN4214C, AN4225C, AN421 15C, N0903HC, N0908C, AN42012C, N410, N1050H, N1108C, N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN4228C, AN4213C, N035C), "Elvaloy AC" series (for example , 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715AC, 3117AC, 3427AC, 3717AC, etc.), Sumitomo Chemical Co., Ltd.'s "Aclift" series, "Evatate" series, etc., Tosoh Corporation's "Ultrasen" series, etc., Prime Polymer's "Prime T PO" series (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. ) etc. can also be used.

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

Examples of commercially available polyester thermoplastic resins include the "DURANEX" series (e.g., 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., the "NOVADURAN" series (e.g., 5010R5, 5010R3-2, etc.) manufactured by Mitsubishi Engineering-Plastics Corporation, and the "Toraycon" series (e.g., 1401X06, 1401X31, etc.) manufactured by Toray Industries, Inc.

－Polyamide thermoplastic resin－
Examples of thermoplastic polyamide resins include polyamides that form the hard segments of the aforementioned thermoplastic polyamide elastomers.
Specific examples of thermoplastic polyamide resins include polyamides obtained by ring-opening polycondensation of ε-caprolactam (amide 6), polyamides obtained by ring-opening polycondensation of undecane lactam (amide 11), polyamides obtained by ring-opening polycondensation of lauryllactam (amide 12), polyamides obtained by polycondensation of diamine and dibasic acid (amide 66), and polyamides having meta-xylenediamine as a constituent unit (amide MX).

Amide 6 can be represented, for example, by {CO--(CH ₂ ) ₅ --NH} _n . Amide 11 can be represented, for example, by {CO-(CH ₂ ) ₁₀ -NH} _n . Amide 12 can be represented, for example, by {CO-(CH ₂ ) ₁₁ -NH} _n . Amide 66 can be represented, for example, by {CO( _CH2 ) _4CONH ( _CH2 ) _6NH } _n . Amide MX can be represented, for example, by the following structural formula (A-1). Here, n represents the number of repeating units.

As a commercial product of amide 6, for example, the "UBE nylon" series (eg, 1022B, 1011FB, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercial product of amide 11, for example, "Rilsan B" series manufactured by Arkema Co., Ltd. can be used. As a commercial product of amide 12, for example, the "UBE nylon" series (eg, 3024U, 3020U, 3014U, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercial product of Amide 66, for example, Asahi Kasei Corp.'s "Leona" series (eg, 1300S, 1700S, etc.) can be used. As a commercial product of Amide MX, for example, Mitsubishi Gas Chemical Company, Inc.'s "MX nylon" series (eg, S6001, S6021, S6011, etc.) can be used.

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

－Polyolefin Thermoplastic Resin－
Examples of the polyolefin-based thermoplastic resin include polyolefins that form the hard segments of the polyolefin-based thermoplastic elastomer.
Specific examples of polyolefin-based thermoplastic resins include polyethylene-based thermoplastic resins, polypropylene-based thermoplastic resins, polybutadiene-based thermoplastic resins, and the like. Among these, from the viewpoint of heat resistance and workability, polypropylene-based thermoplastic resins are preferable as polyolefin-based thermoplastic resins.
Specific examples of polypropylene-based thermoplastic resins include propylene homopolymers, propylene-α-olefin random copolymers, propylene-α-olefin block copolymers, and the like. Examples of α-olefins include α-olefins having about 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[Other ingredients]
The resin member may contain other components such as additives other than the resin within a range that does not impair the effect. Other components include rubber, various fillers (eg, silica, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, color formers, weathering agents, and the like.

(rubber member)
In the resin-rubber composite according to the first embodiment, the rubber member is in contact with the treated surface of the resin member and contains a functional group exhibiting reactivity with the organic reactive group contained in the reactive inorganic compound.
In the resin-rubber composite according to the second embodiment, the rubber member contains a rubber containing a functional group exhibiting reactivity with the organic reactive group contained in the reactive inorganic compound, and the surface of the resin member and the surface of the rubber member are bonded at the interface with the resin member by a cross-linking group obtained by reacting at least one group selected from the group represented by the group [P] with the reactive inorganic compound.

- Rubber The rubber member in the present embodiment includes rubber containing a functional group exhibiting reactivity with the organic reactive group contained in the reactive inorganic compound.

Functional groups contained in rubber include, for example, diene groups, vinyl groups, isocyanate groups, amino groups, hydroxyl groups, carboxy groups, epoxy groups, thiol groups, polysulfides, and the like.
Among them, polysulfides, thiol groups, vinyl groups, isocyanate groups, amino groups, hydroxyl groups, carboxy groups, or epoxy groups are preferable, and polysulfides, vinyl groups, amino groups, carboxy groups, or epoxy groups are more preferable, from the viewpoint of forming good bonds between the organic reactive groups in the reactive inorganic compound and the rubber.

For example, when the reactive inorganic compound has a vinyl group as the organic reactive group, a good bond is formed between the two by using a rubber containing a functional group such as a diene group as the rubber.
When the reactive inorganic compound has a polysulfide group as the organic reactive group, a good bond is formed between the two by using a rubber containing a functional group such as a diene group or a vinyl group.
When the reactive inorganic compound has an amino group as the organic reactive group, a good bond is formed between the two by using a rubber containing a functional group such as an isocyanate group, a carboxy group, or an epoxy group.
When the reactive inorganic compound has an epoxy group as the organic reactive group, a good bond is formed between the two by using a rubber containing functional groups such as amino groups, hydroxyl groups, and carboxy groups.
When the reactive inorganic compound has an isocyanate group as an organic reactive group, a good bond is formed between the two by using a rubber containing functional groups such as amino groups, hydroxyl groups, carboxyl groups, and thiol groups.

Specific examples of rubbers containing functional groups exhibiting reactivity with organic reactive groups include the following.
Natural rubber (example of NR/functional group: diene group, etc.)
Butadiene rubber (BR/Examples of functional groups: diene group, vinyl group, etc.)
Styrene-butadiene rubber (SBR/example of functional group: diene group, etc.)
Styrene/butadiene/styrene rubber (SBS/example of functional group: diene group, etc.)
Polyisoprene rubber (example of functional group: diene group, etc.)
Chloroprene rubber (Examples of functional groups: diene group, vinyl group, etc.)
Acrynitrile-butadiene rubber (Examples of functional groups: diene group, vinyl group, etc.)
Epoxidized natural rubber (Examples of functional groups: diene group, epoxy group, etc.)
Epoxidized styrene-butadiene rubber (Examples of functional groups: diene group, epoxy group, etc.)
Carboxylated nitrile rubber (Examples of functional groups: diene group, carboxy group, etc.)
Butyl rubber, halogenated butyl rubber (example of functional group: diene group, etc.)
Ethylene acrylic rubber (example of functional group: carboxy group, etc.)

Among them, natural rubber, SBR, BR, and polyisoprene rubber are preferable as the rubber containing a functional group exhibiting reactivity with an organic reactive group.

The rubber member may be used together with a rubber that does not contain a functional group that exhibits reactivity with an organic reactive group. However, from the viewpoint of favorably forming a bond between the organic reactive group in the reactive inorganic compound and the rubber, the ratio of the rubber containing a functional group exhibiting reactivity with the organic reactive group to the total rubber component contained in the rubber member is preferably 0.5% by mass or more, more preferably 30% by mass or more, and even more preferably 100% by mass or more.

In addition, although the content of rubber with respect to the total amount of the rubber member is not particularly limited, it is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. On the other hand, the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

The rubber member preferably contains a filler having a silanol group and a silane coupling agent in addition to rubber. By including the above filler and silane coupling agent, the adhesiveness to the resin member is improved.

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

Silica includes not only silicon dioxide (SiO ₂ ) in a narrow sense, but also silicic acid compounds, including hydrous silicic acid, calcium silicate, aluminum silicate, and other silicates in addition to anhydrous silicic acid. The silica is not particularly limited, and those used in commercially available rubber compositions and the like can be used. The aggregation state of the silica is not particularly limited, and includes precipitated silica, gel silica, dry silica, colloidal silica, and the like.

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

From the viewpoint of improving adhesion, the content of the filler having a silanol group in the rubber member is preferably 20 phr to 100 phr, more preferably 30 phr to 90 phr, relative to the total amount of rubber contained.

• Silane Coupling Agent Silane coupling agents include, for example, compounds in which a group having a reactive group exhibiting reactivity with an organic material and an alkoxy group are bonded to a Si atom.
In addition, as an alkoxy group, a methoxy group, an ethoxy group, etc. are mentioned, for example.
Examples of reactive groups include vinyl groups, epoxy groups, styryl groups (that is, vinylphenyl groups), acryl groups, methacryl groups, amino groups, ureido groups, isocyanate groups, isocyanurate groups, mercapto groups, triazinedithiol groups, vinyl groups, and the like.

Examples of the silane coupling agent contained in the rubber member include the following compounds.
Polysulfide-based silane coupling agents having two or more sulfurs (bis-(trialkoxysilylalkyl)-polysulfides such as bis-(3-(triethoxysilyl)propyl)-disulfide, bis-(3-(triethoxysilyl)propyl)-tetrasulfide, and bis-(triethoxysilylpropyl)-polysulfide), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3 -aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, 11-aminoundecyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltriisoproxysilane, (isocyanatomethyl)methyldimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, triethoxysilylpropylenylcarbamate, trimethoxysilylpropylsuccinic anhydride, triethoxysilylpropylsuccinic anhydride, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisoproxysilane, vinyl-t- butoxysilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, allyltriethoxysilane, butenyltrimethoxysilane, butenyltriethoxysilane, hexenyltrimethoxysilane, hexenyltriethoxysilane, octenyltrimethoxysilane, octenyltriethoxysilane, dodecenyltrimethoxysilane, dodecenyltriethoxysilane, styrenetrimethoxysilane, (bicycloheptenyl)triethoxysilane Silane (norbornenetriethoxysilane), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, p-styrene ryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 11-mercaptoundecyltrimethoxysilane, 1 1-mercaptoundecyltriethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriisoproxysilane, 3-mercaptopropyltri-t-butoxysilane and the like.

As the silane coupling agent, it is preferable to use a polysulfide-based silane coupling agent having two or more sulfur atoms from the viewpoint of the dispersibility of the filler having a silanol group.
Among them, the following compounds are preferable as the silane coupling agent from the viewpoint of improving adhesiveness.
Bis-(3-(triethoxysilyl)propyl)-disulfide, bis-(3-(triethoxysilyl)propyl)-tetrasulfide, bis-(triethoxysilylpropyl)-polysulfide, 3-mercaptopropyltriethoxysilane are preferred.

These silane coupling agents may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of improving adhesion, the content of the silane coupling agent in the rubber member is preferably 5 parts by mass or more and 15 parts by mass or less, more preferably 7 parts by mass or more and 12 parts by mass or less with respect to 100 parts by mass of the filler.

Further, in the rubber member, other components such as additives may be added depending on the purpose.
Examples of additives include reinforcing materials such as carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, anti-aging agents, etc., and these can be appropriately blended.

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

(Second rubber member)
The resin-rubber composite according to this embodiment may have a second rubber member in contact with the rubber member.
The second rubber member contains rubber. Examples of the rubber to be used include those listed as the rubber contained in the rubber member described above.
In addition, other components such as additives may be added to the second rubber member according to the purpose, and examples of the additives include those listed above as additives contained in the rubber member.

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

In addition, when the resin-rubber composite is used for a tire, the combinations of the resin member and the rubber member include the following combinations.
- When the resin member is the "belt layer", the rubber member includes at least one member selected from "a tread, a tire frame body, 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 frame and a rubber sheet adhered to the surface of the bead member".
・When the resin member is a “tire frame”, the rubber member includes at least one member selected from “tread, belt layer, bead member, and rubber sheet adhered to the surface of the tire frame”.
- When the resin member is a "belt cord", the rubber member includes at least one member selected from "a cord coating layer that covers 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 that covers the bead wire, and a rubber sheet adhered to the surface of the bead wire".
The "tire frame" as the rubber member described above may be replaced with a member forming a tire skeleton such as a carcass corresponding to a rubber member (for example, a carcass consisting only of a carcass ply in which the periphery of a plurality of wires is coated with rubber).

Further, when the resin-rubber composite has a mode having 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 are possible.
- When the resin member is a "belt layer", the rubber member includes a "rubber sheet", and the second rubber member includes at least one member selected from "tread, tire frame, and side rubber".
- When the resin member is a "bead member", the rubber member may be a "rubber sheet", and the second rubber member may be at least one member selected from "tire frame and side rubber".
- When the resin member is a "tire frame", the rubber member includes a "rubber sheet", and the second rubber member includes at least one member selected from "tread, belt layer, bead member, and side rubber".
- When the resin member is a "belt cord", the rubber member may be a "rubber sheet", and the second rubber member may be a "cord covering layer".
- When the resin member is a "bead wire", the rubber member may be a "rubber sheet", and the second rubber member may be a "wire coating layer".
The "tire frame" as the second rubber member may be replaced with a member forming a tire frame such as a carcass corresponding to the second rubber member (for example, a carcass consisting of only carcass plies in which a plurality of wires are coated with rubber).

Here, the configuration of the tire according to the present embodiment will be described with specific examples and with reference to the drawings. Note that the sizes of the members in each drawing are conceptual, and the relative relationship between the sizes of the members is not limited to this. In addition, members having substantially the same functions are denoted by the same reference numerals throughout the drawings, and redundant description may be omitted.

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

[First embodiment]
FIG. 1 is a cross-sectional view along the tire width direction of the tire of the first embodiment.
In the tire of the first embodiment, the tire case 17 (an example of the tire frame) corresponds to the resin member. In the tire 200 of the first embodiment, as shown in FIG. 1, a belt layer 26 is formed by winding a belt in which a belt cord 26A is coated with a coating resin 26B in the circumferential direction around the outer peripheral surface of the crown portion 16 of the tire case 17. The 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, which correspond to the resin members, have treated surfaces in which at least the surfaces in contact with the cushion rubber 28 are treated by the above-described surface treatment.

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

The tensile elastic modulus of the tire frame body (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 modulus is 50 MPa to 1000 MPa, rim assembly can be efficiently performed while maintaining the shape of the tire frame.

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

The tensile yield strength defined in JIS K7113 (1995) of the tire frame body (eg, 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, the tire can withstand deformation due to a load applied to the tire during running or the like.

The tensile yield elongation defined in JIS K7113 (1995) of the tire frame body (eg, 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 defined in JIS K7113 (1995) of the tire frame body (eg, 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. When the tensile elongation at break is 50% or more, the rim-fitting property is good, and it is possible to make it difficult to break against a collision.

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

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

A cushion rubber 28 is joined so as to be in contact with a region of the outer peripheral surface of the belt layer 26 and the outer peripheral surface of the tire case 17 which is not covered with the belt layer 26, and a tread layer 30 containing rubber is further joined on the outer peripheral surface of the cushion rubber 28. - 特許庁The cushion rubber 28 and the tread layer 30 form a rubber tread, and the cushion rubber 28 corresponds to a rubber member. The tread layer 30 has a tread pattern (not shown) formed of a plurality of grooves on the surface that contacts the road surface.

Next, a method for manufacturing a tire according to the first embodiment, which includes the tire case 17 and the belt layer 26 corresponding to resin members, 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, for example, by extrusion molding of a resin material. Then, the tire case halves are placed face to face and joined together by a method such as pressing at a temperature above the melting point of the resin material forming the tire case to form the tire case 17 .

Belt layer winding process As a method of forming the belt layer 26 on the crown portion 16 of the tire case 17, for example, while rotating the tire case 17, a belt wound on a reel (that is, a member in which the belt cord 26A is coated with the coating resin 26B) is unwound, and the belt layer 26 is formed by winding the belt around the crown portion 16 a predetermined number of times. Note that the coating resin 26B may be welded to the tire case 17 by applying heat and pressure.

Surface treatment process At least the outer peripheral surface of the belt layer 26 that is in contact with the cushion rubber 28 and the area of the outer peripheral surface of the tire case 17 that is not covered by the belt layer 26 and is in contact with the cushion rubber 28 are subjected to surface treatment by the method described above. However, the timing of performing the surface treatment is not particularly limited, and for example, the tire case 17 and the belt layer 26 may be treated collectively after the belt layer 26 is formed. Alternatively, 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 and Vulcanizing Steps Next, the unvulcanized cushion rubber 28 is wound around the outer peripheral surface of the belt layer 26 and the outer peripheral surface of the tire case 17 so as to come into contact with the area not covered with the belt layer 26 . The cushion rubber 28 corresponding to the rubber member contains a filler having a silanol group. After that, the vulcanized, semi-vulcanized, or unvulcanized tread layer 30 is wound around the cushion rubber 28 for one turn. After that, vulcanization is performed to obtain the tire of the first embodiment.

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

In the tire 200 of the first embodiment, the cushion rubber 28 corresponding to the rubber member contains a filler having a silanol group, and the regions of the tire case 17 and the belt layer 26 corresponding to the resin member that are in contact with the cushion rubber 28 are surface-treated by the method described above. Therefore, excellent adhesion between the tire case 17 and the belt layer 26 and the cushion rubber 28 constituting the tread can be obtained without interposing an adhesive between the tire case 17 and the cushion rubber 28 and between the belt layer 26 and the cushion rubber 28.例文帳に追加

(Modification)
In the tire 200 of the first embodiment shown in FIG. 1, the tread is formed on the outer peripheral surface of the tire case 17 by laminating the cushion rubber 28 and the tread layer 30. However, the configuration is not limited to this, and the cushion rubber 28 may not be arranged. In this 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.

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

When a rubber sheet corresponding to a 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 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 a bead member, a belt cord, and a bead wire correspond to resin members will be described as an example.

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

As shown in FIG. 2, the tire 110 has a pair of left and right bead portions 112 (only one bead portion 112 is shown in FIG. 2), a pair of tire side portions 114 extending radially outward from the pair of bead portions 112, and a tread portion 116 extending from one tire side portion 114 to the other tire side portion 114.

A tire 110 shown in FIG. 2 includes a tire case 140 corresponding to a tire frame. The tire case 140 corresponds to a rubber member, is formed using rubber, and contains a filler having a silanol group. Tire case 140 includes bead portion 112 , tire side portion 114 , and tread portion 116 .
In addition, the tire case 140 corresponding to the rubber member in FIG. 2 may be replaced with a member forming the skeleton of the tire such as a carcass corresponding to the rubber member (for example, a carcass consisting of only carcass plies in which the periphery of a plurality of wires is coated with rubber).

A protective layer 122 is provided on the outer side of the tire side portion 114 and the bead portion 112 in the tire width direction, the inner side of the bead portion 112 in the tire radial direction, and a part of the inner side of the bead portion 112 in the tire width direction. The tire case 140 may have the bead portion 112, the tire side portion 114, and the tread portion 116 integrally formed in the same process, or may be a combination of members formed in different processes.

A bead filler 120 is embedded in the bead portion 112 and extends from the bead core 118 outward in the tire radial direction along the protective layer 122 . The bead filler 120 corresponds to a resin member, and the surface that contacts the tire case 140 is a surface treated by the surface treatment described above.

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

The protective layer 122 is provided for the purpose of improving airtightness between the tire case 140 and the rim, and is made of a material such as rubber that is softer and more weather resistant than the tire case 140, but may be omitted.

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

- Production of tire A method for producing the tire case 140 is not particularly limited. For example, tire case halves obtained by dividing the tire case 140 along the equatorial plane (the plane indicated by CL in FIG. 2) may be produced by extrusion molding (for example, injection molding) or the like, and the tire case halves may be joined together at the equatorial plane. Further, when the tire case 140 corresponding to the rubber member is replaced with a carcass, a carcass produced by a conventionally known method may be used.
As a method of forming the belt layer 124A on the tread portion 116 of the tire case 140, for example, while rotating the tire case 140, a belt wound on a reel (a member in which the belt cord 1 shown in FIG. 3A is coated with the cord coating layer 3) is unwound, and the belt layer 124A is formed by winding the belt around the crown portion 16 a predetermined number of times. The cord covering layer 3 may be welded to the tire case 140 by applying heat and pressure.
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, pre-formed annular members for the bead filler 120 and the bead core 118 may be embedded in the bead portion 112 by a known method.

In the tire 110 of the second embodiment, the tire case 140 corresponding to the rubber member contains a filler having a silanol group, and the bead filler 120 (an example of the bead member) corresponding to the resin member contacts the tire case 140. The surface treatment is performed by the method described above. Therefore, excellent adhesiveness between the tire case 140 and the bead filler 120 (an example of the bead member) can be obtained without interposing an adhesive between the tire case 140 and the bead filler 120 .

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

When a rubber sheet corresponding to a 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 preferably 0.1 μm or more and 100 mm or less, and more preferably 1 μm or more and 2 mm or less.

(Form of bead core)
Next, several examples of possible forms of the bead core 118 shown in FIG. 2 will be described.
FIG. 3A is a diagram schematically showing a cross section of a part of the bead core 118 cut perpendicularly to the length direction of the bead wire 1. FIG. In FIG. 3A, the wire covering layer 3 is provided so as to be in direct contact with the three bead wires 1. In FIG. In the embodiment shown in FIG. 3A, the bead wire 1 corresponds to a resin member, and the surface in contact with the wire coating layer 3 is a treated surface treated by the surface treatment described above. The wire coating layer 3 corresponds to a rubber member, is formed using rubber, and contains a filler having a silanol group. Therefore, excellent adhesion between the bead wire 1 and the wire coating layer 3 can be obtained without an adhesive interposed between the bead wire 1 and the wire coating layer 3 .
It should be noted that the bead wire 1 may be formed by stepping it horizontally and vertically while thermally welding one bead wire 1 .

Also, the bead core 118 may have a rubber sheet 2 disposed between the bead wire 1 and the wire covering layer 3 . A part of the bead core 118 shown in FIG. 3B is provided by adhering the rubber sheet 2 to each surface of the three bead wires 1, and further, the wire coating layer 3 is 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. Moreover, the wire coating layer 3 corresponds to the second rubber member, and the wire coating layer 3 may not 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 interposing an adhesive between the bead wire 1 and the rubber sheet 2 .

Although FIGS. 3A and 3B show three bead wires 1 arranged in parallel, the number of bead wires 1 may be two or less or four or more.
The bead core 118 shown in FIG. 2 has a form in which three bead wires 1 and the wire covering layer 3 shown in either FIG. 3A or 3B (and the rubber sheet 2 in FIG. 3B) are laminated in three layers. However, the bead core 118 may be used as a single layer or as a laminate of two or more layers. In that case, it is preferable to weld between the wire coating layers.
In addition, although FIG. 3A and FIG. 3B were mentioned and the form which the bead core 118 can take was demonstrated, it is not limited to this structure.

A 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 surface treatment described above, and then the rubber material for forming the rubber sheet 2 (the rubber material contains a filler having a silanol group) and the rubber material for forming the wire coating layer 3 can be produced by an extrusion molding method.

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

Also, the belt layer 124A may have a rubber sheet disposed between the belt cord and the cord covering layer. This configuration includes a configuration similar to that of the bead core 118 shown in FIG. 3B, that is, a configuration in which a rubber sheet is adhered to the surface of each of the three belt cords, and a cord coating layer is provided on the surface thereof. In this case, the rubber sheet corresponds to the rubber member, and the rubber sheet contains a filler having a silanol group. Also, the cord coating layer corresponds to the second rubber member, and the cord coating layer may not contain a filler having a silanol group. As a result, excellent adhesiveness between the belt cord and the rubber sheet can be obtained without interposing an adhesive between the belt cord and the rubber sheet.

It should be noted that the number of belt cords may be two or less or four or more, instead of being limited to a mode in which three belt cords are arranged in parallel.
Also, the belt layer 124A shown in FIG. 2 has a configuration in which three belt cords and a cord covering 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 between the cord covering layers.
Although the configuration that the belt layer 124A can take has been described above, it is not limited to this configuration.

Although the configuration of the tire according to the present embodiment has been described above with reference to the first and second embodiments, these embodiments are merely examples, and the present embodiment can be implemented with various modifications within the scope of the gist thereof. Moreover, 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 resin-rubber composites, tires, and methods for producing resin-rubber composites.
<1> According to the first aspect of the present disclosure,
A resin member having a treated surface which has been subjected to a first surface treatment by plasma treatment and further subjected to a second surface treatment with a reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group on the surface subjected to the plasma treatment;
a rubber member that is in contact with the treated surface of the resin member and contains a rubber containing a functional group exhibiting reactivity with the organic reactive group;
A resin-rubber composite having
<2> According to the second aspect of the present disclosure,
The treated surface of the resin member is a surface into which at least one selected from peroxy radicals (-O-O), hydroperoxide groups (-O-OH), carbonyl groups (-C(=O)-), aldehyde groups (-C(=O)-H), carboxy groups (-C(=O)-OH), and hydroxyl groups (-OH) are introduced by the plasma treatment.
<3> According to the third aspect of the present disclosure,
There is provided the resin-rubber composite according to the first or second aspect, wherein the water contact angle of 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,
having a resin member and a rubber member in contact with the resin member,
At the interface between the resin member and the rubber member, the surface of the resin member and the surface of the rubber member are bonded by a cross-linking group obtained by reacting at least one selected from the group represented by the following group [P] with the following reactive inorganic compound,
The rubber member includes a rubber containing a functional group exhibiting reactivity with an organic reactive group possessed by the following reactive inorganic compound,
A resin-rubber composite is provided.
・Base [P]
peroxy radical (-O-O), hydroperoxide group (-O-OH), carbonyl group (-C(=O)-), aldehyde group (-C(=O)-H), carboxy group (-C(=O)-OH), and hydroxyl group (-OH)
- Reactive inorganic compound A reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group <5> According to the fifth aspect of the present disclosure,
There is provided the resin-rubber composite according to the fourth aspect, wherein the contact angle of water on the resin member side surface at the interface between the resin member and the rubber member is 20° or more and 98° or less.
<6> According to the sixth aspect of the present disclosure,
A resin-rubber composite according to any one of the first to fifth aspects is provided, wherein the organic reactive group contained in the reactive inorganic compound is at least one group selected from a polysulfide group, a vinyl group, a thiol group, an amino group, an isocyanate group, and an epoxy group.
<7> According to the seventh aspect of the present disclosure,
A resin-rubber composite according to any one of the first to sixth aspects is provided, wherein the reactive inorganic compound contains a Si atom as an inorganic element.
<8> According to the eighth aspect of the present disclosure,
A resin-rubber composite according to any one of the first to seventh aspects is provided, wherein the functional group contained in the rubber is at least one group selected from a diene group, a vinyl group, an isocyanate group, an amino group, a hydroxyl group, a carboxy group, an epoxy group, a thiol group, and a polysulfide group.
<9> According to the ninth aspect of the present disclosure,
A resin-rubber composite according to any one of the first to eighth aspects is provided, wherein the rubber member further contains a filler having a silanol group.
<10> According to the tenth aspect of the present disclosure,
There is provided the resin-rubber composite according to the ninth aspect, wherein the filler having a silanol group is silica.
<11> According to the eleventh aspect of the present disclosure,
There is provided a resin-rubber composite according to the tenth aspect, wherein the silica is hydrophilic silica.
<12> According to the twelfth aspect of the present disclosure,
A resin-rubber composite according to any one of the ninth to eleventh aspects is provided, wherein the rubber member further contains a silane coupling agent.
<13> According to the thirteenth aspect of the present disclosure,
Further, a resin-rubber composite according to any one of the first to twelfth aspects is provided, which has a second rubber member in contact with the rubber member.
<14> According to the fourteenth aspect of the present disclosure,
A resin-rubber composite according to any one of the first to thirteenth aspects is provided, wherein the resin member contains at least one resin selected from a polyester thermoplastic elastomer, a polyester thermoplastic resin, a polyamide thermoplastic elastomer, a polyamide thermoplastic resin, a polystyrene thermoplastic elastomer, a polystyrene thermoplastic resin, a polyurethane thermoplastic elastomer, a polyurethane thermoplastic resin, a polyolefin thermoplastic elastomer, and a polyolefin thermoplastic resin.
<15> According to the fifteenth aspect of the present disclosure,
There is provided the resin-rubber composite according to the fourteenth aspect, wherein the resin member contains at least one resin selected from polyester thermoplastic elastomers and polyester thermoplastic resins.
<16> According to the sixteenth aspect of the present disclosure,
, a tire having a resin-rubber composite according to any one of the first to fifteenth aspects.
<17> According to the seventeenth aspect of the present disclosure,
A tire according to the sixteenth aspect is provided, comprising a belt layer as the resin member, and at least one member selected from a tread as the rubber member, a tire frame body, and a rubber sheet adhered to the surface of the belt layer.
<18> According to the eighteenth aspect of the present disclosure,
A tire according to the sixteenth aspect, comprising a bead member as the resin member, and at least one member selected from a tire frame body as the rubber member and a rubber sheet adhered to the surface of the bead member.
<19> According to the nineteenth aspect of the present disclosure,
A tire according to the sixteenth aspect is provided, comprising a tire frame body as the resin member, and at least one member selected from a tread, a belt layer, a bead member, and a rubber sheet adhered to the surface of the tire frame body as the rubber member.
<20> According to the twentieth aspect of the present disclosure,
The tire according to the sixteenth aspect is provided, wherein the resin-rubber composite is a belt layer having at least one member 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.
<21> According to the twenty-first aspect of the present disclosure,
The tire according to the sixteenth aspect is provided, wherein the resin-rubber composite is a bead core having at least one member 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.
<22> According to the twenty-second aspect of the present disclosure,
a surface treatment step of subjecting at least part of the surface of the resin member to a first surface treatment by plasma treatment, and a second surface treatment of a reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group on the plasma-treated surface;
A bonding step of placing a rubber member containing rubber containing a functional group exhibiting reactivity with the organic reactive group in contact with the surface of the resin member subjected to the first surface treatment and the second surface treatment, and heating to bond the resin member and the rubber member;
A method for producing a resin-rubber composite having

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

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

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

3. Surface treatment First surface treatment A plasma generator (manufactured by Meisho Kiko Co., Ltd., product name K2X02L023) was used as a plasma irradiation apparatus for surface-treating a resin member. As the high-frequency power source of the plasma generator, the frequency of the applied voltage was 13.56 MHz, and as the electrode, a copper tube with an inner diameter of 1.8 mm, an outer diameter of 3 mm, and a length of 165 mm was covered with an alumina tube with an outer diameter of 5 mm, a thickness of 1 mm, and a length of 100 mm. 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.
After sealing the chamber and reducing the pressure to 10 Pa or less with a rotary pump, helium gas was introduced to atmospheric pressure (that is, 1013 hPa). After that, the high-frequency power source was set so that the output power density (that is, the irradiation density) was 5.7 W/cm ² , and the moving speed of the scanning stage was set at 2 mm/sec.
After that, 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 the first surface treatment.

Second Surface Treatment Next, the resin member (that is, square plate) that had been subjected to the first surface treatment by plasma treatment was subjected to the following second treatment using a silane coupling agent.
First, 0.1 mL of acetic acid was added to 100 mL of ethanol to adjust the pH from 8 to 4, and then 2 mL of silane coupling agent A was added and stirred for 45 minutes to prepare a surface treatment liquid. The resin member subjected to the first surface treatment was immersed in this surface treatment liquid for 1 minute.
Then, it was lightly rinsed with ethanol and then lightly rinsed with pure water, and then dried with an _N2 gas spray gun. Further, the substrate was dried at 120° C. for 30 minutes using an electric furnace, ultrasonically cleaned with ethanol for 1 minute, and then dried with a N ₂ gas spray gun to apply a second surface treatment with a silane coupling agent.

Table 1 below shows the contact angles of water on the treated surfaces subjected to the first surface treatment and the second surface treatment. However, the contact angle of water shown in Table 1 is a predicted value obtained from a simulation based on the contact angle of water on a resin member obtained by performing the first surface treatment using a plasma generator with specifications different from the plasma generator described above and performing the second surface treatment with a silane coupling agent.

4. Adhesion A rubber member (that is, a sheet) was attached to a resin member (that is, a square plate) that had been subjected to the first and second surface treatments, 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 test piece was subjected to the following peel test. Table 1 shows the results.

[Examples 2 to 6, Comparative Examples 1 to 3]
A test piece was prepared in the same manner as in Example 1, except that the composition when producing the rubber member (that is, the sheet) was changed to the composition shown in Table 1, and the presence or absence of the first surface treatment by plasma treatment on the resin member (that is, the square plate), the presence or absence of the second surface treatment with a silane coupling agent, and the type of the silane coupling agent used for the second surface treatment were changed to those shown in Table 1, and a peel test was performed.

[Comparative Example 4]
A test piece is prepared in the same manner as in Example 1, except that the composition when producing the rubber member (that is, the sheet) is changed to the composition shown in Table 1, and the presence or absence of the first surface treatment by plasma treatment on the resin member (that is, the square plate), the presence or absence of the second surface treatment with a silane coupling agent, and the type of silane coupling agent used for the second surface treatment are changed to those shown in Table 1, and the peel test is performed.
In addition, about the comparative example 4, it is the predicted value obtained from the simulation.

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

Details of each component shown in Table 1 are as follows.
<Rubber member composition>
・Rubber (SBR)/Styrene-butadiene rubber, JSR Corporation, JSR1502
・ Silica 1 / Tosoh Silica Co., Ltd., product name: Nip Seal AQ
・ Silica 2 / manufactured by Nippon Aerosil Co., Ltd., product name: AEROSIL200
・Silica 3: manufactured by Tosoh Silica Co., Ltd., product name: Nip Seal HQ-N (BET specific surface area: 260 m ² /g)
・Silane coupling agent 1/Shin-Etsu Chemical Co., Ltd., product name: Bis-(triethoxysilylpropyl)-polysulfide Accelerator (DPG)/diphenylguanidine, Ouchi Shinko Kagaku Kogyo, Noxcellar D
・ Accelerator (CZ) / N-cyclohexylbenzothiazylsulfenamide, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Noxcellar CZ
・ Accelerator (DM) / di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Noxceler DM

<Second surface treatment>
・Silane coupling agent A / manufactured by Shin-Etsu Chemical Co., Ltd., product name: bis-(triethoxysilylpropyl)-polysulfide ・Silane coupling agent B / manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-1083

1 bead wire 2 rubber sheet 3 wire coating layer 12 bead portion 16 crown portion 17 tire case (an example of a tire frame)
18 bead core 26 belt layer 26A belt cord 26B coating resin 28 cushion rubber 30 tread layer 110 tire 112 bead portion 114 tire side portion 116 tread portion 118 bead core 122 protective layer 124A belt layer 124B cushion rubber 130 tread layer 140 tire case (an example of a tire frame)
200 Tire CL Tire equatorial plane Q Midpoint

Claims (18)

A resin member having a treated surface that has been subjected to a first surface treatment by plasma treatment, and further subjected to a second surface treatment with a reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group on the surface that has been subjected to the plasma treatment;
a rubber member that is in contact with the treated surface of the resin member and contains a rubber containing a functional group exhibiting reactivity with the organic reactive group , a filler having a silanol group, and a silane coupling agent ;
has
The reactive inorganic compound is a polysulfide-based silane coupling agent having two or more sulfur atoms,
The content of the filler having a silanol group contained in the rubber member is 20 phr or more and 100 phr or less with respect to the total amount of the rubber,
The silane coupling agent contained in the rubber member is a polysulfide-based silane coupling agent having two or more sulfur atoms,
The content of the silane coupling agent in the rubber member is 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the filler having a silanol group.
Resin -rubber composite. 2. The resin-rubber composite according to claim 1, wherein the treated surface of the resin member is a surface into which at least one selected from peroxy radicals (-O-O), hydroperoxide groups (-O-OH), carbonyl groups (-C(=O)-), aldehyde groups (-C(=O)-H), carboxy groups (-C(=O)-OH), and hydroxyl groups (-OH) are introduced by the plasma treatment. 3. The resin-rubber composite according to claim 1, wherein the treated surface of the resin member has a water contact angle of 20[deg.] or more and 98[deg.] or less. having a resin member and a rubber member in contact with the resin member,
At the interface between the resin member and the rubber member, the surface of the resin member and the surface of the rubber member are bonded by a cross-linking group obtained by reacting at least one selected from the group represented by the following group [P] with the following reactive inorganic compound,
The rubber member includes a rubber containing a functional group exhibiting reactivity with the organic reactive group of the reactive inorganic compound described below, a filler having a silanol group, and a silane coupling agent ,
The reactive inorganic compound is a polysulfide-based silane coupling agent having two or more sulfur atoms,
The content of the filler having a silanol group contained in the rubber member is 20 phr or more and 100 phr or less with respect to the total amount of the rubber,
The silane coupling agent contained in the rubber member is a polysulfide-based silane coupling agent having two or more sulfur atoms,
The content of the silane coupling agent in the rubber member is 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the filler having a silanol group.
Resin -rubber composite.
・ Group [P]
peroxy radical (-O-O), hydroperoxide group (-O-OH), carbonyl group (-C(=O)-), aldehyde group (-C(=O)-H), carboxy group (-C(=O)-OH), and hydroxyl group (-OH)
- Reactive inorganic compound A reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group 5. The resin-rubber composite according to claim 4, wherein the contact angle of water on the surface of the resin member at the interface between the resin member and the rubber member is 20[deg.] or more and 98[deg.] or less. The functional group contained in the rubber is at least one group selected from a diene group, a vinyl group, an isocyanate group, an amino group, a hydroxyl group, a carboxy group, an epoxy group, a thiol group, and a polysulfide group. The resin-rubber composite according to any one of claims 1 to 5 . The resin-rubber composite according to any one of claims 1 to 6, wherein the filler having a silanol group is silica. 8. The resin-rubber composite according to claim 7 , wherein said silica is hydrophilic silica. The resin-rubber composite according to any one of claims 1 to 8 , further comprising a second rubber member in contact with said rubber member. The resin-rubber composite according to any one of claims 1 to 9 , wherein the resin member contains at least one resin selected from a polyester thermoplastic elastomer, a polyester thermoplastic resin, a polyamide thermoplastic elastomer, a polyamide thermoplastic resin, a polystyrene thermoplastic elastomer, a polystyrene thermoplastic resin, a polyurethane thermoplastic elastomer, a polyurethane thermoplastic resin, a polyolefin thermoplastic elastomer, and a polyolefin thermoplastic resin. 11. The resin-rubber composite according to claim 10 , wherein the resin member contains at least one resin selected from polyester thermoplastic elastomers and polyester thermoplastic resins. A tire comprising the resin-rubber composite according to any one of claims 1 to 11 . The tire according to claim 12 , comprising a belt layer as the resin member and at least one member selected from a tread as the rubber member, a tire frame body, and a rubber sheet adhered to the surface of the belt layer. The tire according to claim 12 , comprising a bead member as the resin member, and at least one member selected from a tire frame body as the rubber member and a rubber sheet adhered to the surface of the bead member. The tire according to claim 12 , comprising a tire frame body as the resin member, and at least one member selected from a tread, a belt layer, a bead member, and a rubber sheet adhered to the surface of the tire frame body as the rubber member. The tire according to claim 12 , wherein the resin-rubber composite is a belt layer having at least one member 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 , wherein the resin-rubber composite is a bead core having at least one member 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 surface treatment step of subjecting at least part of the surface of the resin member to a first surface treatment by plasma treatment, and a second surface treatment on the plasma-treated surface with a reactive inorganic compound containing at least one group selected from an organic reactive group and a hydroxyl group and an alkoxy group;
a bonding step of placing a rubber member containing a rubber containing a functional group exhibiting reactivity with the organic reactive group, a filler having a silanol group, and a silane coupling agent in contact with the surface of the resin member that has been subjected to the first surface treatment and the second surface treatment, and heating to bond the resin member and the rubber member ;
The reactive inorganic compound used for the second surface treatment in the surface treatment step is a polysulfide-based silane coupling agent having two or more sulfur atoms,
The content of the filler having a silanol group contained in the rubber member used in the bonding step is 20 phr or more and 100 phr or less with respect to the total amount of the rubber,
The silane coupling agent contained in the rubber member is a polysulfide-based silane coupling agent having two or more sulfur atoms,
The content of the silane coupling agent in the rubber member is 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the filler having a silanol group.
A method for producing a resin- rubber composite.