JP2023064477A - Resin-rubber composite and tire - Google Patents

Abstract

To provide a resin-rubber composite excellent in adhesiveness between a resin layer and a rubber layer in direct contact with the resin layer.SOLUTION: The resin-rubber composite includes: a first layer which is a vulcanized product of a rubber composition comprising a rubber containing a diene rubber, carbon black, an oil-modified novolac type phenolic resin, and an amine-based curing agent; and a second layer which is provided in direct contact with the first layer and is a resin layer comprising a resin that contains a polyester-based thermoplastic elastomer and an epoxy resin.SELECTED DRAWING: None

Description

The present invention relates to resin-rubber composites and tires.

BACKGROUND ART In recent years, in the field of tires, for example, from the viewpoint of weight reduction, ease of molding, recycling, and the like, use of a member including a resin layer as part of a tire member has been studied. For example, Patent Literature 1 proposes a tire using a polyamide-based thermoplastic elastomer, which is a thermoplastic polymeric material, as a resin.
On the other hand, when a member including a resin layer is used as part of a tire member, the resin layer may be arranged at a position in contact with the rubber layer of another member. It is not easy to improve the adhesion with the layer. Therefore, for example, by providing a layer of an organic solvent-based adhesive between the resin layer and the rubber layer, separation at the interface between the resin layer and the rubber layer is avoided.

JP 2012-46030 A

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

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin-rubber composite having excellent adhesion between a resin layer and a rubber layer in direct contact with the resin layer, and a tire having the resin-rubber composite.

Specific means for solving the above problems include the following aspects.
<1> A first layer, which is a vulcanized body of a rubber composition containing rubber containing a diene rubber, carbon black, an oil-modified novolak-type phenolic resin, and an amine-based curing agent;
a second layer which is provided in direct contact with the first layer and is a resin layer containing a resin containing a thermoplastic polyester elastomer and an epoxy resin;
A resin-rubber composite having
<2> The resin-rubber composite according to <1>, wherein the content of the thermoplastic polyester elastomer is 50% by mass or more with respect to the entire second layer.
<3> The resin-rubber composite according to <1> or <2>, wherein the content of the epoxy resin is 3% by mass or more with respect to the entire second layer.
<4> The resin-rubber composite according to any one of <1> to <3>, wherein the content of the oil-modified novolak-type phenolic resin is 3 parts by mass or more with respect to 100 parts by mass of the rubber.
<5> The resin-rubber composite according to any one of <1> to <4>, wherein the content of the carbon black is 25 parts by mass to 80 parts by mass with respect to 100 parts by mass of the rubber.
<6> The third layer is directly in contact with the first layer, is provided on the surface of the first layer opposite to the second layer, and is a rubber layer containing a diene rubber, < The resin-rubber composite according to any one of 1> to <5>.
<7> A tire comprising the resin-rubber composite according to any one of <1> to <6>.
<8> an annular tire frame member;
a belt member provided outside the tire frame member in the tire radial direction and including the second layer;
a rubber member provided outside the belt member in the tire radial direction and including the first layer;
The tire according to <7>.
<9> an annular tire frame member including the second layer;
a rubber member provided on at least one of the tire width direction outer side and the tire width direction inner side of the tire frame member and including the first layer;
The tire according to <7>.
<10> Having an annular tire frame member including the first layer,
The tire according to <7>, wherein the bead portion of the tire frame member includes at least one of a bead core including the second layer and a bead filler including the second layer.

According to the present invention, it is possible to provide a resin-rubber composite having excellent adhesiveness between a resin layer and a rubber layer in direct contact with the resin layer, and a tire having the resin-rubber composite.

It is a perspective view showing a section of a portion of the tire concerning a 1st embodiment. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing along the tire width direction which shows the structure of the tire which concerns on 1st Embodiment. It is a cross-sectional view along the tire width direction showing the configuration of a tire according to a second embodiment. It is a cross-sectional view along the tire width direction showing the configuration of a tire according to a third embodiment. It is sectional drawing which expanded the bead part of the tire which concerns on 4th Embodiment.

Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments at all, and can be carried out with appropriate modifications within the scope of the purpose of the present invention. be able to.

As used herein, "resin" is a concept that includes thermoplastic resins, thermoplastic elastomers, and thermosetting resins, and does not include vulcanized rubber.
In this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
In the present specification, the term "step" includes not only an independent step, but also the step, even if it cannot be clearly distinguished from other steps, as long as its purpose is achieved. include.
As used herein, the amount of each component in the composition refers to the sum of the substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means quantity.
As used herein, the term “main component” means the component with the highest content in the mixture on a mass basis, unless otherwise specified.

As used herein, the term "thermoplastic resin" means a polymer compound that softens and flows as the temperature rises, becomes relatively hard and strong when cooled, but does not have rubber-like elasticity.
As used herein, "thermoplastic elastomer" means a copolymer having hard segments and soft segments. Specific examples of the thermoplastic elastomer include, for example, 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. A copolymer having Thermoplastic elastomers include, for example, materials that soften and flow as the temperature rises, become relatively hard and strong when cooled, and have rubber-like elasticity.
The hard segment has, for example, a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure that enables intermolecular packing due to intermolecular hydrogen bonding or π-π interaction. segment. 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.

[Resin-rubber composite]
The resin-rubber composite (hereinafter also referred to as “composite”) according to the present embodiment is a rubber composition containing rubber containing a diene rubber, carbon black, an oil-modified novolak-type phenolic resin, and an amine curing agent. A first layer (hereinafter also referred to as a "specific rubber layer") that is a sulfur body, and a resin layer that is provided in direct contact with the specific rubber layer and contains a resin containing a polyester thermoplastic elastomer and an epoxy resin. 2 layers (hereinafter also referred to as “resin layers”).
Hereinafter, a rubber composition containing a diene rubber-containing rubber, carbon black, an oil-modified novolak-type phenolic resin, and an amine curing agent is also referred to as a "specific rubber composition."

As described above, in a composite in which the resin layer is in contact with the rubber layer, it is not easy to increase the adhesiveness between the resin layer and the rubber layer due to the difference in materials. On the other hand, in the method of providing an organic solvent-based adhesive layer between the resin layer and the rubber layer, although the adhesiveness is improved, the solvent must be volatilized after the coating film is formed, which simplifies the manufacturing process. , there is room for improvement in terms of cost reduction and the like.
Therefore, in a composite in which a resin layer and a rubber layer 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 intervening therebetween. ing.

On the other hand, in the composite of the present embodiment, the rubber layer in direct contact with the resin layer is a specific rubber composition containing rubber containing diene rubber, carbon black, oil-modified novolak-type phenolic resin, and amine-based curing agent. The specific rubber layer is a vulcanized body, and the resin layer contains a resin containing a thermoplastic polyester elastomer and an epoxy resin. Therefore, the adhesion between the resin layer and the rubber layer in direct contact with the resin layer is excellent. Although the reason is not clear, it is presumed as follows.
At the interface between the resin layer and the specific rubber composition, which is the unvulcanized specific rubber layer, the epoxy group of the epoxy resin contained in the resin layer is ring-opened at the vulcanization temperature, and is contained in the specific rubber composition. It reacts with part of the hydroxyl groups of the oil-modified novolac-type phenolic resin, either directly or via an amine-based curing agent, to form covalent bonds. Reactive hydroxyl groups generated by an addition reaction between the carboxyl groups of the polyester thermoplastic elastomer contained in the resin layer and the epoxy resin during kneading are added to the oil-modified novolac phenolic resin contained in the resin composition. A covalent bond is formed by reacting with another part of the hydroxyl group directly or via an amine-based curing agent. In particular, by using an oil-modified novolac-type phenolic resin as the phenolic resin, the phenolic resin is more easily dispersed in the diene rubber than when only an unmodified phenolic resin is used, and the interface between the resin layer and the specific rubber composition The above-mentioned covalent bonds are easily formed evenly over the entire surface. Furthermore, inside the resin layer, the carboxy groups of the thermoplastic polyester elastomer react with the epoxy groups of the epoxy resin to form covalent bonds. A network of these covalent bonds realizes high adhesion between the resin layer and the specific rubber layer, which is a vulcanized product of the specific rubber composition. In addition, since the specific rubber composition contains carbon black, it is possible to reinforce the specific rubber layer, which is a vulcanized body of the specific rubber composition, without inhibiting the functional groups of the phenolic resin. The cohesive force of the specific rubber layer is increased, and the interfacial adhesion between the resin layer and the specific rubber layer is also improved. For example, when silica is used instead of carbon black, the hydroxyl groups of the phenolic resin are thought to bond with silica, reducing the amount of hydroxyl groups that contribute to adhesion to the resin. On the other hand, since carbon black is used in the present embodiment, the hydroxyl groups that contribute to adhesion with the resin are less likely to decrease, and the resin layer and the rubber layer are more firmly adhered.
For the above reasons, in this embodiment, it is presumed that the adhesiveness between the resin layer and the rubber layer in direct contact with the resin layer is excellent.

In this embodiment, since the adhesion between the resin layer and the rubber layer in direct contact with the resin layer is excellent as described above, it is necessary to provide a layer of an organic solvent-based adhesive between the resin layer and the rubber layer. It is possible to obtain a composite with high adhesion between the resin layer and the rubber layer while improving workability.

As described above, the composite of the present embodiment only needs to have at least the specific rubber layer and the resin layer in direct contact with the specific rubber layer, and may further have other layers as necessary. good. As the other layer, for example, a third layer (hereinafter referred to as a third layer) that is provided on the surface opposite to the resin layer in the specific rubber layer that is in direct contact with the resin layer, is in direct contact with the specific rubber layer, and is a rubber layer containing a diene rubber. Also referred to as "another rubber layer") and the like.
Each layer constituting the composite according to the present embodiment will be described below.

<Specific rubber layer (first layer)>
The composite according to this embodiment has a specific rubber layer in direct contact with the resin layer.
The specific rubber layer is a vulcanized product of a specific rubber composition containing at least rubber containing a diene rubber, carbon black, an oil-modified novolak-type phenolic resin, and an amine curing agent. The specific rubber composition may contain other components as necessary.

(rubber)
The specific rubber composition preferably contains rubber as a main component.
The rubber content relative to the total amount of the specific rubber composition may be, for example, 50% by mass or more, may be 55% by mass or more, or may be 60% by mass or more. Moreover, the content of rubber with respect to the total amount of the specific rubber composition may be 80% by mass or less.

The rubber contains at least a diene rubber, and may further contain other rubbers as necessary.
The content of the diene rubber is preferably 50% by mass or more, preferably 70% by mass or more, relative to the total amount of rubber from the viewpoint of excellent repeated fatigue resistance when used in tires and the like. is more preferable, more preferably 90% by mass or more, and particularly preferably 100% by mass.

Examples of diene rubber include natural rubber (NR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), isoprene rubber (IR), and synthetic rubber such as polychloroprene rubber (CR).
The diene rubber may be used singly, or two or more may be used as a mixture.
Among these, the diene rubber preferably contains natural rubber.

When the rubber includes other rubbers, the types of other rubbers are not particularly limited.
Other rubbers include, for example, non-diene rubbers. Other rubbers may be used singly or as a mixture of two or more.

(Carbon black)
The carbon black contained in the specific rubber composition is not particularly limited, and examples thereof include furnace black obtained by the furnace method, channel black obtained by the channel method, acetylene black obtained by the acetylene method, and obtained by the thermal method. thermal black and the like. Carbon black may be used alone or in combination of two or more.
The content of carbon black contained in the specific rubber composition is 25 parts by mass with respect to 100 parts by mass of rubber contained in the specific rubber composition, from the viewpoint of reinforcing the specific rubber layer and improving adhesion with the resin layer. It is preferably 80 parts by mass, more preferably 30 parts by mass to 75 parts by mass, even more preferably 35 parts by mass to 72 parts by mass.

The nitrogen adsorption surface area of the carbon black is not particularly limited, and from the viewpoint of improving adhesion to the resin layer, it is preferably 20 m ² /g or more, more preferably 25 m ² /g or more, It is more preferably 30 m ² /g or more. The upper limit of the nitrogen adsorption surface area of carbon black is not particularly limited. The nitrogen adsorption surface area of carbon black may be 250 m ² /g or less.
The nitrogen adsorption surface area of carbon black can be obtained by measuring using N ₂ gas according to ASTM D3037-88 by the BET method.

(Oil-modified novolak-type phenolic resin)
The specified rubber composition contains an oil-modified novolak-type phenolic resin.
Here, the oil-modified novolak-type phenolic resin is obtained by modifying a novolac-type phenolic resin with oil.
The novolak-type phenolic resins are obtained, for example, by condensation reaction of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, and resorcinol with aldehydes such as formaldehyde using an acid catalyst. Condensates are mentioned.
Examples of the oil used for modifying the novolac-type phenolic resin include rosin oil, tall oil, cashew oil, drying oil (linseed oil, tung oil, castor oil, etc.), linoleic acid, oleic acid, α-linolenic acid, and the like. , these oils may be used alone, or two or more of them may be used.
Among these, the oil-modified novolak-type phenol resin is preferably tall oil-modified novolac-type phenol resin or cashew oil-modified novolak-type phenol resin.
The oil-modified novolac-type phenolic resin may be used alone or in combination of two or more.

The hydroxyl group equivalent of the oil-modified novolak-type phenolic resin is preferably 100 g/eq to 300 g/eq, more preferably 100 g/eq to 200 g/eq, and further preferably 100 g/eq to 150 g/eq. preferable.
When the hydroxyl equivalent of the oil-modified novolac-type phenolic resin is within the above range, there is an advantage that the adhesiveness is superior to the case where the hydroxyl group equivalent is larger than the above range. In addition, the oil-modified novolac-type phenolic resin having a hydroxyl equivalent within the above range has the advantage that it is structurally more readily available than the oil-modified novolac-type phenolic resin having a hydroxyl equivalent less than the above range.
The hydroxyl equivalent is measured according to JIS K0070:1992.

The content of the oil-modified novolac-type phenolic resin is preferably 3 parts by mass or more, and 4 parts by mass with respect to 100 parts by mass of the rubber contained in the specific rubber composition, from the viewpoint of improving adhesion with the resin layer. It is more preferably 5 parts by mass or more, and more preferably 5 parts by mass or more.
The content of the oil-modified novolak-type phenolic resin is preferably 30 parts by mass or less, and 25 parts by mass, from the viewpoint of compatibility with rubber during kneading and reduction of rolling resistance when used as a tire. It is more preferably 20 parts by mass or less, more preferably 20 parts by mass or less.
The content of the oil-modified novolac-type phenolic resin is preferably 3 parts by mass to 30 parts by mass, more preferably 4 parts by mass to 25 parts by mass, and further preferably 5 parts by mass to 20 parts by mass. preferable.

(Amine-based curing agent)
The specific rubber composition contains an amine curing agent. Examples of amine-based curing agents include hexamethylenetetramine, paraformaldehyde, hexamethoxymethylmelamine, acetaldehyde ammonia, α-polyoxymethylene, polymethylolmelamine derivatives, oxazolidine derivatives, polymethylolated acetylene urea, and the like. Hexamethylenetetramine and hexamethoxymethylmelamine are preferably used. Particularly preferred is hexamethylenetetramine.

From the viewpoint of improving adhesion with the resin layer, the content of the amine-based curing agent is preferably 0.1 parts by mass or more, and preferably 0.2 parts by mass, with respect to 100 parts by mass of the rubber contained in the specific rubber composition. It is more preferably 0.3 parts by mass or more, more preferably 0.3 parts by mass or more. In addition, the content of the amine curing agent should be 15 parts by mass or less with respect to 100 parts by mass of the rubber contained in the specific rubber composition from the viewpoint of suppressing aged deterioration of the rubber and adjacent members due to the reaction of unreacted amine. is preferred, 12 parts by mass or less is more preferred, and 10 parts by mass or less is even more preferred.
The content of the amine-based curing agent is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 12 parts by mass, with respect to 100 parts by mass of the rubber contained in the specific rubber composition. is more preferable, and 0.3 parts by mass to 10 parts by mass is even more preferable.

In addition, the content of the amine-based curing agent is preferably 0.05 times or more, and preferably 0.07 times or more, the content of the oil-modified novolac-type phenolic resin from the viewpoint of improving adhesion to the resin layer. is more preferably 0.09 times or more. In addition, the content of the amine-based curing agent is preferably 0.5 times or less the content of the oil-modified novolac-type phenolic resin, from the viewpoint of suppressing aged deterioration of the rubber and adjacent members due to the reaction of unreacted amine. , is more preferably 0.45 times or less, and more preferably 0.4 times or less.
The content of the amine-based curing agent is preferably 0.05 to 0.5 times, more preferably 0.07 to 0.45 times, the content of the oil-modified novolac-type phenolic resin. More preferably, it is 0.09 to 0.4 times.

(other ingredients)
Other components contained in the specific rubber composition include, for example, reinforcing materials other than carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, and Oils, anti-aging agents, tackifiers, anti-scorch agents and the like. These may be used alone or in combination of two or more.

Examples of reinforcing materials other than carbon black include silica. When silica is used together with carbon black as a reinforcing material, a silane coupling agent may be further used for the purpose of improving the dispersibility of silica.
When using a reinforcing material such as silica as other components, the content of the entire reinforcing material containing carbon black and silica is specified from the viewpoint of reinforcing the rubber layer and from the viewpoint of making it difficult to generate heat when repeated strain occurs. With respect to 100 parts by mass of rubber contained in the rubber composition, it is preferably 25 parts by mass to 80 parts by mass, more preferably 30 parts by mass to 75 parts by mass, and 35 parts by mass to 72 parts by mass. is more preferred.

As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides and resin vulcanizing agents are used. Among them, it is preferable to use sulfur as a vulcanizing agent.
As the vulcanization accelerator, known vulcanization accelerators such as aldehydes, ammonias, amines, guanidines, thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates and the like are used. be done.
Examples of fatty acids include stearic acid, palmitic acid, myristic acid and lauric acid, and these may be blended in the form of salts such as zinc stearate. Among these, stearic acid is preferred.
Moreover, as the metal oxide, zinc white (ZnO), iron oxide, magnesium oxide, and the like can be mentioned, among which zinc white is preferable.
Aromatic, naphthenic, or paraffin-based process oils may be used. Anti-aging agents include amine-ketone-based, imidazole-based, amine-based, phenol-based, sulfur-based, and phosphorus-based anti-aging agents.
Examples of tackifiers include phenol-based resins, rosin-based resins, terpene-based resins, and the like.
Anti-scorch agents include, for example, N-cyclohexylthiophthalimide and the like.

<Resin layer (second layer)>
The composite according to this embodiment has a resin layer in direct contact with the specific rubber layer.
The resin layer contains a resin containing at least a thermoplastic polyester elastomer and an epoxy resin, and may contain other components as necessary. The resin layer may be a layer that is a reaction product of a resin composition containing a resin containing a thermoplastic polyester elastomer and an epoxy resin.
The resin layer preferably contains a resin as a main component. Specifically, the content of the resin with respect to the total amount of the resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 75% by mass or more.

The resin contains at least a thermoplastic polyester elastomer and an epoxy resin, and may further contain other resins as necessary.

The content of the polyester thermoplastic elastomer is preferably 50% by mass or more, more preferably 55% by mass or more, relative to the total amount of the resin layer, from the viewpoint of improving adhesion with the specific rubber layer. , more preferably 60% by mass or more. The upper limit of the content of the thermoplastic polyester elastomer is not particularly limited. The content of the thermoplastic polyester elastomer is, for example, in the range of 99% by mass or less with respect to the total amount of the resin layer.
The thermoplastic polyester elastomer may be used singly or as a mixture of two or more.

From the viewpoint of improving adhesion with the specific rubber layer, the content of the epoxy resin is preferably 3% by mass or more, more preferably 4% by mass or more, more preferably 5% by mass, relative to the total amount of the resin layer. % or more is more preferable.
In addition, from the viewpoint of reducing rolling resistance when used as a tire, the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and 20% by mass or less. is more preferred.
The content of the epoxy resin is preferably 3% by mass to 30% by mass, more preferably 4% by mass to 25% by mass, even more preferably 5% by mass to 20% by mass.
Here, the content of the epoxy resin is a value including those in a state of being covalently bonded by reacting with other components such as a polyester-based thermoplastic elastomer.
Epoxy resins may be used singly or as a mixture of two or more.

(polyester thermoplastic elastomer)
As a polyester-based thermoplastic elastomer, for example, 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. The material forming is mentioned.

An aromatic polyester can be used as the polyester forming the hard segment. 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 include, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5 - Dicarboxylic acid components such as 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, etc.) 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′- aromatic diols such as dihydroxy-p-terphenyl and 4,4'-dihydroxy-p-quarterphenyl; It may be polymerized polyester. 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.
Aliphatic polyethers include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly(propylene oxide ) ethylene oxide addition polymers of glycols, 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, poly(propylene oxide) glycol, and poly(propylene oxide) glycol are examples of polymers forming the soft segment from the viewpoint of the elastic properties of the obtained polyester block copolymer. ethylene oxide adducts, poly(ε-caprolactone), polybutylene adipate, polyethylene adipate and the like are preferred.

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, the combination of the hard segment and the soft segment described above is preferably a combination in which the hard segment is polybutylene terephthalate and the soft segment is an aliphatic polyether, and the hard segment is polybutylene terephthalate and the soft segment is is poly(ethylene oxide) glycol is more preferred.

Examples of commercially available polyester thermoplastic elastomers include the "Hytrel" series (e.g., 3046, 5557, 6347, 4047N, 4767N, etc.) manufactured by DuPont Toray Co., Ltd., and the "Pelprene" series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, E450B, 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.

(Epoxy resin)
The type of epoxy resin is not particularly limited. Epoxy resins include, for example, novolac type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, glycidylamine type epoxy resins, naphthalene type epoxy resins, and linear fats. group epoxy resins and the like.
Among these epoxy resins, biphenyl type epoxy resins and dicyclopentadiene type epoxy resins are preferable.

From the viewpoint of miscibility with the thermoplastic polyester elastomer, the epoxy resin is preferably solid at room temperature (25°C). For example, an epoxy resin having a softening point of 50° C. to 100° C. as measured by the ring and ball method is preferred.

The epoxy equivalent of the epoxy resin is preferably 80 g/eq to 500 g/eq, more preferably 100 g/eq to 400 g/eq, even more preferably 120 g/eq to 300 g/eq.
When the epoxy equivalent of the epoxy resin is within the above range, there is an advantage that the adhesiveness is excellent compared to the case where it is larger than the above range, and there is an advantage that the storage stability is excellent compared to the case where it is smaller than the above range.

(Other resins)
When the resin contains other resins, the types of other resins are not particularly limited.
Other resins include thermoplastic resins such as polyester thermoplastic resins, polyamide thermoplastic resins, polystyrene thermoplastic resins, polyurethane thermoplastic resins, polyolefin thermoplastic resins, and vinyl chloride thermoplastic resins; thermoplastic elastomers other than polyester-based thermoplastic elastomers; thermosetting resins; and the like. Other resins may be used singly or as a mixture of two or more.
Among these resins, polyester-based thermoplastic resins are preferable from the viewpoint of improving adhesion to the specific rubber layer. Further, the other resin may be a polyester thermoplastic resin having the same structure as the hard segment of the polyester thermoplastic elastomer contained in the resin layer.

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-based thermoplastic resins include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly(ε-caprolactone), polyenantholactone, polycaprylolactone, and polybutylene. Examples include aliphatic polyesters such as adipate and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene naphthalate. Among these, 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 "DURANEX" series (e.g., 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., and "NOVADURAN" series (e.g., 5010R5) manufactured by Mitsubishi Engineering-Plastics Corporation. , 5010R3-2, etc.), Toray Industries, Inc.'s "Toraycon" series (eg, 1401X06, 1401X31, etc.) and the like can be used.

(carbodiimide compound)
The resin layer may contain a carbodiimide compound as another component.
The carbodiimide compound is not particularly limited as long as it is a compound having at least one carbodiimide group (-N=C=N-) in the molecule as a functional group.
Examples of carbodiimide compounds include N,N'-diisopropylcarbodiimide, N,N'-di(o-toluyl)carbodiimide, N,N'-dicyclohexylcarbodiimide, and N,N'-bis(2,6-diisopropylphenyl)carbodiimide. monofunctional carbodiimide compounds such as; bifunctional carbodiimide compounds such as cyclohexane-1,4-bis(methylene-t-butylcarbodiimide); polyfunctional carbodiimide compounds such as condensates of organic isocyanates; and the like.

Organic isocyanates include aromatic isocyanates, aliphatic isocyanates, and mixtures thereof. The organic group of the organic isocyanate may be either an aromatic organic group or an aliphatic organic group, or a combination of the aromatic organic group and the aliphatic organic group.
Specific examples of organic isocyanates include 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and hexamethylene. Organic diisocyanates such as diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate; isophorone isocyanate, phenyl isocyanate, cyclohexyl isocyanate, butyl organic monoisocyanates such as isocyanate and naphthyl isocyanate;

A carbodiimide compound may be used individually by 1 type, and may be used as a mixture of 2 or more types.
Among these, polyfunctional carbodiimide compounds are preferred as the carbodiimide compound. Here, the polyfunctional carbodiimide compound means a compound having two or more carbodiimide groups.

In addition, you may use a commercial item as a carbodiimide compound. Examples of commercially available products include Carbodilite (registered trademark) manufactured by Nisshinbo Chemical Co., Ltd. (eg, HMV-15CA, LA-1, and Stabaxol (registered trademark) manufactured by Rhein Chemie (eg, P, P-100, etc.).

The content of the carbodiimide compound may be 0.1% by mass to 10% by mass, 0.3% by mass to 8% by mass, or 0.5% by mass to 6% by mass. good.
Here, the content of the carbodiimide compound is a value including those in a state of being covalently bonded by reacting with other components such as a polyester thermoplastic elastomer.

(zinc cyanurate)
The resin layer may contain zinc cyanurate as another component. By including zinc cyanurate in the resin layer, there is an advantage that when the resin layer is applied as a coating layer for coating a metal wire such as a belt member of a tire, the adhesiveness and rust prevention effect are excellent.
When the resin layer contains zinc cyanurate, the zinc cyanurate content is preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass, with respect to the entire resin layer. is more preferable.

(other ingredients)
The resin layer may contain other components such as additives as long as the effects are not impaired. Other components include, for example, various fillers (eg, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weathering agents, and the like.

<Another rubber layer (third layer)>
In the composite according to this embodiment, if necessary, another rubber layer directly contacting the specific rubber layer may be provided on the surface of the specific rubber layer opposite to the resin layer.
The other rubber layer contains at least a diene rubber, and may contain other components as necessary, and may be a rubber layer having a composition different from that of the specific rubber layer. The other rubber layer may be a vulcanized layer of a rubber composition containing a diene rubber.
The other rubber layer preferably contains rubber as a main component. The rubber contains at least a diene rubber, and may further contain other rubbers as necessary. The preferred content of the diene rubber relative to the total amount of rubber is the same as the preferred content of the diene rubber in the specific rubber layer.
Further, specific examples of diene rubber, specific examples of other rubbers, and specific examples of components other than rubber are the same as those described in the specific rubber layer.

<Method for producing composite>
As a method for producing the composite of the present embodiment, for example, a laminate having a specific rubber composition as an unvulcanized specific rubber layer and a resin layer provided in direct contact with the unvulcanized specific rubber layer and a step of vulcanizing the unvulcanized specific rubber layer by heating the laminate.

The unvulcanized specific rubber layer can be obtained, for example, by kneading the materials constituting the specific rubber composition and molding into the desired shape. The kneading temperature for forming the unvulcanized specific rubber layer is, for example, in the range of 80° C. to 180° C. from the viewpoint of maintaining the unvulcanized state. Examples of the kneader include ordinary kneaders such as a mixing roll, a sigma rotary blade kneader, a Banbury mixer, a high-speed twin-screw continuous mixer, and a single-screw, twin-screw, or multi-screw extruder kneader. . Examples of molding methods include extrusion molding and roll molding.

The resin layer can be obtained, for example, by melt-kneading the material constituting the resin layer and molding it into a desired shape. The kneading temperature during the formation of the resin layer is, for example, in the range of Tm°C to (Tm+80)°C, where Tm°C is the melting point of the thermoplastic polyester elastomer. Further, when the resin layer contains another resin having a higher melting point than the polyester thermoplastic elastomer, the kneading temperature is preferably higher than the melting point of the other resin. The kneader used for melt-kneading is the same as the kneader used for obtaining the unvulcanized specific rubber layer. Examples of molding methods include injection molding, vacuum molding, pressure molding, and melt casting.

In the step of forming the laminate, the resin layer is brought into direct contact with the unvulcanized specific rubber layer.
In the present embodiment, since the specific rubber layer and the resin layer have the above-described structures, , high adhesiveness can be obtained even if they are brought into contact without processing such as surface treatment.
The vulcanization temperature in the step of vulcanizing the unvulcanized specific rubber layer is appropriately set according to the composition of the specific rubber layer, and is, for example, in the range of 110°C to 220°C. Further, the vulcanization time is, for example, 1 minute to 30 hours.

When manufacturing a composite having a specific rubber layer, a resin layer, and another rubber layer, for example, the specific unvulcanized rubber layer and the resin layer provided in direct contact with the specific unvulcanized rubber layer and a step of forming a laminate having another unvulcanized rubber layer provided on the opposite side of the resin layer in the specific unvulcanized rubber layer in direct contact with the specific unvulcanized rubber layer; and vulcanizing the unvulcanized specific rubber layer and the other unvulcanized rubber layer by heating the body to produce the composite. The other unvulcanized rubber layer can be obtained in the same manner as the specific unvulcanized rubber layer.

<Application of composite>
The composite according to the present embodiment is applied to various fields in which a member including a resin layer and a member including a rubber layer are used. Examples include fields such as golf balls, bellows, seismic isolation rubber, sealing materials, caulking materials, and bicycles.

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

Moreover, when the composite has a resin layer, a specific rubber layer, and another rubber layer, examples of combinations thereof include the following combinations.
- A combination of a belt member as a resin layer, a rubber sheet as a specific rubber layer, and at least one member selected from the group consisting of a tread and a tire frame member as another rubber layer.
- A combination of a bead member as a resin layer, a rubber sheet as a specific rubber layer, and a tire frame member as another rubber layer.
- A combination of a tire frame member as a resin layer, a rubber sheet as a specific rubber layer, and at least one member selected from the group consisting of a tread, a belt member, and a bead member as another rubber layer.
A combination of a belt cord as a resin layer, a rubber sheet as a specific rubber layer, and a cord covering layer as another rubber layer.
- A combination of a ply cord as a resin layer, a rubber sheet as a specific rubber layer, and a cord covering layer as another rubber layer.
- A combination of a bead wire as a resin layer, a rubber sheet as a specific rubber layer, and a wire coating layer as another rubber layer.

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

<First embodiment>
The tire of the first embodiment includes an annular tire frame member containing a resin, a belt member provided outside the tire frame member in the tire radial direction and containing a plurality of reinforcing cords and a covering resin covering the reinforcing cords, a belt A rubber sheet, which is a rubber member provided on the tire radially outer surface of the member in direct contact with the coating resin of the belt member, and a tread provided on the tire radially outer surface of the rubber sheet in direct contact with the rubber sheet. , has In the first embodiment, there is provided a composite having a belt member coating resin corresponding to the resin layer, a rubber sheet corresponding to the specific rubber layer, and a tread corresponding to the other rubber layer. Hereinafter, the rubber member corresponding to the specific rubber layer is also referred to as "specific rubber member". The tread may be a composite of multiple other rubber layers.
A tread corresponding to another rubber layer may be used instead of a tread corresponding to another rubber layer. It is good also as a specific rubber member provided by.

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

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

-Tire frame member-
The tire case 17 is made of, for example, a thermoplastic elastomer, which is an example of a resin material, and is formed in an annular shape in the tire circumferential direction.
The tire case 17 includes a pair of bead portions 14 spaced apart in the tire width direction, a pair of side portions 16 extending outward from the pair of bead portions 14 in the tire radial direction, and a pair of side portions. , and a crown portion 18 that connects 16 to each other. The bead portion 14 is a portion that contacts a rim (not shown). Further, the side portion 16 forms a side portion of the tire 10 and is gently curved so as to protrude outward in the tire width direction from the bead portion 14 toward the crown portion 18 .

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

Moreover, in this embodiment, the crown portion 18 has a substantially constant thickness. 18 A of outer peripheral surfaces in the crown part 18 of the tire case 17 may be formed flat in the cross section in the tire width direction, or may have a curved shape bulging outward in the tire radial direction. Note that the outer peripheral surface 18A of the crown portion 18 of the present embodiment is the outer periphery of the tire case 17 on which the belt member 12 is provided.

In addition, the tire case 17 forms a pair of annular tire halves 17H having one bead portion 14, one side portion 16, and a half-width crown portion 18, and these tire halves 17H face each other, It is formed by joining the ends of each half-width crown portion 18 to each other at the tire equatorial plane CL. The ends are joined together using, for example, a welding resin material 17A.

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

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

In addition, a reinforcing material (polymeric material, metal fiber, cord, nonwoven fabric, woven fabric, etc.) may be embedded in the tire case 17 .

Moreover, a coating layer 21 may be formed on the surface of the bead portion 14 at a portion in contact with a rim (not shown) to improve airtightness with the rim. Examples of the material of the coating layer 21 include a material such as rubber that is softer than the tire case 17 and has high weather resistance. The coating layer 21 is folded back from the inner surface of the bead portion 14 on the inner side in the tire width direction to the outer side in the tire width direction, and extends to the vicinity of the outer end portion of the belt member 12 in the tire width direction via the outer surface of the side portion 16 . may be provided as follows. Moreover, the extended end portion of the coating layer may be covered with a tread 30 which will be described later. However, if the bead portion 14 of the tire case 17 alone can ensure the sealing performance (airtightness) between the tire case 17 and the rim (not shown), the covering layer 21 may not be provided.
When the coating layer 21 contains rubber, the tire case 17 corresponds to a resin layer containing a polyester-based thermoplastic elastomer and an epoxy resin, and the coating layer 21 includes a diene-based rubber, carbon black, and an oil-modified novolac-type phenolic resin. A composite corresponding to a specific rubber layer, which is a vulcanized product of a specific rubber composition containing an amine curing agent, may also be used.

-Belt material-
Next, the belt member 12 will be explained.
The belt member 12 is joined to the tire case 17 by spirally winding the resin-coated cord 28 around the outer periphery of the tire case 17 in the tire circumferential direction. It is configured by being joined. The resin-coated cord 28 is configured by coating the reinforcing cord 24 with the coating resin 26.

The reinforcing cord 24 is composed of a monofilament (single wire) such as a metal fiber or an organic fiber, or a multifilament (twisted wire) obtained by twisting these fibers, and the coating resin 26 contains a polyester thermoplastic elastomer and an epoxy resin. It is composed of a resin material containing a resin that
Examples of the reinforcing cord 24 include a monofilament (single wire) made of a single metal cord and a multifilament (twisted wire) made by twisting a plurality of metal cords. multifilament is preferred. The number of multiple metal cords is, for example, 2 to 10, preferably 5 to 9.
From the viewpoint of achieving both resistance to internal pressure and weight reduction of the tire, the thickness of the reinforcing cords 24 is preferably 0.2 mm to 2 mm, more preferably 0.8 mm to 1.6 mm.

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

Although the belt member 12 shown in FIGS. 1 and 2 is configured by spirally winding and joining the resin-coated cord 28 to the outer peripheral surface of the tire case 17, the configuration is not limited to this. For example, it may be a belt member configured by winding a sheet-like integrated sheet of a plurality of reinforcing cords 24 and coating resin 26 around the outer peripheral surface of the tire case 17 .

-Rubber sheet and tread-
Next, the rubber sheet 11 (an example of the specific rubber member) and the tread 30 are described.
As shown in FIGS. 1 and 2 , the rubber sheet 11 is arranged on the outer side of the belt member 12 in the tire radial direction in direct contact with the belt member 12 , and the rubber sheet 11 is arranged on the outer side of the rubber sheet 11 in the tire radial direction in direct contact with the rubber sheet 11 to form a tread. 30 are placed.
The rubber sheet 11 is made of a rubber material that is a vulcanized product of a specific rubber composition containing rubber containing diene rubber, carbon black, an oil-modified novolac type phenolic resin, and an amine curing agent. Constructed of a rubber material containing rubber. The tread 30 may be a multi-layer body in which a plurality of layers of a rubber material containing diene rubber are laminated.
The rubber sheet 11 and the tread 30 are, for example, laminated on the belt member 12 on the tire case 17 in an unvulcanized state, and then vulcanized and bonded.
The thickness of the rubber sheet 11 is not particularly limited, and may be in the range of 0.1 mm to 100 mm, for example.

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

In FIGS. 1 and 2, the tread 30 is provided on the belt member 12 via the rubber sheet 11. However, the present invention is not limited to this. A tread, which is a vulcanized body of a resin composition containing a phenolic resin and an amine curing agent, may be provided in direct contact with the belt member 12 .

- tire manufacturing method -
Next, a method for manufacturing the tire 10 of this embodiment will be described. First, a set of tire halves 17H including the bead core 20 is formed by injection molding using a thermoplastic material.
Next, the pair of tire halves 17H are opposed to each other, the ends of the portions to be crown portions 18 are butted against each other, and the molten welding resin material 17A is adhered to the butted portions to join the pair of tire halves 17H. do. Thus, an annular tire case 17 is formed.

Next, the process of winding the resin-coated cord 28 around the outer circumference of the tire case 17 will be described. Specifically, while feeding the resin-coated cord 28 toward the outer peripheral surface 18A of the crown portion 18, the thermoplastic resin of the resin-coated cord 28 and the outer peripheral surface 18A of the crown portion 18 are heated and melted by blowing hot air. Then, the resin-coated cord 28 in which the thermoplastic resin is melted is pressed against the outer peripheral surface 18A of the crown portion 18 in the melted state to be joined, and solidified by cooling.
In this manner, a layer of the resin-coated cord 28 is formed on the outer circumference of the tire case 17 , more specifically, on the outer circumference of the crown portion 18 to form the belt member 12 .
Note that an adhesive layer may be provided between the tire case 17 and the belt member 12 as necessary.

Next, the rubber sheet 11 and the tread 30 are formed on the outer peripheral surface of the belt member 12 .
Specifically, first, an unvulcanized rubber sheet is wound around the outer peripheral surface of the belt member 12 . Next, an unvulcanized tread is wound around the outer peripheral surface of the unvulcanized rubber sheet. The winding of the unvulcanized rubber sheet and the winding of the unvulcanized tread may be performed while rotating the tire case 17 provided with the belt member 12 .
Then, the belt member 12, the unvulcanized rubber sheet, and the unvulcanized tread layered tire case 17 (that is, raw tire) are vulcanized. Specifically, for example, by housing the tire case 17 in a vulcanization can or a mold and heating it, the unvulcanized rubber sheet is vulcanized to form the rubber sheet 11 and the unvulcanized tread. is vulcanized to form the tread 30 . The vulcanization temperature is, for example, 110° C. to 220° C., and the vulcanization time is, for example, 1 minute to 30 hours.
As described above, the tire 10 of the first embodiment is obtained.

<Second embodiment>
The tire of the second embodiment includes an annular tire frame member containing rubber, a belt member provided outside the tire frame member in the tire radial direction and containing a plurality of reinforcing cords and a covering resin covering the reinforcing cords, and a belt. A tread provided on the tire radially outer surface of the member, and a specific rubber member provided between the tire skeleton member and the belt member and between the belt member and the tread in direct contact with the tire skeleton member and the tread. and a rubber sheet. In the second embodiment, the coating resin of the belt member corresponding to the resin layer, the rubber sheet corresponding to the specific rubber layer, the tire frame member having the rubber layer corresponding to the other rubber layer, and the other and a tread corresponding to a rubber layer. The tread may be a composite of multiple other rubber layers.
Also in the second embodiment, a tread corresponding to another rubber layer may be used instead of a tread corresponding to another rubber layer, and the tread corresponding to the specific rubber layer may be attached to the belt without a rubber sheet. A specific rubber member provided in direct contact with the coating resin of the member may be used. Further, instead of a tire skeleton member having a rubber layer corresponding to another rubber layer, a tire skeleton member having a rubber layer corresponding to another rubber layer may be used, and a tire having a rubber layer corresponding to the specific rubber layer The skeleton member may be a specific rubber member in which the rubber layer is in direct contact with the coating resin of the belt member without a rubber sheet interposed therebetween.

A second embodiment will be described below with reference to FIG.
FIG. 3 is a cross-sectional view along the tire width direction showing the configuration of the tire according to the second embodiment. In FIG. 3, the same reference numerals are assigned to members that are common to other drawings, and description thereof is omitted.
As shown in FIG. 3, a tire 80 according to the second embodiment includes a tire case 94, which is an example of an annular tire frame member configured to include a rubber material containing rubber, a belt member 12, a specific rubber It has a rubber sheet 11 which is an example of a member, and a tread 30 .
Since the belt member 12, the rubber sheet 11, and the tread 30 are the same as those in the first embodiment, description thereof is omitted.

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

The carcass ply 82 is formed by coating a plurality of cords (not shown) extending in the radial direction of the pneumatic tire 80 with coating rubber (not shown). Examples of the cord material of the carcass ply 82 include PET, but other conventionally known materials may be used. The coating rubber is a rubber material containing diene rubber, and constitutes a coating layer (not shown) corresponding to another rubber layer.

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

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

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

In FIG. 3, the belt member 12 is provided outside the carcass 86 in the tire radial direction via the rubber sheet 11. However, the belt member 12 is not limited to this. A belt member 12 is provided in direct contact with a carcass composed of a carcass ply formed by coating cords with coating rubber, which is a vulcanized body of a specific rubber composition containing a modified novolak-type phenolic resin and an amine curing agent. good too.
In FIG. 3, the tread 30 corresponding to another rubber layer is arranged on the outer side of the belt member 12 in the tire radial direction with the rubber sheet 11 interposed therebetween. A tread, which is a vulcanized body of a specific rubber composition containing rubber, carbon black, an oil-modified novolak-type phenolic resin, and an amine curing agent, may be provided in direct contact with the belt member 12 .
The tread 30 is formed with grooves 30A for drainage. Conventionally known patterns are used for the grooves 30A of the tread 30. As shown in FIG.

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

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

Next, the belt member 12 in which the resin-coated cords 28 are cooled and the coating resin 26 is solidified is removed from the belt forming drum. Then, after attaching the unvulcanized rubber sheet 11 to the inner peripheral surface of the removed belt member 12, the belt member 12 is arranged radially outward of the unvulcanized tire case 94 on the tire building drum. . After that, the tire case 94 is expanded, and the outer peripheral surface of the tire case 94 , in other words, the outer peripheral surface of the carcass 86 is pressed against the inner peripheral surface of the belt member 12 .
Finally, after attaching the unvulcanized rubber sheet 11 to the outer peripheral surface of the belt member 12, the unvulcanized tread 30 is attached on the unvulcanized rubber sheet 11 to complete the raw tire.
The raw tire manufactured in this way is vulcanized and molded in a vulcanizing molding mold to complete the tire 80 .

<Third Embodiment>
The tire of the third embodiment includes an annular tire frame member containing a resin, a belt member provided outside the tire frame member in the tire radial direction and containing a plurality of reinforcing cords and a covering resin covering the reinforcing cords, a belt A rubber sheet provided on the tire radially outer surface of the member in direct contact with the covering resin of the belt member, a tread provided on the tire radially outer surface of the rubber sheet in direct contact with the rubber sheet, and a tire frame member. and a side rubber that is a specific rubber member provided on the outside in the tire width direction of the. The third embodiment has a composite body including a tire frame member corresponding to the resin layer and a side rubber corresponding to the specific rubber layer.
In the third embodiment, the side rubber corresponding to the specific rubber layer is provided in direct contact with the tire frame member. may be provided with a side rubber corresponding to .
In addition, in the third embodiment, the coating resin of the belt member also corresponds to the resin layer, the rubber sheet corresponds to the specific rubber layer, and the tread corresponds to the other rubber layer, but the present invention is limited to these. isn't it. Also, the tread may be a multilayer body of a plurality of other rubber layers.

FIG. 4 is a cross-sectional view along the tire width direction showing the configuration of the tire according to the third embodiment. In FIG. 4, the same reference numerals are assigned to members that are common to other drawings, and description thereof is omitted.
As shown in FIG. 4, a tire 110 according to the third embodiment includes a tire case 17 that is an annular tire frame member made of a resin material containing resin, and a A belt member 12 and a rubber sheet provided on a region of the tire radially outer surface of the tire case 17 where the belt member 12 is not provided, and on the tire radially outer surface and the tire width direction outer surface of the belt member 12. 11, a tread 30 provided on the outer surface of the rubber sheet 11 in the tire radial direction, and a side rubber 13 which is an example of a specific rubber member provided on the outer surface of the tire case 17 in the tire width direction. .
Since the tire case 17, the belt member 12, the rubber sheet 11, and the tread 30 are the same as those in the first embodiment, description thereof is omitted. The side rubber 13 is made of a rubber material that is a vulcanizate of a specific rubber composition containing rubber containing diene rubber, carbon black, an oil-modified novolac phenolic resin, and an amine curing agent.

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

<Fourth Embodiment>
The fourth embodiment is an example of a configuration in which the composite is provided in the bead portion of an annular tire frame member containing rubber. Specifically, a carcass having a bead core in which a bead wire is coated with a coating resin, a body portion located between the bead cores, and a folded portion folded back from the inside to the outside around the bead core, the bead core and the body portion. A resin bead filler provided between and the folded portion, a rubber sheet as a specific rubber member provided around the bead core and the bead filler, and another rubber member provided around the rubber sheet , constitute a tire frame member. That is, in the fourth embodiment, the bead core coating resin and bead filler corresponding to the resin layer, the rubber sheet corresponding to the specific rubber layer, and the other rubber member corresponding to the other rubber layer are provided. have a complex.
In the fourth embodiment, another rubber member is provided around the bead core and the bead filler via a rubber sheet corresponding to the specific rubber layer. Another rubber member may be a specific rubber member provided in direct contact with the bead core and the bead filler without the rubber sheet interposed therebetween.
Moreover, in the fourth embodiment, both the bead core and the bead filler have a resin layer, but at least one of the bead core and the bead filler may have a resin layer. For example, when the bead filler is made of rubber, the bead filler corresponding to the other rubber layer is provided around the coating resin of the bead core corresponding to the resin layer via a rubber sheet corresponding to the specific rubber layer. Alternatively, a bead filler corresponding to the specific rubber layer may be provided in direct contact with the coating resin of the bead core corresponding to the resin layer.

FIG. 5 is an enlarged sectional view of the bead portion of the tire according to the fourth embodiment. In FIG. 5, the same reference numerals are assigned to members that are common to other drawings, and description thereof is omitted.
As shown in FIG. 5, the bead portion 14 of the tire according to the fourth embodiment includes a rubber member 91, a resin bead filler 89, a bead core 20, and a rubber sheet 11 surrounding the bead filler 89 and the bead core 20. and a carcass 86.
In the bead portion 14 shown in FIG. 5, the bead core 20 and the bead filler 89 are embedded in the rubber member 91, and the bead core 20 and the bead filler 89 form an integrated core/filler member 50. A rubber sheet 11 is provided around it. However, the bead core 20 and the bead filler 89 may be separate bodies.

As shown in FIG. 5, each of the bead cores 20 includes a bead wire bundle 62 and a coating layer 65 that surrounds the bead wire bundle 62 and is made of a resin material when viewed in cross section in the tire width direction. have.
In the example of FIG. 5 , the bead filler 89 is formed integrally with the coating layer 65 of the bead core 20 and made of the same resin material as the coating layer 65 . However, the resin material forming the bead filler 89 may be different from the covering layer 65 of the bead core 20 . Moreover, the resin material forming the bead filler 89 may be different for each portion of the bead filler 89 .

In the example of FIG. 5 , the bead wire bundle 62 of the bead core 20 simply refers to a configuration in which a plurality of cross sections of the bead wires constituting the bead core 20 appear when viewed in the cross section in the tire width direction. The actual number of bead wires used may be one or more. That is, the bead wire bundle 62 may be configured by winding one bead wire a plurality of times in the tire circumferential direction, or by winding a plurality of bead wires one or more times in the tire circumferential direction. It may be configured by winding over.
The bead wire can be of any known material, for example steel cord. The steel cords may consist, for example, of steel monofilaments or strands. Organic fibers, carbon fibers, and the like can also be used.

The coating layer 65 of the bead core 20 continuously extends along the tire circumferential direction, and in at least a part of the tire circumferential direction, the bead wire bundle 62 of the bead core 20 when viewed in cross section in the tire width direction. is configured in an annular shape so as to surround the entire circumference of the The covering layer 65 does not have to be ring-shaped when viewed in cross section in the tire width direction in a part in the tire circumferential direction, and may be, for example, C-shaped.
In this example, each bead wire is coated with a coating resin 63 made of a resin material inside the annular shape formed by the coating layer 65 when viewed in a cross section in the tire width direction. In other words, the gap region between the coating layer 65 and each bead wire is filled with the coating resin 63 .
In this example, the resin material forming the coating resin 63 is different from the resin material forming the coating layer 65 . However, the resin material forming the coating resin 63 may be the same as the resin material forming the coating layer 65 .
In this example, both the coating layer 65 of the bead core 20 and the bead filler 89 are made of a resin material, but at least one of them may be made of a resin material. That is, when the coating layer 65 of the bead core 20 is made of a resin material, the bead filler 89 may be made of rubber, and when the bead filler 89 is made of resin, the coating layer 65 is made of a rubber material. may be
The present invention is not limited to this example, and each bead wire may be coated with a coating rubber made of rubber instead of the coating resin 63 inside the annular shape formed by the coating layer 65 when viewed in the cross section in the tire width direction. good. In other words, the gap region between the coating layer 65 and each bead wire may be filled with the coating rubber.

The tire of this embodiment is manufactured in the same manner as the tire of the second embodiment described above.
In this embodiment, the core-filler member 50 obtained by integrally molding the bead filler 89 and the bead core 20 is used. In this embodiment, after an unvulcanized rubber sheet is attached around the core/filler member 50, an unvulcanized rubber member 91 is attached to form an unvulcanized tire case. Then, a green tire obtained by providing a belt member and an unvulcanized tread as necessary is vulcanized to obtain a tire.

An example of a method for manufacturing the core-filler member 50 will be described below.
The manufacturing method of the core/filler member 50 includes, for example, a ring forming process, an injection molding process, and a cooling process.

In the annular body forming step, a strip member formed by coating one or more bead wires with a coating resin 63 is wound to form an annular body. In the bead core 20 shown in FIG. 5, for example, a strip member formed by coating three bead wires with a coating resin 63 is spirally wound and stacked in three layers.
In this example, in the annular body forming step, the outer peripheral side of the bead wire is coated with a molten coating resin 63 and solidified by cooling to form the strip member. The annular body can be formed by winding and tiering the strip member. This can be done by solidifying the melted coating resin 63 . Alternatively, the tiers can be joined together by adhering them with an adhesive or the like.

Subsequent to the annular body forming process, in the injection molding process, the annular body formed in the annular body forming process is coated with a resin material to form the coating layer 65 and the bead filler 89 integrated with the coating layer 65. .

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

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

The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these descriptions. In addition, "part" represents a mass standard unless otherwise specified.

<Production of unvulcanized rubber layer>
Among the components shown in Tables 1 and 2, the vulcanization accelerator and components other than the vulcanization agent are mixed and stirred at 110° C. for 3 minutes in Laboplastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and then the vulcanization accelerator is added. and a vulcanizing agent were added and stirred at 90°C for 1.5 minutes. Then, rubbers 1 to 8, which are unvulcanized rubber sheets having a thickness of 2.5 mm, were obtained by roll forming.

<Preparation of resin layer>
The components shown in Tables 3 and 4 are extruded at 230 ° C. to 250 ° C. with a twin screw extruder (manufactured by Technobell Co., Ltd., product name: KZW31TW-45HG, screw diameter 30 mm, L / D = 45) at a shaft rotation speed of 100 rpm. The mixture was kneaded at a rate of 10 kg/h, and injection molded to obtain Resins 1 to 9, which are resin sheets with a thickness of 2 mm.

The numbers in the table mean "addition amount (parts by mass)". Blanks in Tables 1 to 4 mean that the corresponding component is not included.
The details of each component shown in Tables 1 to 4 are as follows.
・Diene rubber 1: natural rubber (TSR20)
・Diene rubber 2: Synthetic isoprene rubber (manufactured by JSR Corporation, product name: IR2200)
・ Diene rubber 3: Butadiene rubber (manufactured by JSR Corporation, product name: BR01)
Carbon black: N330 carbon black (Asahi Carbon Co., Ltd., product name: Asahi #70K, BET method, nitrogen adsorption specific surface area: 71 m ² /g)

・ Oil: Process oil (manufactured by ENEOS, product name: process oil)
Fatty acid: stearic acid Tackifier 1: Alkylphenol resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: Durez19900)
- Tackifier 2: Butylphenol acetylene condensate resin (manufactured by BASF, product name: Koresin)
・ Phenolic resin 1: unmodified novolak phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: Sumilite Resin PR-50235)
・ Phenolic resin 2: Tall oil-modified novolak phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: Sumilite Resin PR-51587)
・ Phenolic resin 3: cashew oil-modified novolak phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: Sumilite Resin PR-55886)
・ Amine-based curing agent: hexamethylenetetramine (manufactured by Sanshin Chemical Industry Co., Ltd., product name: Suncellar HT)
・Metal oxide: Zinc white ・Vulcanizing agent: Sulfur ・Anti-scorch agent: N-cyclohexylthiophthalimide (manufactured by Toray Industries, Inc., product name: retarder CTP)
The anti-aging agent and the vulcanization accelerator were used by appropriately combining the above-described known ones.

・TPC1: Polyester-based thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 4767N)
・TPC2: Polyester-based thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 4777N)
・TPC3: Polyester-based thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 5557)
・TPC4: Polyester-based thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 5577)
・TPC5: Polyester-based thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 6347)
・PBT1: Polybutylene terephthalate (manufactured by Toray Industries, Inc., product name: TORAYCON 1401X04)
・PBT2: Polybutylene terephthalate (manufactured by Toray Industries, Inc., product name: TORAYCON 1401X06)

・ Epoxy resin 1: dicyclopentadiene type epoxy resin (containing less than 20% bisphenol type epoxy resin) (manufactured by Nippon Kayaku Co., Ltd., product name: CER-1000-L, epoxy equivalent: 226 g / eq)
・ Epoxy resin 2: biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name: YL6677, epoxy equivalent: 162 g / eq)
・ Epoxy resin 3: dicyclopentadiene type epoxy resin (manufactured by Nippon Kagaku Co., Ltd., product name: XD-1000, epoxy equivalent: 252 g / eq)
- Zinc cyanurate: (Nissan Chemical Co., Ltd., "Starfine F-10")
・ Carbodiimide: Carbodiimide compound (manufactured by Nisshinbo Chemical Co., Ltd., product name: Carbodilite HMV-15CA)

[Examples 1 to 10, Comparative Examples 1 to 6]
<Preparation of test piece>
Using the obtained resin sheet and unvulcanized rubber sheet, the resin sheet, the unvulcanized rubber sheet ("rubber sheet" in the table), and the resin sheet are laminated in this order so as to be in contact with each other. Vulcanization was performed at the vulcanization temperatures and vulcanization times shown in Tables 5 to 7 to obtain test pieces.
The content of carbon black with respect to 100 parts by mass of rubber in the rubber sheet of the obtained test piece (“CB amount (parts by mass)” in the table), the content of oil-modified novolak-type phenolic resin with respect to 100 parts by mass of rubber (in the table "PH amount (parts by mass)" of ), content of amine curing agent per 100 parts by mass of rubber ("curing agent amount (parts by mass") in the table), and content of polyester thermoplastic elastomer in the entire resin sheet Tables 5 to 7 show the ratio (“TPC amount (mass%)” in the table) and the content of epoxy resin (“EP amount (mass%)” in the table).

<Evaluation of adhesive force>
Using the test piece obtained in each example, with a precision universal testing machine (Autograph AG-X 5kN, manufactured by Shimadzu Corporation), in an environment of 25 ° C., at a tensile speed of 100 mm / min with one resin sheet A peel test was performed by pulling the other resin sheet at 180 degrees, and the average value in the stroke range of 20 mm to 70 mm, in which the peel resistance is relatively stable, was determined as the peel resistance (unit: N/25 mm). The results and fracture locations are shown in Tables 5 to 7 below. In the table, "base material/interface" indicates that fracture occurred at both the base material and the interface.

As can be seen from the evaluation results shown in Tables 5 to 7, this example has a higher peel resistance and is superior in adhesiveness between the rubber layer and the resin layer as compared with the comparative example.

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

Claims (10)

a first layer, which is a vulcanizate of a rubber composition containing rubber containing a diene rubber, carbon black, an oil-modified novolak-type phenolic resin, and an amine-based curing agent;
a second layer which is provided in direct contact with the first layer and is a resin layer containing a resin containing a thermoplastic polyester elastomer and an epoxy resin;
A resin-rubber composite having 2. The resin-rubber composite according to claim 1, wherein a content of said polyester thermoplastic elastomer is 50% by mass or more with respect to said second layer as a whole. 3. The resin-rubber composite according to claim 1, wherein the content of said epoxy resin is 3% by mass or more with respect to said entire second layer. The resin-rubber composite according to any one of claims 1 to 3, wherein the content of said oil-modified novolak-type phenolic resin is 3 parts by mass or more with respect to 100 parts by mass of said rubber. The resin-rubber composite according to any one of claims 1 to 4, wherein the content of said carbon black is 25 parts by mass to 80 parts by mass with respect to 100 parts by mass of said rubber. Claims 1 to 1, further comprising a third layer that is in direct contact with the first layer, is provided on the surface of the first layer opposite to the second layer, and is a rubber layer containing a diene rubber. The resin-rubber composite according to claim 5. A tire comprising the resin-rubber composite according to any one of claims 1 to 6. an annular tire frame member;
a belt member provided outside the tire frame member in the tire radial direction and including the second layer;
a rubber member provided outside the belt member in the tire radial direction and including the first layer;
8. A tire according to claim 7, having a an annular tire frame member including the second layer;
a rubber member provided on at least one of the tire width direction outer side and the tire width direction inner side of the tire frame member and including the first layer;
8. A tire according to claim 7, having a Having an annular tire frame member including the first layer,
The tire according to claim 7, wherein the bead portion of the tire frame member includes at least one of a bead core including the second layer and a bead filler including the second layer.

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