Resin-rubber composite and tire

Abstract

To provide a resin-rubber composite excellent in adhesiveness at 90°C 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 rubber layer comprising a rubber containing an epoxidized diene rubber, and carbon black; 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 a phenolic resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin-rubber composite and a tire. [Background technology]

[0002] In recent years, in the field of tires and the like, the use of components including a resin layer as a part of tire components has been considered from the viewpoints of weight reduction, ease of molding, recycling, etc. For example, Patent Document 1 proposes a tire that uses a polyamide-based thermoplastic elastomer, which is a thermoplastic polymer material, as a resin. On the other hand, when a member including a resin layer is used as a part of a tire member, the resin layer may be disposed at a position where it contacts a rubber layer of another member, but due to differences in materials, it is not easy to improve the adhesion between the resin layer and the rubber layer. Therefore, for example, an organic solvent-based adhesive layer is provided between the resin layer and the rubber layer to prevent peeling at the interface between the resin layer and the rubber layer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2012-46030 A Summary of the Invention [Problem to be solved by the invention]

[0004] As mentioned above, when using an organic solvent-based adhesive, the solvent needs to be evaporated after the coating is formed, and the drying process takes time. In addition, the installation of an exhaust system may be required from the viewpoint of the working environment, and there is room for further improvement in terms of simplifying the manufacturing process and reducing costs. 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, it is desirable to obtain excellent adhesion between the two even when the two are in direct contact without an adhesive. In particular, in products such as tires in which the material is subjected to repeated input, the temperature may become high during use, and it is desirable to maintain excellent adhesion even at high temperatures.

[0005] In view of the above circumstances, an object of the present invention is to provide a resin-rubber composite having excellent adhesion at 90°C between a resin layer and a rubber layer directly in contact with the resin layer, and a tire having the resin-rubber composite. [Means for solving the problem]

[0006] Specific means for solving the above problems include the following aspects. <1> A first layer is a rubber layer including a rubber containing an epoxidized diene rubber and carbon black; a second layer provided in direct contact with the first layer and being a resin layer including a resin containing a polyester-based thermoplastic elastomer and a phenolic resin; A resin-rubber composite having the above structure. <2> The content of the carbon black is 25 parts by mass to 65 parts by mass relative to 100 parts by mass of the rubber. <1> The resin-rubber composite according to claim 1. <3> The content of the polyester-based thermoplastic elastomer is 50% by mass or more based on the entire second layer. <1> or <2> The resin-rubber composite according to claim 1. <4> The content of the phenol resin is 3% by mass or more based on the entire second layer. <1> ~ <3> 13. The resin-rubber composite according to claim 12 . <5> The epoxidation ratio in the rubber is 30% to 60%. <1> ~ <4> 13. The resin-rubber composite according to claim 12 . <6> the second layer comprises a carbodiimide compound; <1> ~ <5> 13. The resin-rubber composite according to claim 12 . <7> The third layer is a rubber layer containing a diene rubber, and is directly in contact with the first layer and provided on a surface of the first layer opposite to the second layer. <1> ~ <6> 13. The resin-rubber composite according to claim 12 . <8> <1> ~ <7> A tire having the resin-rubber composite according to any one of claims 1 to 5. <9> An annular tire frame member; a belt member provided on the tire radial direction outer side of the tire frame member and including the second layer; a rubber member provided on the outer side of the belt member in the tire radial direction and including the first layer; having <8> A tire as described in. <10> an annular tire frame member including the second layer; a rubber member provided on at least one of an outer side and an inner side in the tire width direction of the tire frame member, the rubber member including the first layer; having <8> A tire as described in. <11> a tire frame member having an annular shape including the first layer, The bead portion in the tire frame member includes at least one of a bead core including the second layer and a bead filler including the second layer. <8> A tire as described in. Effect of the Invention

[0007] According to the present invention, it is possible to provide a resin-rubber composite having excellent adhesion at 90° C. between a resin layer and a rubber layer directly in contact with the resin layer, and a tire having the resin-rubber composite. [Brief description of the drawings]

[0008] [Figure 1] 1 is a perspective view showing a cross section of a portion of a tire according to a first embodiment. [Diagram 2] 1 is a cross-sectional view taken along the tire width direction, showing a configuration of a tire according to a first embodiment. [Diagram 3] FIG. 11 is a cross-sectional view taken along the tire width direction, showing the configuration of a tire according to a second embodiment. [Figure 4]FIG. 11 is a cross-sectional view taken along the tire width direction, showing the configuration of a tire according to a third embodiment. [Diagram 5] FIG. 11 is an enlarged cross-sectional view of a bead portion of a tire according to a fourth embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Specific embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments and can be modified as appropriate within the scope of the object of the present invention.

[0010] In this specification, the term "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 expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the process achieves its purpose. In this specification, the amount of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified. In this specification, unless otherwise specified, the term "major component" refers to the component that has the highest content by mass in a mixture.

[0011] In addition, in this specification, "thermoplastic resin" refers to a polymer compound that softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubber-like elasticity. In this specification, the term "thermoplastic elastomer" refers to a copolymer having a hard segment and a soft segment. Specific examples of thermoplastic elastomers include copolymers having a polymer that is crystalline and has a high melting point or a hard segment with high cohesive strength, and a polymer that is amorphous and has a soft segment with a low glass transition temperature. Examples of thermoplastic elastomers include materials that soften and flow with increasing temperature, become relatively hard and strong when cooled, and have rubber-like elasticity. The hard segment may be, for example, a segment having a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure that enables intermolecular packing by intermolecular hydrogen bonds or π-π interactions, etc. The soft segment may be, for example, a segment having a long-chain group (e.g., a long-chain alkylene group) in the main chain, with a high degree of freedom in molecular rotation and stretchability.

[0012] [Resin-rubber composite] The resin-rubber composite (hereinafter also referred to as "composite") according to this embodiment has a first layer which is a rubber layer containing a rubber containing an epoxidized diene-based rubber and carbon black, and a second layer which is a resin layer provided in direct contact with the first layer and contains a resin containing a polyester-based thermoplastic elastomer and a phenolic resin. Hereinafter, the first layer will also be referred to as an “epoxy rubber layer,” and the second layer will also be referred to as a “resin layer.” In addition, a rubber member including the first layer will also be referred to as an “epoxy rubber member.”

[0013] As described above, in a composite in which a resin layer is disposed at a position where it contacts a rubber layer, it is not easy to increase the adhesion between the resin layer and the rubber layer due to the difference in materials used. On the other hand, in a method in which an organic solvent-based adhesive layer is provided between the resin layer and the rubber layer, although the adhesion is increased, the solvent needs to be volatilized after the coating film is formed, and therefore there is room for improvement in terms of simplifying the manufacturing process and reducing costs. Therefore, in a composite body in which a resin layer and a rubber layer are arranged so as to be in contact with each other, it is desirable to obtain excellent adhesion between the two even when the two are in direct contact with each other without the use of an adhesive. Furthermore, for example, when the composite is applied to tires, it often generates heat naturally due to repeated strain during driving and reaches temperatures of around 90°C, and it is desirable to obtain excellent adhesion even at 90°C.

[0014] In contrast, in the composite of the present embodiment, the rubber layer directly in contact with the resin layer is an epoxy rubber layer containing a rubber containing an epoxidized diene rubber and carbon black, and the resin layer contains a resin containing a polyester thermoplastic elastomer and a phenolic resin. Therefore, the adhesiveness between the resin layer and the rubber layer directly in contact with the resin layer at 90°C is excellent. The reason for this is unclear, but is presumed to be as follows. At the interface between the resin layer and the epoxy rubber layer, the epoxy group of the epoxidized diene rubber contained in the epoxy rubber layer reacts with the carboxy group of the polyester thermoplastic elastomer contained in the resin layer to form a covalent bond. The epoxy group of the epoxidized diene rubber then undergoes ring-opening at high temperatures such as vulcanization temperature, and a part of the opened epoxy group reacts with a part of the hydroxyl group of the phenolic resin contained in the resin layer to form a covalent bond, while another part of the hydroxyl group of the phenolic resin reacts with the carboxyl group of the polyester thermoplastic elastomer to form a covalent bond. In addition, since the epoxy rubber layer contains carbon black, the reinforcing effect of the carbon black of the epoxidized diene rubber can be expressed without impairing the reactivity of the epoxy group, so that the resin layer and the rubber layer are more firmly bonded, and it is presumed that the adhesiveness is excellent even at a high temperature of 90°C.

[0015] In the present embodiment, since the resin layer and the rubber layer directly in contact with the resin layer have excellent adhesion as described above, there is no need to provide an organic solvent-based adhesive layer between the resin layer and the rubber layer, and a composite with excellent adhesion between the resin layer and the rubber layer can be obtained while improving workability.

[0016] As described above, the composite of the present embodiment has at least an epoxy rubber layer and a resin layer in direct contact with the epoxy rubber layer, and may further have other layers as necessary. Examples of the other layers include a third layer (hereinafter also referred to as a "diene rubber layer") that is a rubber layer containing a diene rubber and is provided on the surface of the epoxy rubber layer opposite to the resin layer and in direct contact with the epoxy rubber layer. Each layer constituting the composite body according to this embodiment will be described below.

[0017] <Epoxy rubber layer> The composite body according to this embodiment has an epoxy rubber layer as a rubber layer that is in direct contact with the resin layer. The epoxy rubber layer contains at least a rubber containing an epoxidized diene rubber and carbon black, and may contain other components as necessary. The epoxy rubber layer may be a layer that is a vulcanizate of a rubber composition containing a rubber containing an epoxidized diene rubber and carbon black. In other words, the epoxy rubber layer may be a vulcanizate layer in which an unvulcanized epoxy rubber layer that is a rubber composition containing a rubber containing an epoxidized diene rubber and carbon black is vulcanized in a state of being in direct contact with a resin layer. The rubber composition may also contain other components as necessary.

[0018] (Rubber) The epoxy rubber layer preferably contains rubber as a main component. The content of the rubber in the total amount of the epoxy rubber layer is, for example, 50% by mass or more, may be 55% by mass or more, or may be 60% by mass or more, and may be 80% by mass or less.

[0019] The rubber contains at least an epoxidized diene rubber, and may further contain other rubbers as necessary. From the viewpoint of improving adhesion to the resin layer, the content of the epoxidized diene rubber is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass% based on the total amount of rubber.

[0020] Here, the epoxidized diene rubber is a rubber in which some of the carbon-carbon double bonds contained in the diene rubber have been epoxidized, and the diene rubber contains carbon-carbon double bonds in the main chain of the rubber. Examples of diene rubbers include natural rubber (NR) and synthetic rubbers such as polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), isoprene rubber (IR), and polychloroprene rubber (CR). The epoxidized diene rubber may be used alone or in a mixture of two or more kinds. Of these, the epoxidized diene rubber preferably contains epoxidized natural rubber obtained by epoxidizing natural rubber.

[0021] When the rubber contains other rubbers, the type of the other rubbers is not particularly limited. Examples of the other rubber include non-epoxidized diene rubber and non-diene rubber. Among these, the other rubber is preferably non-epoxidized diene rubber, and more preferably non-epoxidized natural rubber, from the viewpoint of improving adhesion to the resin layer. The other rubber may be used alone or in combination of two or more kinds.

[0022] The epoxidation ratio of the rubber contained in the epoxy rubber layer is preferably 30% or more, more preferably 35% or more, and even more preferably 40% or more from the viewpoint of improving adhesion to the resin layer. Also, the epoxidation ratio of the rubber contained in the epoxidized rubber layer is preferably 60% or less, more preferably 55% or less, and even more preferably 50% or less from the viewpoints of suppressing heat generation in the epoxy rubber layer, suppressing low-temperature embrittlement, and improving fatigue durability against mechanical input, etc. The epoxidation ratio of the rubber contained in the epoxidized rubber layer is preferably 30% to 60%, more preferably 35% to 55%, and further preferably 40% to 50%.

[0023] Here, the epoxidation ratio refers to a value represented by the following formula (1), where Ep is the number of epoxy groups contained in the entire rubber, and En is the number of double bonds remaining that have not been epoxidized among the carbon-carbon double bonds contained in the entire rubber. Equation (1): Epoxidation ratio (%) = (Ep / (Ep+En)) x 100 When the rubber contained in the epoxy rubber layer contains a rubber other than the epoxidized diene rubber, the number of double bonds En is a value including the number of double bonds in the other rubber.

[0024] The epoxidation ratio of the rubber contained in the epoxy rubber layer of the composite can be determined, for example, by measuring a test piece of the epoxy rubber layer cut out from the composite by Fourier transform nuclear magnetic resonance spectroscopy.

[0025] (Carbon Black) The carbon black contained in the epoxy rubber layer 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, thermal black obtained by the thermal method, etc. Carbon black may be used alone or in combination of two or more kinds. From the viewpoint of reinforcing the epoxy rubber layer and improving adhesion to the resin layer, the content of carbon black in the epoxy rubber layer is preferably 25 parts by mass to 65 parts by mass, more preferably 30 parts by mass to 60 parts by mass, and even more preferably 35 parts by mass to 55 parts by mass, per 100 parts by mass of rubber in the epoxy rubber layer.

[0026] The nitrogen adsorption surface area of ​​the carbon black is not particularly limited, but from the viewpoint of improving the adhesion to the resin layer, it is preferable to use a surface area of ​​20 m 2 / g or more, and 25m 2 / g or more is more preferable, and 30m 2 The upper limit of the nitrogen adsorption surface area of ​​carbon black is preferably 250 m / g or more. 2 / g or less. The nitrogen adsorption surface area of ​​carbon black is measured by the BET method in accordance with ASTM D3037-88. 2 It can be determined by measuring using gas.

[0027] (Other Ingredients) Examples of other components contained in the epoxy rubber layer include reinforcing materials other than carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, oils other than process oils, antioxidants, tackifiers, scorch inhibitors, etc. These may be used alone or in combination of two or more.

[0028] Examples of reinforcing materials other than carbon black include silica. When silica is used in addition to carbon black as a reinforcing material, a silane coupling agent may be further used to improve the dispersibility of the silica. When a reinforcing material such as silica is used as another component, the total content of the reinforcing materials including carbon black and silica is, from the viewpoint of the reinforcing property of the rubber layer and from the viewpoint of making it difficult for heat to be generated when repeated strain occurs, preferably 25 parts by mass to 65 parts by mass, more preferably 30 parts by mass to 60 parts by mass, and even more preferably 35 parts by mass to 55 parts by mass, per 100 parts by mass of rubber contained in the epoxy rubber layer.

[0029] As the vulcanizing agent, a known vulcanizing agent, for example, sulfur, an organic peroxide, a resin vulcanizing agent, etc., is used. Among them, it is preferable to use sulfur as the vulcanizing agent. As the vulcanization accelerator, known vulcanization accelerators such as aldehydes, ammonias, amines, guanidines, thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, etc. can be used. Examples of fatty acids include stearic acid, palmitic acid, myristic acid, and lauric acid, which may be blended in the form of a salt such as zinc stearate. Among these, stearic acid is preferred. Examples of metal oxides include zinc oxide (ZnO), iron oxide, and magnesium oxide, with zinc oxide being preferred. The process oil may be any of aromatic, naphthenic, and paraffinic. Antiaging agents include amine-ketone, imidazole, amine, phenol, sulfur and phosphorus based agents. Examples of the tackifier include phenol-based resins, rosin-based resins, and terpene-based resins. An example of the scorch inhibitor is N-cyclohexylthiophthalimide.

[0030] <Resin layer> The composite body according to this embodiment has a resin layer that is in direct contact with the epoxy rubber layer. The resin layer contains at least a resin containing a polyester-based thermoplastic elastomer and a phenolic 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 polyester-based thermoplastic elastomer and a phenolic resin. The resin composition may contain other components as necessary. The resin layer preferably contains a resin as a main component. Specifically, the content of the resin in 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.

[0031] The resin contains at least a polyester-based thermoplastic elastomer and a phenolic resin, and may further contain other resins as necessary.

[0032] From the viewpoint of improving adhesion with the epoxidized rubber layer, the content of the polyester thermoplastic elastomer is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, based on the total amount of the resin layer. The upper limit of the content of the polyester thermoplastic elastomer is not particularly limited. The content of the polyester thermoplastic elastomer may be, for example, in the range of 99% by mass or less based on the total amount of the resin layer. The polyester-based thermoplastic elastomer may be used alone or in a mixture of two or more kinds.

[0033] From the viewpoint of improving adhesion to the epoxidized rubber layer, the content of the phenol resin is preferably 3 mass % or more, more preferably 5 mass % or more, and even more preferably 7 mass % or more, based on the total amount of the resin layer. The content of the phenolic resin is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. When the content of the phenolic resin is within the above range, the durability of the resin layer at low temperatures (for example, -10°C or less) is improved compared to when the content is higher than the above range. When the content of the phenolic resin is within the above range, for example, when the resin layer of the composite is applied to a tire frame member, the rolling resistance of the tire tends to be lower compared to when the content is higher than the above range. The content of the phenol resin is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 35% by mass, and further preferably from 7% by mass to 30% by mass. The content of the phenol resin herein is a value including that in a covalent bond state resulting from reaction with other components such as polyester-based thermoplastic elastomer. The phenol resin may be used alone or in a mixture of two or more kinds.

[0034] (Polyester-based thermoplastic elastomer) Examples of polyester-based thermoplastic elastomers include materials in which at least a 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.

[0035] As the polyester forming the hard segment, an aromatic polyester can be used. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. The aromatic polyester is preferably polybutylene terephthalate derived from at least one of terephthalic acid and dimethyl terephthalate and 1,4-butanediol. The aromatic polyester can be formed, for example, from a dicarboxylic acid component 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 an ester-forming derivative thereof, and a diol having a molecular weight of 300 or less (for example, an aliphatic diol such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, or decamethylene glycol; 1,4-cyclohexanedimethanol, tricyclodecanedimethylol, or the like). or an aromatic diol such as 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, or 4,4'-dihydroxy-p-quaterphenyl; or a polyester derived from these dicarboxylic acid components and diol components, or a copolymer polyester using two or more of these dicarboxylic acid components and diol components in combination. It is also possible to copolymerize a polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component, or the like having three or more functionalities in the range of 5 mol % or less. Examples of polyesters forming the hard segment include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, with polybutylene terephthalate being preferred.

[0036] Examples of the polymer that forms 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, and copolymers of ethylene oxide and tetrahydrofuran. Examples of the aliphatic polyester include poly(ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. Among these aliphatic polyethers and aliphatic polyesters, from the viewpoint of the elastic properties of the resulting polyester block copolymer, preferred polymers for forming soft segments include poly(tetramethylene oxide) glycol, an ethylene oxide adduct of poly(propylene oxide) glycol, poly(ε-caprolactone), polybutylene adipate, and polyethylene adipate.

[0037] From the viewpoints of toughness and low-temperature flexibility, the number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000. From the viewpoint of moldability, the mass ratio (x:y) of the hard segment (x) to the soft segment (y) is preferably 99:1 to 20:80, more preferably 98:2 to 30:70.

[0038] The combination of the hard segment and the soft segment may be, for example, the combination of the hard segment and the soft segment described above. Among these, the combination of the hard segment and the soft segment described above is preferably a combination in which the hard segment is polybutylene terephthalate and the soft segment is an aliphatic polyether, and more preferably a combination in which the hard segment is polybutylene terephthalate and the soft segment is poly(ethylene oxide) glycol.

[0039] Examples of commercially available polyester thermoplastic elastomers that can be used include 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, E450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) manufactured by Toyobo Co., Ltd.

[0040] The polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.

[0041] (Phenol Resin) Examples of phenolic resins include condensates of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, and resorcin with aldehydes such as formaldehyde.Specific examples of phenolic resins include novolac-type phenolic resins obtained by subjecting the various phenols and the aldehydes to a condensation reaction using an acid catalyst, and resol-type phenolic resins obtained by subjecting the various phenols and the aldehydes to an addition reaction using an alkali catalyst. Examples of the phenolic resin include unmodified straight phenolic resin, terpene-modified phenolic resin, aralkyl-modified phenolic resin, xylylene-modified phenolic resin, melamine-modified phenolic resin, and oil-modified phenolic resin.

[0042] Of these, from the viewpoint of the physical properties of the resin layer and the workability during formation of the resin layer, the phenolic resin is preferably a novolac-type phenolic resin, and among these, it is more preferable to include at least one selected from the group consisting of novolac-type straight phenolic resins, novolac-type terpene-modified phenolic resins, novolac-type oil-modified phenolic resins, novolac-type aralkyl-modified phenolic resins, novolac-type xylylene-modified phenolic resins, and novolac-type melamine-modified phenolic resins, and it is even more preferable to include at least one selected from the group consisting of novolac-type straight phenolic resins, novolac-type terpene-modified phenolic resins, and novolac-type oil-modified phenolic resins.

[0043] The hydroxyl equivalent of the phenol resin is preferably from 100 g / eq to 300 g / eq, more preferably from 100 g / eq to 200 g / eq, and further preferably from 100 g / eq to 150 g / eq. The phenolic resin having a hydroxyl equivalent in the above range has the advantage of being more excellent in adhesiveness than a phenolic resin having a hydroxyl equivalent greater than the above range, and has the advantage of being structurally easier to obtain than a phenolic resin having a hydroxyl equivalent less than the above range. The hydroxyl equivalent is measured in accordance with JIS K0070:1992.

[0044] (Other resins) When the resin contains other resins, the types of the other resins are not particularly limited. Examples of the 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 thermoplastic elastomers; thermosetting resins; etc. The other resins may be used alone or in combination of two or more. Among these, the other resin is preferably a polyester thermoplastic resin from the viewpoint of improving adhesion to the epoxidized rubber layer, and may be a polyester thermoplastic resin having the same structure as the hard segment of the polyester thermoplastic elastomer contained in the resin layer.

[0045] Examples of the polyester-based thermoplastic resin include the polyesters that form the hard segments of the above-mentioned polyester-based thermoplastic elastomers. Specific examples of polyester-based thermoplastic resins include aliphatic polyesters such as polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly(ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Among these, polybutylene terephthalate is preferred as the polyester-based thermoplastic resin from the viewpoints of heat resistance and processability.

[0046] Commercially available examples of 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 "Trecon" series (e.g., 1401X06, 1401X31, etc.) manufactured by Toray Industries, Inc., and the like.

[0047] (Carbodiimide compounds) The resin layer preferably contains a carbodiimide compound as another component. The carbodiimide compound may be contained in the resin layer in a state in which it reacts with another component such as a polyester-based thermoplastic elastomer to form a covalent bond. In other words, the resin layer may be a layer that is a reaction product of a resin composition that contains a carbodiimide compound as another component. When the resin layer contains a carbodiimide compound, the mechanical durability of the resin layer is improved and the adhesiveness to the epoxy rubber layer is also improved. The reason is unclear, but it is speculated as follows. Specifically, the carbodiimide compound has a bifunctional carbodiimide group (-N=C=N-), which reacts with a group (e.g., a carboxy group (-COOH)) of the polyester thermoplastic elastomer to form a covalent bond. The polyester thermoplastic elastomer is crosslinked and bonded to the carbodiimide compound, which is speculated to improve the mechanical durability of the resin layer and to improve the adhesiveness to the epoxy rubber layer by forming a new carboxy group derived from the crosslinked carbodiimide compound.

[0048] 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 the carbodiimide compound include monofunctional carbodiimide compounds such as N,N'-diisopropylcarbodiimide, N,N'-di(o-toluyl)carbodiimide, N,N'-dicyclohexylcarbodiimide, and N,N'-bis(2,6-diisopropylphenyl)carbodiimide; bifunctional carbodiimide compounds such as p-phenylene-bis(2,6-xylylcarbodiimide), p-phenylene-bis(t-butylcarbodiimide), p-phenylene-bis(mesitylcarbodiimide), tetramethylene-bis(t-butylcarbodiimide), and cyclohexane-1,4-bis(methylene-t-butylcarbodiimide); and polyfunctional carbodiimide compounds such as condensates of organic isocyanates.

[0049] The organic isocyanate may be an aromatic isocyanate, an aliphatic isocyanate, or a mixture thereof. The organic group of the organic isocyanate may be either an aromatic organic group or an aliphatic organic group, or may be a combination of an aromatic organic group and an aliphatic organic group. Specific examples of the organic isocyanate include organic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,3-phenylene diisocyanate; and organic monoisocyanates such as isophorone isocyanate, phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

[0050] The carbodiimide compound may be used alone or in a mixture of two or more kinds. Among these, the carbodiimide compound is preferably a polyfunctional carbodiimide compound, which means a compound having two or more carbodiimide groups.

[0051] The carbodiimide compound may be a commercially available product. Examples of commercially available products include Carbodilite (registered trademark) (e.g., HMV-15CA, LA-1) manufactured by Nisshinbo Chemical Co., Ltd., and Stavaxol (registered trademark) (e.g., P, P-100, etc.) manufactured by Rhein Chemie.

[0052] The functional group equivalent of the carbodiimide compound is preferably from 100 g / eq to 500 g / eq, more preferably from 100 g / eq to 400 g / eq, and further preferably from 100 g / eq to 300 g / eq. When the functional group equivalent of the carbodiimide compound is within the above range, the mechanical durability of the resin layer is improved compared to when it is greater than the above range, and the storage stability is higher compared to when it is less than the above range.

[0053] The carbodiimide compound preferably has a softening point (softening temperature) of 50° C. or more and 150° C. or less from the viewpoints of supply stability during twin-screw kneading and compounding and ease of melt kneading with the polyester-based thermoplastic elastomer.

[0054] The content of the carbodiimide compound is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the entire resin layer from the viewpoint of improving mechanical durability and adhesion to the epoxy rubber layer, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the entire resin layer from the viewpoint of improving processability by suppressing an increase in viscosity during production of the resin layer. The content of the carbodiimide compound is preferably from 0.1 to 10% by mass, more preferably from 0.3 to 5% by mass, and further preferably from 0.5 to 3% by mass. The content of the carbodiimide compound herein is a value including that which has reacted with other components such as polyester-based thermoplastic elastomer and is covalently bonded thereto.

[0055] (hardening agent) The resin layer may contain a curing agent as another component. As the curing agent, a formaldehyde donor that generates formaldehyde by heating is used. As the curing agent, for example, hexamethylenetetramine, paraformaldehyde, hexamethoxymethylmelamine, acetaldehyde ammonia, α-polyoxymethylene, polyfunctional methylolmelamine derivatives, oxazolidine derivatives, polyfunctional methylolated acetylene urea, etc. are mentioned, and preferably hexamethylenetetramine and hexamethoxymethylmelamine are used. Hexamethoxymethylmelamine is particularly preferred.

[0056] The content of the curing agent is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the entire resin layer. The content of the curing agent within the above range has the advantage that the increase in viscosity due to the increase in the curing speed is suppressed compared to when the content is greater than the above range, and the processability is excellent. In addition, when the resin layer contains a curing agent, the content of the curing agent may be 0.1% by mass or more based on the entire resin layer. In addition, the content of the curing agent is preferably 0.5 times or less, more preferably 0.4 times or less, and even more preferably 0.3 times or less, of the phenolic resin content, from the viewpoint of increasing the compatibility between the phenolic resin and the polyester-based thermoplastic elastomer and maintaining the moldability of the resin after kneading. When the resin layer contains a curing agent, the content of the curing agent may be 0.01 times or more of the phenolic resin content. The content of the curing agent herein is a value including that which has reacted with other components such as polyester-based thermoplastic elastomer and is covalently bonded thereto.

[0057] (Other Ingredients) The resin layer may contain other components such as additives within a range that does not impair the effect, such as various fillers (e.g., silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weather resistance agents, etc.

[0058] <Diene rubber layer> In the composite body according to the present embodiment, if necessary, a diene rubber layer that is in direct contact with the epoxy rubber layer may be provided on the surface of the epoxy rubber layer opposite to the resin layer. The diene rubber layer contains at least a diene rubber, and may contain other components as necessary. The diene 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 epoxidized diene rubber in the epoxy rubber layer. Moreover, specific examples of the diene rubber, the other rubbers, and the components other than rubber are the same as those explained in the epoxy rubber layer.

[0059] <Method of manufacturing the composite> An example of a method for producing the composite of the present embodiment includes a step of forming a laminate having an unvulcanized epoxy rubber layer and a resin layer provided in direct contact with the unvulcanized epoxy rubber layer, and a step of vulcanizing the unvulcanized epoxy rubber layer by heating the laminate.

[0060] The unvulcanized epoxy rubber layer can be obtained, for example, by kneading the materials constituting the epoxy rubber layer and molding it into a desired shape. The kneading temperature when forming the unvulcanized epoxy rubber layer can be, for example, in the range of 80°C to 180°C from the viewpoint of maintaining the unvulcanized state. In addition, examples of the kneader include ordinary kneaders such as a mixing roll, a sigma type rotary blade kneader, a Banbury mixer, a high-speed twin-screw continuous mixer, and a single-screw, twin-screw, or multi-screw extruder type kneader. Examples of the molding method include extrusion molding, rolling molding, and the like.

[0061] The resin layer is obtained, for example, by melt-kneading the material constituting the resin layer and molding it into a desired shape. The kneading temperature when forming 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 polyester-based thermoplastic elastomer. In addition, when the resin layer contains another resin having a melting point higher than that of the polyester-based 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 epoxy rubber layer. Examples of the molding method include injection molding, vacuum molding, pressure molding, melt casting, etc.

[0062] In the process of forming the laminate, the resin layer is brought into direct contact with the unvulcanized epoxy rubber layer. In this embodiment, since the epoxy rubber layer and the resin layer have the above-described configurations, high adhesion can be obtained even when the surface of the resin layer that contacts the unvulcanized epoxy rubber layer and the surface of the unvulcanized epoxy rubber layer that contacts the resin layer are brought into contact with each other without being subjected to any processing such as surface treatment. The vulcanization temperature in the step of vulcanizing the unvulcanized epoxy rubber layer is appropriately set depending on the composition of the epoxy rubber layer, and may be, for example, in the range of 110° C. to 220° C. The vulcanization time may be, for example, 1 minute to 30 hours.

[0063] In addition, when manufacturing a composite having an epoxy rubber layer, a resin layer, and a diene rubber layer, for example, the composite is manufactured through a process of forming a laminate having an unvulcanized epoxy rubber layer, a resin layer provided in direct contact with the unvulcanized epoxy rubber layer, and an unvulcanized diene rubber layer provided in direct contact with the unvulcanized epoxy rubber layer on the side of the unvulcanized epoxy rubber layer opposite to the resin layer, and a process of vulcanizing the unvulcanized epoxy rubber layer and the unvulcanized diene rubber layer by heating the laminate. The unvulcanized diene rubber layer can be obtained by the same method as the unvulcanized epoxy rubber layer.

[0064] <Use of the composite> The composite according to this embodiment is applicable to various fields in which a member including a resin layer and a member including a rubber layer are used, such as tires, anti-vibration rubber, rubber hoses, rubber-resin composite hoses, belts, rubber crawlers, golf balls, bellows, seismic isolation rubber, sealing materials, caulking materials, bicycles, and the like.

[0065] When the composite body is used for a tire, examples of the combination of the resin layer and the epoxy rubber layer in the composite body 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 an epoxy rubber layer, a tire frame member, and a rubber sheet adhered to the surface of the belt member. A combination of a bead component as a resin layer, a tire frame component as an epoxy rubber layer, and at least one member selected from the group consisting of a rubber sheet adhered to the surface of the bead component. A combination of a tire frame 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 frame member as an epoxy rubber layer. A combination of a belt cord as a resin layer, a cord covering layer that covers the belt cord as an epoxy rubber layer, and at least one member selected from the group consisting of a rubber sheet adhered to the surface of the belt cord (i.e., the belt member is a composite). A combination of a ply cord as a resin layer, a cord covering layer covering the ply cord as an epoxy rubber layer, and at least one member selected from the group consisting of a rubber sheet adhered to the surface of the ply cord (i.e., the carcass ply is a composite). A combination of a bead wire as a resin layer, a wire coating layer that covers the bead wire as an epoxy rubber layer, and at least one member selected from the group consisting of a rubber sheet adhered to the surface of the bead wire (i.e., the bead core is a composite).

[0066] Furthermore, when the composite body has a resin layer, an epoxy rubber layer, and a diene rubber layer, examples of the combinations thereof include the following combinations. A combination of a belt member as a resin layer, a rubber sheet as an epoxy rubber layer, and at least one member selected from the group consisting of a tread and a tire frame member as a diene rubber layer. A combination of a bead component as a resin layer, a rubber sheet as an epoxy rubber layer, and a tire frame component as a diene rubber layer. A combination of a tire frame member as a resin layer, a rubber sheet as an epoxy rubber layer, and at least one member selected from the group consisting of a tread, a belt member, and a bead member as a diene rubber layer. A combination of a belt cord as a resin layer, a rubber sheet as an epoxy rubber layer, and a cord covering layer as a diene rubber layer. A combination of a ply cord as a resin layer, a rubber sheet as an epoxy rubber layer, and a cord covering layer as a diene rubber layer. A combination of a bead wire as a resin layer, a rubber sheet as an epoxy rubber layer, and a wire coating layer as a diene rubber layer.

[0067] [tire] The tire of the present invention comprises at least the above-mentioned composite. Hereinafter, embodiments of a tire having the above-mentioned composite will be described with reference to the drawings, but the tire of the present invention is not limited to these examples.

[0068] First Embodiment The tire of the first embodiment has an annular tire frame member including a resin, a belt member provided on the tire radial direction outer side of the tire frame member and including a plurality of reinforcing cords and a coating resin that coats the reinforcing cords, a rubber sheet that is an epoxy rubber member provided on the tire radial direction outer side surface of the belt member in direct contact with the coating resin of the belt member, and a tread provided on the tire radial direction outer side surface of the rubber sheet in direct contact with the rubber sheet. In the first embodiment, the tire has a composite having the coating resin of the belt member corresponding to the resin layer, the rubber sheet corresponding to the epoxy rubber layer, and the tread corresponding to the diene rubber layer. The tread may be a laminate of a plurality of diene rubber layers. In addition, a tread corresponding to another rubber layer may be used instead of the tread corresponding to the diene rubber layer, and the tread corresponding to the epoxy rubber layer may be an epoxy rubber member provided in direct contact with the coating resin of the belt member without a rubber sheet therebetween.

[0069] The first embodiment will be described below with reference to Fig. 1 and Fig. 2. In Fig. 2, arrow W indicates a direction parallel to the tire rotation axis (hereinafter, may be referred to as the "tire width direction"), and arrow S indicates a direction passing through the tire rotation axis and perpendicular to the tire width direction (hereinafter, may be referred to as the "tire radial direction"). Furthermore, dashed dotted line CL indicates the center line of the tire (hereinafter, may be referred to as the "tire equatorial plane").

[0070] FIG. 1 is a perspective view showing a cross section of a portion of a tire according to a first embodiment, and FIG. 2 is a cross section taken along the tire width direction and showing the configuration of the tire according to the first embodiment. 1 and 2, a 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 a resin, a belt member 12 provided on the tire radially outer side of the tire case 17, a rubber sheet 11 which is an example of an epoxy rubber member provided on an area 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 tire width direction outer surface of the belt member 12, and a tread 30 provided on the tire radially outer surface of the rubber sheet 11. The belt member 12 also includes a plurality of reinforcing cords 24 coated with a coating resin 26.

[0071] -Tire frame components- The tire case 17 is made of, for example, a thermoplastic elastomer, which is an example of a resin material, and is formed into 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 each extending radially outward from the pair of bead portions 14, and a crown portion 18 connecting the pair of side portions 16. The bead portions 14 are portions that come into contact with a rim (not shown). The side portions 16 form the sides of the tire 10, and are gently curved from the bead portions 14 toward the crown portion 18 so as to be convex outward in the tire width direction.

[0072] The crown portion 18 is a portion that connects the radially outer end of one side portion 16 to the radially outer end of the other side portion 16, and supports a tread 30 disposed on the radially outer side of the tire.

[0073] In this embodiment, the crown portion 18 has a substantially constant thickness. An outer peripheral surface 18A of the crown portion 18 of the tire case 17 may be formed flat in a cross section in the tire width direction, or may be curved and bulged outward in the tire radial direction. The outer peripheral surface 18A of the crown portion 18 in this embodiment is the outer periphery of the tire case 17 on which the belt member 12 is provided.

[0074] The tire case 17 is formed by forming a pair of annular tire halves 17H each having one bead portion 14, one side portion 16, and a half-width crown portion 18, and by facing these tire halves 17H to each other and joining ends of the half-width crown portions 18 at the tire equatorial plane CL. These ends are joined together using, for example, a welding resin material 17A.

[0075] An annular bead core 20 extending along the tire circumferential direction is embedded in the bead portion 14. This bead core 20 is made of a bead cord (not shown). This bead cord is made of a metal cord such as a steel cord, an organic fiber cord, a resin-coated organic fiber cord, a hard resin, or the like. Note that if the rigidity of the bead portion 14 can be sufficiently ensured, the bead core 20 itself may be omitted.

[0076] The tire case 17 may be an integrally molded product, or may be manufactured by dividing the tire case 17 into three or more resin members and then joined together to form the tire case 17. For example, the tire case 17 may be manufactured by dividing each portion (e.g., the bead portion 14, the side portion 16, the crown portion 18) and then joined together to form the tire case 17. In this case, each portion (e.g., the bead portion 14, the side portion 16, the crown portion 18) of the tire case 17 may be made of resin materials having different characteristics.

[0077] Further, in the tire case 17, a reinforcing material (polymeric material or metallic fiber, cord, nonwoven fabric, woven fabric, etc.) may be embedded and disposed.

[0078] Also, a covering layer 21 may be formed on the surface of the bead portion 14 at a contact portion with the rim (not shown) to enhance airtightness between the bead portion 14 and the rim. Examples of materials for the covering layer 21 include a material such as rubber that is softer and more weather resistant than the tire case 17. The covering layer 21 may be provided so as to be folded back from the inner surface of the inner side in the tire width direction of the bead portion 14 to the outer side in the tire width direction, and extend to the vicinity of the outer end of the belt member 12 in the tire width direction via the outer surface of the side portion 16. Also, the extending end of the covering layer may be covered by the tread 30 described later. However, if the sealing (airtightness) between the bead portion 14 of the tire case 17 and the rim (not shown) can be ensured only by the bead portion 14, the covering layer 21 may not be provided. In addition, when the coating layer 21 contains rubber, the tire case 17 may correspond to a resin layer containing a polyester-based thermoplastic elastomer and a phenolic resin, and the coating layer 21 may correspond to an epoxy rubber layer containing an epoxidized diene-based rubber and carbon black, making the composite.

[0079] -Belt material- Next, the belt member 12 will be described. The belt member 12 is configured by winding a resin-coated cord 28 spirally around the outer periphery of the tire case 17 in the tire circumferential direction and joining the tire case 17, and by joining adjacent portions of the resin-coated cord 28 in the tire width direction. The resin-coated cord 28 is configured by coating the reinforcing cord 24 with a coating resin 26.

[0080] The reinforcing cord 24 is composed of a monofilament (single wire) of metal fiber or organic fiber, or a multifilament (twisted wire) made of these fibers twisted together, and the coating resin 26 is composed of a resin material containing a resin containing a polyester-based thermoplastic elastomer and a phenolic resin. Examples of the reinforcing cord 24 include a monofilament (single wire) made of one metal cord and a multifilament (twisted wire) made of multiple twisted metal cords, with the multifilament being preferred from the viewpoint of further improving the durability of the tire. The number of multiple metal cords may be, for example, 2 to 10, and preferably 5 to 9. From the viewpoint of achieving both the internal pressure resistance and the weight reduction of the tire, the thickness of the reinforcing cord 24 is preferably 0.2 mm to 2 mm, and more preferably 0.8 mm to 1.6 mm.

[0081] 1 and 2, the layer of the resin-coated cord 28 is a single layer, and the reinforcing cords 24 are arranged in a row in the tire width direction, but this is not limited to the above. The belt member 12 may be a laminated belt member in which the resin-coated cord 28 is wound spirally in the tire circumferential direction to form a layer, and then another resin-coated cord 28 is wound around the outer circumferential surface of the layer.

[0082] 1 and 2 is configured by spirally winding and joining the resin-coated cord 28 around the outer circumferential surface of the tire case 17, but is not limited thereto. For example, the belt member may be configured by winding a sheet in which a plurality of reinforcing cords 24 and the coating resin 26 are integrated into one piece around the outer circumferential surface of the tire case 17.

[0083] -Rubber sheets and treads- Next, the rubber sheet 11 (an example of an epoxy rubber member) and the tread 30 will be described. As shown in Figures 1 and 2, a rubber sheet 11 is arranged in direct contact with the belt member 12 on the outer side of the tire radial direction of the belt member 12, and a tread 30 is arranged in direct contact with the rubber sheet 11 on the outer side of the rubber sheet 11 in the tire radial direction. The rubber sheet 11 is made of a rubber material containing a rubber containing an epoxidized diene rubber and carbon black, and the tread 30 is made of a rubber material containing a diene rubber. The tread 30 may be a multi-layer body in which multiple layers of a rubber material containing a diene rubber are laminated. The rubber sheet 11 and the tread 30 are laminated in an unvulcanized state to the belt member 12 on the tire case 17, for example, and then bonded by vulcanization. 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.

[0084] Drainage grooves 30A extending in the tire circumferential direction are formed on the outer peripheral surface in the tire radial direction of the tread 30. In this embodiment, two grooves 30A are formed, but this is not limited, and more grooves 30A may be formed. In addition, a known tread pattern can be used.

[0085] In addition, in Figures 1 and 2, the tread 30 is provided on the belt member 12 via the rubber sheet 11, but this is not limited to this. For example, a tread containing a rubber containing an epoxidized diene rubber and carbon black may be provided in direct contact with the belt member 12.

[0086] -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 cores 20 is formed by injection molding using a thermoplastic material. Next, the pair of tire halves 17H are placed facing each other, the ends of the portions that will become the crown portion 18 are butted together, and molten welding resin material 17A is applied to the butted portions to join the pair of tire halves 17H. In this manner, the annular tire case 17 is formed.

[0087] Next, a process of winding the resin-coated cord 28 around the outer periphery of the tire case 17 will be described. Specifically, while feeding the resin-coated cord 28 toward the outer periphery 18A of the crown portion 18, hot air is blown onto the thermoplastic resin of the resin-coated cord 28 and the outer periphery 18A of the crown portion 18 to heat and melt the resin-coated cord 28. Then, the resin-coated cord 28 in a state where the thermoplastic resin is molten is pressed against the outer periphery 18A of the crown portion 18 in a molten state to be bonded, and these are cooled to solidify. In this manner, a layer of the resin-coated cord 28 is formed on the outer periphery of the tire case 17, specifically, on the outer periphery of the crown portion 18, thereby forming the belt member 12. If necessary, an adhesive layer may be provided between the tire case 17 and the belt member 12.

[0088] Next, the rubber sheet 11 and the tread 30 are formed on the outer circumferential 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. Note that 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 tire case 17 (i.e., raw tire) in which the belt member 12, the unvulcanized rubber sheet, and the unvulcanized tread are laminated is vulcanized. Specifically, for example, the tire case 17 is housed in a vulcanizer or mold and heated, whereby the unvulcanized rubber sheet is vulcanized to form the rubber sheet 11, and the unvulcanized tread is vulcanized to form the tread 30. Examples of the vulcanization temperature include 110°C to 220°C, and examples of the vulcanization time include 1 minute to 30 hours. In this manner, the tire 10 of the first embodiment is obtained.

[0089] <Second embodiment> The tire of the second embodiment has an annular tire frame member including rubber, a belt member provided on the tire radial direction outer side of the tire frame member and including a plurality of reinforcing cords and a coating resin that coats the reinforcing cords, a tread provided on the tire radial direction outer surface of the belt member, and a rubber sheet that is an epoxy rubber member provided between the tire frame member and the belt member and between the belt member and the tread in direct contact with the tire frame member and the tread. In the second embodiment, the tire has a composite including the coating resin of the belt member corresponding to the resin layer, the rubber sheet corresponding to the epoxy rubber layer, a tire frame member having a rubber layer corresponding to the diene rubber layer, and a tread corresponding to the diene rubber layer. The tread may be a multi-layer body of a plurality of diene rubber layers. In the second embodiment, a tread corresponding to another rubber layer may be used instead of the tread corresponding to the diene rubber layer, and the tread corresponding to the epoxy rubber layer may be an epoxy rubber member provided in direct contact with the coating resin of the belt member without a rubber sheet. Also, a tire frame member having a rubber layer corresponding to another rubber layer may be used instead of the tire frame member having a rubber layer corresponding to the diene rubber layer, and the tire frame member having a rubber layer corresponding to the epoxy rubber layer may be an epoxy rubber member provided in direct contact with the coating resin of the belt member without a rubber sheet.

[0090] The second embodiment will be described below with reference to FIG. Fig. 3 is a cross-sectional view taken along the tire width direction, showing the configuration of a tire according to the second embodiment. In Fig. 3, members common to other figures are given the same reference numerals, and description thereof will be 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 formed including a rubber material containing rubber, a belt member 12, a rubber sheet 11 which is an example of an epoxy rubber member, and a tread 30. The belt member 12, the rubber sheet 11, and the tread 30 are similar to those in the first embodiment, and therefore the description thereof will be omitted.

[0091] As shown in Fig. 3, the tire 80 of this embodiment is, for example, a so-called radial tire, and includes a pair of bead portions 14 in which the bead cores 20 are embedded, and a carcass 86 consisting of one carcass ply 82 is straddled between one bead portion 14 and the other bead portion 14. Note that Fig. 3 shows the shape of the tire 80 in its natural state before it is filled with air.

[0092] The carcass ply 82 is formed by covering a plurality of cords (not shown) extending in the radial direction of the pneumatic tire 80 with a coating rubber (not shown). The material of the cords of the carcass ply 82 may be, for example, PET, but may be other conventionally known materials. The coating rubber is a rubber material containing diene rubber, and constitutes a covering layer (not shown) equivalent to the diene rubber layer.

[0093] The carcass ply 82 has end portions in the tire width direction folded back toward the outside in the tire radial direction at the bead cores 20. The portion of the carcass ply 82 that spans from one bead core 20 to the other bead core 20 is called a main body portion 82A, and the portion that is folded back from the bead core 20 is called a folded back portion 82B.

[0094] A bead filler 88 having a thickness gradually decreasing from the bead core 20 toward the tire radially outward is disposed between the main body portion 82A and the folded-back portion 82B of the carcass ply 82. In the tire 80, a portion of the bead filler 88 extending from an outer end 88A in the tire radial direction to an inner side in the tire radial direction is defined as a bead portion 14.

[0095] An inner liner 90 made of rubber is disposed on the inner side of the carcass 86 in the tire width direction, and a side rubber layer 92 made of a rubber material containing rubber is disposed on the outer side of 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 form a tire case 94.

[0096] In FIG. 3, the belt member 12 is provided on the tire radial outside of the carcass 86 via the rubber sheet 11, but this is not limited thereto. For example, the belt member 12 may be provided in direct contact with a carcass consisting of a carcass ply formed by coating a cord with a coating rubber containing a rubber containing an epoxidized diene rubber and carbon black. In addition, in FIG. 3, a tread 30 corresponding to a diene rubber layer is arranged on the radially outer side of the belt member 12 via a rubber sheet 11, but this is not limited to this. For example, a tread containing a rubber containing an epoxidized diene rubber and carbon black may be provided in direct contact with the belt member 12. Drainage grooves 30A are formed in the tread 30. The grooves 30A of the tread 30 have a conventional, generally known pattern.

[0097] (Tire manufacturing method) Next, an example of a method for manufacturing the tire 80 of the present embodiment will be described. First, an unvulcanized tire case 94 is formed around the outer periphery of a known tire building drum (not shown), and is composed of an inner liner 90 made of a rubber material, a bead core 20, a bead filler 88 made of a rubber material, a carcass ply 82 in which cords are coated with a rubber material, and a side rubber layer 92.

[0098] On the other hand, the belt member 12 is formed as follows. Specifically, the resin-coated cord 28 is sent out toward the outer circumferential surface of a belt-forming drum (not shown). The resin-coated cord 28 is heated by hot air and pressed against the outer circumferential surface of the belt-forming drum in a molten state, and then cooled. In this manner, the resin-coated cord 28 is spirally wound around the outer circumferential surface of the belt-forming drum and pressed against the outer circumferential surface, thereby forming a layer of the resin-coated cord 28 on the outer circumferential surface of the belt-forming drum.

[0099] Next, the belt member 12 in which the resin-coated cord 28 has been cooled and the coating resin 26 has solidified is removed from the belt forming drum. Then, an unvulcanized rubber sheet 11 is attached to the inner peripheral surface of the removed belt member 12, and then the belt member 12 is disposed radially outside the unvulcanized tire case 94 on the tire forming drum. Thereafter, 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 pressure-bonded to the inner peripheral surface of the belt member 12. Finally, an unvulcanized rubber sheet 11 is attached to the outer peripheral surface of the belt member 12, and then an unvulcanized tread 30 is attached onto the unvulcanized rubber sheet 11, thereby completing a green tire. The green tire thus manufactured is vulcanized in a vulcanization mold, and the tire 80 is completed.

[0100] <Third embodiment> A tire according to a third embodiment includes an annular tire frame member including a resin, a belt member provided on the tire radially outer side of the tire frame member and including a plurality of reinforcing cords and a coating resin that coats the reinforcing cords, a rubber sheet provided on the tire radially outer surface of the belt member in direct contact with the coating 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 side rubber that is an epoxy rubber member provided on the tire widthwise outer side of the tire frame member. In the third embodiment, the tire has a composite including the tire frame member corresponding to the resin layer and the side rubber corresponding to the epoxy rubber layer. In the third embodiment, the side rubber corresponding to the epoxy rubber layer is provided in direct contact with the tire frame member, but the present invention is not limited to this. A configuration in which a side rubber corresponding to a diene rubber layer is provided via a rubber sheet corresponding to the epoxy rubber layer may also be used. In the third embodiment, the coating resin of the belt member corresponds to the resin layer, the rubber sheet corresponds to the epoxy rubber layer, and the tread corresponds to the diene rubber layer, but is not limited thereto. The tread may be a multi-layer body of a plurality of diene rubber layers.

[0101] Fig. 4 is a cross-sectional view taken along the tire width direction, showing the configuration of a tire according to a third embodiment. In Fig. 4, members common to other figures are given the same reference numerals, and description thereof will be omitted. As shown in FIG. 4, a tire 110 according to the third embodiment includes a tire case 17 which is an annular tire frame member made of a resin material containing resin, a belt member 12 provided on the tire radially outer side of the tire case 17, a rubber sheet 11 provided on an area of ​​the tire radially outer surface of the tire case 17 where the belt member 12 is not provided, as well as on the tire radially outer surface and tire width direction outer surface of the belt member 12, a tread 30 provided on the tire radially outer surface of the rubber sheet 11, and a side rubber 13 which is an example of an epoxy rubber member provided on the tire width direction outer surface of the tire case 17. The tire case 17, the belt member 12, the rubber sheet 11, and the tread 30 are similar to those in the first embodiment, and therefore the description thereof will be omitted. The side rubber 13 is made of a rubber material containing a rubber containing an epoxidized diene rubber and carbon black.

[0102] In the third embodiment, the side rubber 13 is provided as an epoxy rubber member in direct contact with the outer side of the tire case 17 in the tire width direction. However, an inner rubber equivalent to an epoxy rubber layer may be provided in direct contact with the inner side of the tire case 17 in the tire width direction, or an inner rubber equivalent to a diene rubber layer may be provided on the inner side of the tire case 17 in the tire width direction via a rubber sheet equivalent to the epoxy rubber layer.

[0103] <Fourth embodiment> The fourth embodiment is an example of a form in which the composite is provided in the bead portion of an annular tire frame member containing rubber. Specifically, the tire frame member is configured by bead cores in which bead wires are coated with a coating resin, a carcass having a main portion located between the bead cores and a folded portion folded from the inside to the outside around the bead cores, a resin bead filler provided between the bead cores, the main portion and the folded portion, a rubber sheet which is an epoxy rubber member provided around the bead cores and the bead filler, and a rubber member provided around the rubber sheet. That is, the fourth embodiment has a composite having the coating resin of the bead core and the bead filler which correspond to the resin layer, the rubber sheet which corresponds to the epoxy rubber layer, and the rubber member which corresponds to the diene rubber layer. In the fourth embodiment, a rubber member is provided around the bead core and the bead filler via a rubber sheet corresponding to the epoxy rubber layer, but this is not limited to this. The rubber member corresponding to the epoxy rubber layer may be an epoxy rubber member provided in direct contact with the bead core and the bead filler without a rubber sheet. 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 diene rubber layer may be provided around the coating resin of the bead core corresponding to the resin layer via a rubber sheet corresponding to the epoxy rubber layer, or the bead filler corresponding to the epoxy rubber layer may be provided in direct contact with the coating resin of the bead core corresponding to the resin layer.

[0104] Fig. 5 is an enlarged cross-sectional view of a bead portion of a tire according to a fourth embodiment. In Fig. 5, members common to other figures are given the same reference numerals and description thereof will be 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, a rubber sheet 11 surrounding the bead filler 89 and the bead core 20, and a carcass 86. 5, the bead core 20 and the bead filler 89 are embedded in a rubber member 91, and the bead core 20 and the bead filler 89 constitute an integral core filler member 50, and a rubber sheet 11 is provided around the core filler member 50. However, the bead core 20 and the bead filler 89 may be separate bodies.

[0105] As shown in FIG. 5, when viewed in cross section in the tire width direction, each bead core 20 has a bead wire bundle 62 and a covering layer 65 that surrounds the periphery of the bead wire bundle 62 and is made of a resin material. 5, the bead filler 89 is integral with the covering layer 65 of the bead core 20 and is made of the same resin material as the covering layer 65. However, the resin material constituting the bead filler 89 may be different from that of the covering layer 65 of the bead core 20. Also, the resin material constituting the bead filler 89 may be different for each portion of the bead filler 89.

[0106] 5, the bead wire bundle 62 of the bead core 20 merely refers to a configuration in which multiple cross sections of the bead wires constituting the bead core 20 appear when viewed in a cross section in the tire width direction, and the actual number of bead wires constituting the bead core 20 may be one or multiple. In other words, the bead wire bundle 62 may be configured by winding one bead wire multiple times in the tire circumferential direction, or may be configured by winding each of multiple bead wires once or multiple times in the tire circumferential direction. The bead wires may be made of any known material, for example a steel cord, which may be made of a steel monofilament or stranded wire, or may be made of organic or carbon fibers.

[0107] The covering layer 65 of the bead core 20 extends continuously along the tire circumferential direction, and is configured to be annular in at least a portion of the tire circumferential direction so as to surround the entire circumference of the bead wire bundle 62 of the bead core 20 when viewed in a tire width direction cross section. The covering layer 65 does not have to be annular in a portion of the tire circumferential direction when viewed in a tire width direction cross section, and may be, for example, C-shaped. In this example, when viewed in a cross section in the tire width direction, each bead wire is covered with a covering resin 63 made of a resin material inside the ring shape formed by the covering layer 65. In other words, the gap region between the covering layer 65 and each bead wire is filled with the covering resin 63. In this example, the resin material constituting the coating resin 63 is different from the resin material constituting the coating layer 65. However, the resin material constituting the coating resin 63 may be the same as the resin material constituting the coating layer 65. In this example, both the covering layer 65 of the bead core 20 and the bead filler 89 are made of a resin material, but it is sufficient if at least one of them is made of a resin material. In other words, when the covering layer 65 of the bead core 20 is made of a resin material, the bead filler 89 may be made of rubber, and when the bead filler 89 is made of resin, the covering layer 65 may be made of a rubber material. Without being limited to this example, when viewed in a cross section in the tire width direction, inside the ring shape formed by the covering layer 65, each bead wire may be covered with a covering rubber made of rubber instead of the covering resin 63. In other words, the gap region between the covering layer 65 and each bead wire may be filled with the covering rubber.

[0108] The tire of this embodiment is manufactured in the same manner as the tire of the above-described second embodiment. In this embodiment, a core filler member 50 obtained by integrally molding the bead filler 89 and the bead core 20 is used. In this embodiment, an unvulcanized rubber sheet is attached around the core filler member 50, and then an unvulcanized rubber member 91 is attached to form an unvulcanized tire case. Then, a belt member and an unvulcanized tread are provided as necessary to obtain a green tire, which is then vulcanized and molded to obtain a tire.

[0109] An example of a method for manufacturing the core filler member 50 will now be described. A method for manufacturing the core filler member 50 includes, for example, an annular body forming step, an injection molding step, and a cooling step.

[0110] In the annular body forming process, a strip member formed by coating one or more bead wires with 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 coating resin 63 is spirally wound and stacked in three layers. In this example, in the annular body forming step, the molten coating resin 63 is applied to the outer periphery of the bead wire and solidified by cooling to form a strip member. The annular body can be formed by winding and stacking the strip member in layers, and the layers can be joined together by, for example, winding the strip member while melting the coating resin 63 by hot plate welding or the like, and solidifying the molten coating resin 63. Alternatively, the layers can be joined together by bonding them together with an adhesive or the like.

[0111] In the injection molding process following the annular body forming process, the annular body formed in the annular body forming process is covered with a resin material to form a covering layer 65 and a bead filler 89 integral with the covering layer 65.

[0112] In the cooling process following the injection molding process, the covering layer 65 and the bead filler 89 are solidified by cooling. The bead core 20 in the core filler member 50 is configured such that the periphery of the annular body is covered with the solidified covering layer 65. In addition, on the outer side of the covering layer 65 in the tire radial direction, the bead filler 89 is configured integrally with the covering layer 65.

[0113] Although an example of an embodiment of the present invention has been described above, the present invention is not limited to this embodiment, and various other embodiments are possible. Furthermore, the first to fourth embodiments can be combined as appropriate. EXAMPLES

[0114] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these descriptions. In addition, unless otherwise specified, "parts" are based on mass.

[0115] <Preparation of unvulcanized rubber layer> Among the components shown in Tables 1 and 2, the components other than the vulcanization accelerator and vulcanizing agent were mixed and stirred in a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 110°C for 3 minutes, and then the vulcanization accelerator and vulcanizing agent were added and stirred for 1.5 minutes at 90°C. After that, the mixture was rolled and molded with a roll to obtain Rubber 1 to Rubber 11, which were unvulcanized rubber sheets with a thickness of 2.5 mm, respectively.

[0116] <Preparation of resin layer> Among the components shown in Tables 3 and 4, polyester thermoplastic elastomer, polybutylene terephthalate (PBT), and carbodiimide compound were kneaded in the amounts (parts by mass) shown in Tables 3 and 4 below using a twin-screw extruder (manufactured by Technobel Co., Ltd., product name: KZW31TW-45HG, screw diameter 30 mm, L / D = 45) at 230 ° C to 250 ° C, at a shaft rotation speed of 100 rpm, and at an extrusion rate of 10 kg / h. Thereafter, the phenolic resin shown in Tables 3 and 4 below was added to the obtained kneaded resin in the amounts (parts by mass) shown in Tables 3 and 4 below, and the mixture was put into the twin-screw extruder, and further kneaded at 230 ° C to 250 ° C, at a shaft rotation speed of 100 rpm, and at an extrusion rate of 10 kg / h, and injection molding was performed to obtain resins 1 to 7, which are resin sheets having a thickness of 2 mm, respectively. It should be noted that in the case of Resin 5, kneading was performed without using a carbodiimide compound.

[0117] Among the components shown in Table 4, polyester thermoplastic elastomer, polybutylene terephthalate (PBT), and carbodiimide compound were added in the amounts (parts by mass) shown in Table 4 below to a twin-screw extruder (manufactured by Technobel Co., Ltd., product name: KZW31TW-45HG, screw diameter 30 mm, L / D=45) and kneaded under conditions of 230°C to 250°C, shaft rotation speed 100 rpm, and extrusion rate 10 kg / h. Thereafter, the phenolic resin shown in Table 4 below was added to the obtained kneaded resin in the amounts (parts by mass) shown in Table 4 below, and the mixture was added to the twin-screw extruder and further kneaded under conditions of 230°C to 250°C, shaft rotation speed 100 rpm, and extrusion rate 10 kg / h. Further, the curing agent shown in Table 4 below was added to the obtained kneaded resin in the amount (parts by mass) shown in Table 4 below, and the mixture was fed into the twin-screw extruder and further kneaded at 230°C to 250°C, a shaft rotation speed of 100 rpm, and an extrusion rate of 10 kg / h. Resin 8, a resin sheet having a thickness of 2 mm, was obtained by injection molding.

[0118] The components shown in Table 4 were added to a twin-screw extruder (manufactured by Technovel Co., Ltd., product name: KZW31TW-45HG, screw diameter 30 mm, L / D = 45) in the amounts (parts by mass) shown in Table 4 below, and kneaded at 230°C to 250°C, a shaft rotation speed of 100 rpm, and an extrusion rate of 10 kg / h, and then injection molding was performed to obtain Resin 9, a resin sheet with a thickness of 2 mm.

[0119] [Table 1]

[0120] [Table 2]

[0121] [Table 3]

[0122] [Table 4]

[0123] The numbers in the tables indicate the “addition amount (parts by mass).” Additionally, blank spaces in Tables 1 to 4 indicate that the corresponding component is not included. Details of each component shown in Tables 1 to 4 are as follows. Diene rubber 1: Natural rubber (TSR20) Diene rubber 2: Butadiene rubber (JSR, product name: BR01) Epoxy rubber 1: Epoxidized natural rubber (manufactured by Muang Mai Guthrie Company Limited, product name: ENR25, epoxidization ratio: 25%) Epoxy rubber 2: Epoxidized natural rubber (manufactured by Muang Mai Guthrie Company Limited, product name: ENR50, epoxidization ratio: 50%)

[0124] Carbon black 1: N330 carbon black (manufactured by Asahi Carbon Co., Ltd., product name: Asahi #70K, BET method) Nitrogen adsorption specific surface area: 71 m 2 / g) Carbon black 2: N550 carbon black (manufactured by Asahi Carbon Co., Ltd., product name: Asahi #65, BET method) Nitrogen adsorption specific surface area: 42 m 2 / g) Oil 1: Process oil (ENEOS, product name: process oil) Oil 2: Tris(2-ethylhexyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TOP) Fatty acid: stearic acid Tackifier 1: Butylphenol acetylene condensate resin (manufactured by BASF, product name: Koresin) Tackifier 2: Alkylphenol resin (Sumitomo Bakelite Co., Ltd., product name: Durez 19900) Metal oxide: zinc oxide Vulcanizing agent: Sulfur Scorch prevention agent: N-cyclohexylthiophthalimide (manufactured by Toray Industries, Inc., product name: Retarder CTP) The antioxidants and vulcanization accelerators used were the above-mentioned known ones in appropriate combination.

[0125] TPC1: Polyester thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 5557) TPC2: Polyester thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 4767N) TPC3: Polyester thermoplastic elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 6347) PBT: Polybutylene terephthalate (manufactured by Toray Industries, Inc., product name: Toraycon 1401X06) Carbodiimide: Carbodiimide compound (manufactured by Nisshinbo Chemical Inc., product name: Carbodilite HMV-15CA) Phenolic resin 1: Unmodified solid straight novolac type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-50731) Phenolic resin 2: Unmodified solid straight novolac type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-50235) Phenolic resin 3: Terpene-modified solid novolac-type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-12603) Hardener: Hexamethylenetetramine (manufactured by Sanshin Chemical Industry Co., Ltd., product name: Suncerer HT)

[0126] [Examples 1 to 17, Comparative Examples 1 to 4] <Preparation of test specimen> The obtained resin sheet and unvulcanized rubber sheet were used to bond the resin sheet, unvulcanized rubber sheet 1 ("Rubber sheet 1" in the table), unvulcanized rubber sheet 2 ("Rubber sheet 2" in the table), unvulcanized rubber sheet 1 ("Rubber sheet 1" in the table), and resin sheet together in that order, and vulcanized at a pressure of 2 MPa at the vulcanization temperatures and for the times shown in Tables 5 to 8 below to obtain test specimens. In the table, "-" indicates that the unvulcanized rubber sheet 2 was not used, and the resin sheet, the unvulcanized rubber sheet 1, and the resin sheet were laminated in this order. The carbon black content ("CB amount (parts by mass)" in the table) and the epoxidation ratio of the rubber in the rubber sheet of the obtained test specimen, as well as the polyester thermoplastic elastomer content ("TPC amount (% by mass)" in the table), phenol resin content ("PH amount (% by mass)" in the table), and carbodiimide compound content ("CI amount (% by mass)" in the table) in the entire resin sheet are shown in Tables 5 to 8.

[0127] <Adhesive strength evaluation> Using the test pieces obtained in each example, a peel test was performed in which one resin sheet was pulled 180 degrees from the other resin sheet at a tensile speed of 100 mm / min in an environment of 90°C using a precision universal testing machine (Autograph AG-X 5kN, manufactured by Shimadzu Corporation), and the average value in the stroke range of 20 mm to 70 mm, where the peel resistance was relatively stable, was obtained as the peel resistance (unit: N / 25 mm). The results and the locations of failure are shown in Tables 5 to 8 below. In the tables, "Base material / interface" indicates that failure occurred in both the base material and the interface.

[0128] [Table 5]

[0129] [Table 6]

[0130] [Table 7]

[0131] [Table 8]

[0132] As can be seen from the evaluation results shown in Tables 5 to 8, the present examples have higher peel resistance at 90° C. and are superior in adhesion between the rubber layer and the resin layer, as compared with the comparative examples. [Explanation of symbols]

[0133] 10 Tires 11 Rubber sheet 12 Belt member 13 Side rubber 14 Bead section 16 Side section 17 Tire Case 17A Resin material for welding 17H Tire half 18 Crown section 18A Crown outer surface 20 Bead Core 24 Reinforcement cord 26 Coating resin 28 Resin-coated cord 30 Tread 30A Tread Groove 50 Core filler material 62 Bead wire bundle 63 Coating Resin 65 Covering layer 80 Tires 82 Carcass ply 86 Carcass 88 Bead filler 89 Bead filler 90 Inner Liner 91 Rubber parts 92 Side rubber layer 94 Tire Case 110 Tires

Claims

1. a first layer which is a rubber layer including a rubber containing an epoxidized diene-based rubber and carbon black; a second layer provided in direct contact with the first layer and being a resin layer containing a resin containing a polyester-based thermoplastic elastomer and a phenolic resin; the content of the epoxidized diene rubber is 50 to 100 mass% based on the total amount of the rubber; The epoxidation rate of the epoxidized diene rubber is 30 to 60%, The content of the phenol resin is 3% by mass or more based on the entire second layer. Resin rubber composite.

2. The resin-rubber composite according to claim 1, wherein the carbon black is contained in an amount of 25 to 65 parts by mass per 100 parts by mass of the rubber.

3. The resin-rubber composite according to claim 1 or 2, wherein a content of the polyester-based thermoplastic elastomer is 50% by mass or more with respect to the entire second layer.

4. The resin-rubber composite according to any one of claims 1 to 3, wherein the second layer contains a carbodiimide compound.

5. The resin-rubber composite according to any one of claims 1 to 4, further comprising a third layer which is a rubber layer containing a diene-based rubber and is in direct contact with the first layer and is provided on a surface of the first layer opposite to the second layer.

6. A tire comprising the resin-rubber composite according to any one of claims 1 to 5.

7. An annular tire frame member; a belt member provided on an outer side in a tire radial direction of the tire frame member and including the second layer; a rubber member provided on an outer side of the belt member in the tire radial direction and including the first layer; 7. The tire of claim 6, having

8. an annular tire frame member including the second layer; a rubber member provided on at least one of an outer side and an inner side in the tire width direction of the tire frame member, the rubber member including the first layer; 7. The tire of claim 6, having

9. a tire frame member having an annular shape including the first layer, The tire according to claim 6 , wherein a bead portion in 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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