Resin-rubber composite and tire

Abstract

To provide a resin-rubber composite excellent in adhesiveness at 150°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, carbon black, and an organophosphorus compound; 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 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 the resin. On the other hand, when a component including a resin layer is used as part of a tire component, the resin layer may be disposed in a position where it contacts a rubber layer of another component, 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, by providing a layer of an organic solvent-based adhesive between the resin layer and the rubber layer, peeling at the interface between the resin layer and the rubber layer is prevented. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-46030 Summary of the Invention [Problem to be solved by the invention]

[0004] As mentioned above, when using organic solvent-based adhesives, the solvent needs to be evaporated after the coating is formed, which requires a long drying process. In addition, the installation of exhaust equipment 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 force, 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, the present invention aims to provide a resin-rubber composite having excellent adhesion between a resin layer and a rubber layer in direct contact with the resin layer at 150°C, 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 which is a rubber layer containing 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; 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 with respect to 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 with respect to the entire second layer. <1> ~ <3> 10. The resin-rubber composite according to claim 9, wherein the resin-rubber composite is a rubber-based composite. <5> The epoxidation ratio of the rubber is 30% to 60%. <1> ~ <4> 10. The resin-rubber composite according to claim 9, wherein the resin-rubber composite is a rubber-based composite. <6> The content of the organic phosphorus compound is 0.5 parts by mass or more relative to 100 parts by mass of the rubber. <1> ~ <5> 10. The resin-rubber composite according to claim 9, wherein the resin-rubber composite is a rubber-based composite. <7> the second layer comprises a carbodiimide compound; <1> ~ <6> 10. The resin-rubber composite according to claim 9, wherein the resin-rubber composite is a rubber-based composite. <8> The tire further includes a third layer, which is a rubber layer containing a diene 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. <1> ~ <7> 10. The resin-rubber composite according to claim 9, wherein the resin-rubber composite is a rubber-based composite. <9> <1> ~ <8> A tire having the resin-rubber composite according to any one of the above. <10> 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 <9> A tire as described in <11> 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 <9> A tire as described in <12> an annular tire frame member including the first layer; The bead portion of the tire frame member includes at least one of a bead core including the second layer and a bead filler including the second layer. <9> A tire as described in [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a resin-rubber composite having excellent adhesion at 150°C between a resin layer and a rubber layer in direct contact with the resin layer, and a tire having the resin-rubber composite. [Brief explanation 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. [Figure 2] 1 is a cross-sectional view taken along the tire width direction, showing the configuration of a tire according to a first embodiment. [Figure 3]FIG. 10 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. 10 is a cross-sectional view taken along the tire width direction showing the configuration of a tire according to a third embodiment. [Figure 5] FIG. 10 is an enlarged cross-sectional view of a bead portion of a tire according to a fourth embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be implemented with appropriate modifications 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, but 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, unless otherwise specified, when multiple substances corresponding to each component are present in the composition. In this specification, unless otherwise specified, the term "major component" means the component that is contained in the mixture in the largest amount by mass.

[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. As used herein, the term "thermoplastic elastomer" refers to a copolymer having hard segments and soft segments. Specific examples of thermoplastic elastomers include copolymers having a polymer that is crystalline and comprises a hard segment with a high melting point or a hard segment with high cohesive strength, and a polymer that is amorphous and comprises 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. Examples of the hard segments include segments with 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 through intermolecular hydrogen bonding or π-π interactions. Examples of the soft segments include segments with a long-chain group (e.g., a long-chain alkylene group) in the main chain, which allows for a high degree of freedom in molecular rotation and has elasticity.

[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, carbon black, and an organic phosphorus compound, and a second layer which is provided in direct contact with the first layer and is a resin layer containing a resin containing a polyester-based thermoplastic elastomer and a phenolic resin. Hereinafter, the first layer will also be referred to as the “epoxy rubber layer,” and the second layer will also be referred to as the “resin layer.” Furthermore, a rubber member including the first layer will also be referred to as the “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 improve 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 improved, the solvent needs to be evaporated after the coating film is formed, and therefore there is room for improvement in terms of simplifying the manufacturing process, reducing costs, etc. Therefore, in a composite in which a resin layer and a rubber layer are arranged so as to be in contact with each other, it is desirable to obtain excellent adhesion between the two even when the two are in direct contact without the use of an adhesive. Furthermore, for example, when the composite is applied to a tire, repeated strain during driving can cause spontaneous heating, which can reach around 150°C, and it may be desirable to obtain excellent adhesion even at 150°C.

[0014] In contrast, in the composite of the present embodiment, the rubber layer in direct contact with the resin layer is an epoxy rubber layer containing a rubber containing an epoxidized diene rubber, carbon black, and an organic phosphorus compound, and the resin layer contains a resin containing a polyester-based thermoplastic elastomer and a phenolic resin. Therefore, the adhesiveness between the resin layer and the rubber layer in direct contact with the resin layer is excellent at 150°C. 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 groups of the epoxidized diene rubber contained in the epoxy rubber layer react with the carboxyl groups of the polyester-based thermoplastic elastomer contained in the resin layer to form a covalent bond. Then, some of the hydroxyl groups of the phenolic resin contained in the resin layer react with the epoxy groups of the epoxidized diene rubber to form a covalent bond, and other hydroxyl groups of the phenolic resin react with the carboxyl groups of the polyester-based thermoplastic elastomer to form a covalent bond. Additionally, the inclusion of carbon black in the epoxy rubber layer allows the reinforcing effect of the carbon black in the epoxidized diene rubber to be exerted without impairing the reactivity of the epoxy groups, thereby further strengthening the adhesion between the resin layer and the rubber layer. The organophosphorus compound contained in the epoxy rubber layer promotes the reaction between the epoxy groups of the epoxidized diene rubber and the hydroxyl groups of the phenolic resin, further strengthening the adhesion between the resin layer and the rubber layer, presumably resulting in excellent adhesion even at temperatures as high as 150°C.

[0015] In particular, in this embodiment, since the organic phosphorus compound is contained in the epoxy rubber layer, it is believed that the reaction-accelerating effect of the organic phosphorus compound is more easily achieved when bonding the resin layer and the epoxy rubber layer than when the organic phosphorus compound is contained in the resin layer. Specifically, when the organic phosphorus compound is contained in a resin layer containing a polyester-based thermoplastic elastomer and a phenolic resin, kneading the resin layer at a temperature above the melting point of the polyester-based thermoplastic elastomer (e.g., around 250°C) during the resin layer formation process can reduce the number of functional groups due to reactions between the functional groups, making it difficult to achieve adhesive strength to the epoxy rubber layer. In contrast, when the organic phosphorus compound is contained in the epoxy rubber layer, the reduction in the number of functional groups is less likely to occur, and it is believed that the reaction-accelerating effect is more easily achieved. Note that in the composite according to this embodiment, the resin layer may contain an organic phosphorus compound.

[0016] In this embodiment, since the resin layer and the rubber layer that is in direct 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.

[0017] As described above, the composite of this embodiment only needs to have 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 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, in direct contact with the epoxy rubber layer. Each layer constituting the composite body according to this embodiment will be described below.

[0018] <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, carbon black, and an organic phosphorus compound, and may contain other components as needed. The epoxy rubber layer may be a layer that is a vulcanizate of a rubber composition containing a rubber containing an epoxidized diene rubber, carbon black, and an organic phosphorus compound. That is, 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, carbon black, and an organic phosphorus compound is vulcanized in direct contact with a resin layer. The rubber composition may also contain other components as necessary.

[0019] (rubber) The epoxy rubber layer preferably contains rubber as a main component. The rubber content relative to the total amount of the epoxy rubber layer is, for example, 50% by mass or more, or may be 55% by mass or more, or 60% by mass or more, and may be 80% by mass or less.

[0020] The rubber contains at least an epoxidized diene rubber, and may further contain other rubbers as required. From the viewpoint of improving adhesion to the resin layer, the content of the epoxidized diene rubber is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass, relative to the total amount of rubber.

[0021] Here, the epoxidized diene rubber is a diene rubber in which some of the carbon-carbon double bonds contained therein 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), as well as 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. Among these, the epoxidized diene rubber preferably contains epoxidized natural rubber obtained by epoxidizing natural rubber.

[0022] When the rubber contains other rubbers, the types of the other rubbers are not particularly limited. Examples of the other rubber include non-epoxidized diene rubber and non-diene rubber. Among these, from the viewpoint of improving adhesion to the resin layer, non-epoxidized diene rubber is preferred, and non-epoxidized natural rubber is more preferred. One type of the other rubber may be used alone, or two or more types may be used as a mixture.

[0023] 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 even more preferably 40% to 50%.

[0024] Here, the epoxidation ratio refers to a value expressed by the following formula (1), where Ep is the number of epoxy groups contained in the entire rubber, and En is the number of carbon-carbon double bonds contained in the entire rubber that remain unepoxidized. Equation (1): Epoxidation ratio (%) = (Ep / (Ep+En)) × 100 When the rubber contained in the epoxy rubber layer contains rubber other than the epoxidized diene rubber, the number of double bonds En is a value including the number of double bonds contained in the other rubber.

[0025] 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.

[0026] (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. One type of carbon black may be used alone, or two or more types may be used in combination. From the viewpoint of reinforcing the epoxy rubber layer and improving adhesion to the resin layer, the content of carbon black contained 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 contained in the epoxy rubber layer.

[0027] The nitrogen adsorption surface area of ​​the carbon black is not particularly limited, but from the viewpoint of improving adhesion to the resin layer, it is preferred to use a surface area of ​​20 m 2 / g or more, and 25m 2 / g or more is more preferable, and 30m 2 / g or more is more preferable. The upper limit of the nitrogen adsorption surface area of ​​carbon black is not particularly limited. The nitrogen adsorption surface area of ​​carbon black is preferably 250 m 2 / g or less. The nitrogen adsorption surface area of ​​carbon black can be determined by the BET method using N2 gas in accordance with ASTM D3037-88.

[0028] (organophosphorus compounds) The organic phosphorus compound is not particularly limited as long as it is an organic compound containing a carbon-phosphorus bond, and examples thereof include phosphines, phosphine oxides, phosphonium salts, and diphosphines. Examples of phosphines include trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-propylphosphine, tri-tert-butylphosphine, triisobutylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, diethylphenylphosphine, dichloro(ethyl)phosphine, dichloro(phenyl)phosphine, and chlorodiphenylphosphine.

[0029] Examples of phosphine oxides include tri-n-octylphosphine oxide, triphenylphosphine oxide, and diphenylphosphinylhydroquinone. Examples of phosphonium salts include tetrabutylphosphonium bromide, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-propyltriphenylphosphonium bromide, i-propyltriphenylphosphonium iodide, n-butyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tri-tert-butylphosphonium tetraphenylborate, and triphenylphosphinetriphenylborane. Examples of diphosphines include 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, and 1,4-bis(diphenylphosphino)butane.

[0030] Among these, the organic phosphorus compound is preferably a phosphine from the viewpoint of improving adhesion to the resin layer, and among them, a phosphine having an aromatic ring is more preferable, a phosphine having three or more aromatic rings is even more preferable, and a triarylphosphine is particularly preferable. Furthermore, from the viewpoint of improving adhesion to the resin layer, the organic phosphorus compound preferably contains at least one selected from the group consisting of triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, and tri-p-tolylphosphine. The organic phosphorus compounds may be used alone or in combination of two or more.

[0031] From the viewpoint of improving adhesiveness, the content of the organophosphorus compound is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, and even more preferably 0.9 parts by mass or more, relative to 100 parts by mass of rubber contained in the epoxy rubber layer. From the viewpoint of improving dispersibility of the organophosphorus compound itself in the epoxy rubber layer, the content of the organophosphorus compound is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less, relative to 100 parts by mass of rubber contained in the epoxy rubber layer. The content of the organic phosphorus compound is preferably 0.5 parts by mass to 10 parts by mass, more preferably 0.7 parts by mass to 8 parts by mass, and even more preferably 0.9 parts by mass to 6 parts by mass, per 100 parts by mass of rubber contained in the epoxy rubber layer.

[0032] (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.

[0033] 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 material including carbon black and silica is preferably 25 to 65 parts by mass, more preferably 30 to 60 parts by mass, and even more preferably 35 to 55 parts by mass per 100 parts by mass of rubber contained in the epoxy rubber layer, from the viewpoint of reinforcing the rubber layer and making it less likely to generate heat when repeated strain occurs.

[0034] As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, etc. 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, and xanthates can be used. Examples of fatty acids include stearic acid, palmitic acid, myristic acid, and lauric acid, which may be incorporated in the form of a salt such as zinc stearate. Of 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 types. Examples of antioxidants include amine-ketone, imidazole, amine, phenol, sulfur, and phosphorus antioxidants. Examples of the tackifier include phenolic resins, rosin resins, and terpene resins. An example of the scorch inhibitor is N-cyclohexylthiophthalimide.

[0035] <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 a resin containing at least a polyester-based thermoplastic elastomer and a phenolic resin, and may contain other components as needed. The resin layer may be a layer that is a reaction product of a resin composition containing a polyester-based thermoplastic elastomer and a phenolic resin. The resin composition may contain other components as needed. The resin layer preferably contains a resin as a main component. Specifically, the resin content of 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.

[0036] The resin contains at least a polyester-based thermoplastic elastomer and a phenolic resin, and may further contain other resins as required.

[0037] From the viewpoint of improving adhesion to the epoxidized rubber layer, the content of the polyester-based 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, relative to the total amount of the resin layer. There is no particular upper limit to the content of the polyester-based thermoplastic elastomer. The content of the polyester-based thermoplastic elastomer may be, for example, in the range of 99% by mass or less, relative to 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.

[0038] From the viewpoint of improving adhesion to the epoxidized rubber layer, the content of the phenol resin is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more, relative to the total amount of the resin layer. Furthermore, 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 (e.g., −10°C) is improved compared to when the content is higher than the above range. Furthermore, when the resin layer of the composite is used as a tire frame member, when the content of the phenolic resin is within the above range, 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 3% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, and even more preferably 7% by mass to 30% by mass. Here, the content of the phenolic resin is a value including that which has reacted with other components such as polyester-based thermoplastic elastomer and is covalently bonded thereto. The phenol resin may be used alone or in a mixture of two or more kinds.

[0039] (Polyester-based thermoplastic elastomer) Examples of polyester-based thermoplastic elastomers include materials in which at least polyester forms crystalline hard segments with a high melting point, and other polymers (e.g., polyesters or polyethers) form amorphous soft segments with a low glass transition temperature.

[0040] An aromatic polyester can be used as the polyester forming the hard segment. 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 also be formed 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, etc.). The polyester may be a polyester derived from 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 copolymerized polyester containing two or more of these dicarboxylic acid components and diol components. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component, or the like in an amount of 5 mol % or less. Examples of polyesters that form hard segments include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, with polybutylene terephthalate being preferred.

[0041] Examples of polymers that form soft segments 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 that form soft segments include poly(tetramethylene oxide) glycol, ethylene oxide adducts of poly(propylene oxide) glycol, poly(ε-caprolactone), polybutylene adipate, and polyethylene adipate.

[0042] 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.

[0043] Examples of the combination of the hard segment and the soft segment include the combinations 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.

[0044] Commercially available polyester thermoplastic elastomers include, for example, the "Hytrel" series (e.g., 3046, 5557, 6347, 4047N, 4767N, etc.) manufactured by DuPont-Toray Co., Ltd., and the "Pelprene" series (e.g., P30B, P40B, P40H, P55B, P70B, P150B, P280B, E450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) manufactured by Toyobo Co., Ltd.

[0045] The polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer that forms a hard segment and a polymer that forms a soft segment by a known method.

[0046] (phenolic resin) Examples of phenolic resins include condensates of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, and resorcinol 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 phenolic resins include unmodified straight phenolic resins, terpene-modified phenolic resins, aralkyl-modified phenolic resins, xylylene-modified phenolic resins, melamine-modified phenolic resins, and oil-modified phenolic resins.

[0047] Among these, from the viewpoint of the physical properties of the resin layer and workability during resin layer formation, the phenolic resin is preferably a novolac phenolic resin, and among these, it is more preferable to include at least one selected from the group consisting of novolac straight phenolic resins, novolac terpene-modified phenolic resins, novolac oil-modified phenolic resins, novolac aralkyl-modified phenolic resins, novolac xylylene-modified phenolic resins, and novolac melamine-modified phenolic resins, and it is even more preferable to include at least one selected from the group consisting of novolac straight phenolic resins, novolac terpene-modified phenolic resins, and novolac oil-modified phenolic resins.

[0048] The hydroxyl group equivalent of the phenolic resin is preferably 100 g / eq to 300 g / eq, more preferably 100 g / eq to 200 g / eq, and even more preferably 100 g / eq to 150 g / eq. A phenolic resin having a hydroxyl equivalent weight within the above range has the advantage of being superior in adhesiveness compared to phenolic resins having a hydroxyl equivalent weight greater than the above range, and also has the advantage of being structurally more readily available compared to phenolic resins having a hydroxyl equivalent weight less than the above range. The hydroxyl equivalent weight is measured in accordance with JIS K0070:1992.

[0049] (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. One type of the other resins may be used alone, or two or more types may be used as a mixture. 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.

[0050] Examples of the polyester thermoplastic resin include polyesters that form the hard segments of the above-mentioned polyester thermoplastic elastomers. Specific examples of polyester-based thermoplastic resins include aliphatic polyesters such as polylactic acid, polyhydroxy-3-butylbutyrate, polyhydroxy-3-hexylbutyrate, 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.

[0051] Commercially available polyester thermoplastic resins include, for example, 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.

[0052] (Carbodiimide compounds) The resin layer preferably contains a carbodiimide compound as another component. The inclusion of a carbodiimide compound in the resin layer improves the mechanical durability of the resin layer and also improves adhesion to the epoxy rubber layer. The reason for this is unclear, but is presumed to be 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)) possessed by the polyester-based thermoplastic elastomer to form a covalent bond. It is presumed that the polyester-based thermoplastic elastomer is crosslinked and bonded to the carbodiimide compound, thereby improving the mechanical durability of the resin layer and also improving adhesion to the epoxy rubber layer due to the formation of new carboxy groups derived from the crosslinked carbodiimide compound.

[0053] 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.

[0054] Examples of the organic isocyanate include aromatic isocyanates, aliphatic isocyanates, and mixtures thereof. The organic group contained in the organic isocyanate may be either an aromatic organic group or an aliphatic organic group, or 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.

[0055] 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 refers to a compound having two or more carbodiimide groups.

[0056] Commercially available carbodiimide compounds may be used, such as Carbodilite (registered trademark) manufactured by Nisshinbo Chemical Inc. (e.g., HMV-15CA, LA-1), and Stavaxol (registered trademark) manufactured by Rhein Chemie (e.g., P, P-100, etc.).

[0057] The functional group equivalent of the carbodiimide compound is preferably 100 g / eq to 500 g / eq, more preferably 100 g / eq to 400 g / eq, and even more preferably 100 g / eq to 300 g / eq. When the functional group equivalent weight 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 storage stability is higher compared to when it is less than the above range.

[0058] The carbodiimide compound preferably has a softening point (softening temperature) of 50° C. or higher and 150° C. or lower from the viewpoints of supply stability during twin-screw kneading and ease of melt-kneading with the polyester-based thermoplastic elastomer.

[0059] 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 viewpoints 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 viewpoints of improving processability by suppressing an increase in viscosity during production of the resin layer. The content of the carbodiimide compound is preferably 0.1% by mass to 10% by mass, more preferably 0.3% by mass to 5% by mass, and even more preferably 0.5% by mass to 3% by mass. Here, the content of the carbodiimide compound is a value including those in a covalent bond state resulting from reaction with other components such as polyester-based thermoplastic elastomers.

[0060] (hardening agent) The resin layer may contain a curing agent as another component. A formaldehyde donor that generates formaldehyde upon heating is used as the curing agent. Examples of the curing agent include hexamethylenetetramine, paraformaldehyde, hexamethoxymethylmelamine, acetaldehyde ammonia, α-polyoxymethylene, polymethylolmelamine derivatives, oxazolidine derivatives, and polymethylolated acetylene urea. Hexamethylenetetramine and hexamethoxymethylmelamine are preferred. Hexamethoxymethylmelamine is particularly preferred.

[0061] 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. By having the curing agent content within the above range, the increase in viscosity accompanying an increase in curing rate is suppressed compared to when the content is higher than the above range, resulting in the advantage of excellent processability. 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, 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, 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, the content of the phenolic resin. When the resin layer contains a curing agent, the content of the curing agent may be 0.01 times or more the content of the phenolic resin. Here, the content of the curing agent is a value including that which has reacted with other components such as polyester-based thermoplastic elastomer and formed covalent bonds.

[0062] (Other ingredients) The resin layer may contain other components such as additives to the extent that the effect is not impaired. Examples of other components include various fillers (e.g., silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, and weather resistance agents.

[0063] <Diene rubber layer> In the composite body according to this 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 needed. 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. Specific examples of the diene rubber, other rubbers, and components other than rubber are the same as those described for the epoxy rubber layer.

[0064] <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.

[0065] The unvulcanized epoxy rubber layer can be obtained, for example, by kneading the materials constituting the epoxy rubber layer and molding them into a desired shape. The kneading temperature during formation of 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. Examples of kneaders include ordinary kneaders such as mixing rolls, Sigma-type rotary blade kneaders, Banbury mixers, high-speed twin-screw continuous mixers, and single-screw, twin-screw, and multi-screw extruder kneaders. Examples of molding methods include extrusion molding and roll molding.

[0066] The resin layer can be obtained, for example, by melt-kneading the materials constituting the resin layer and molding them into a desired shape. The kneading temperature during resin layer formation can be, 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. Furthermore, when the resin layer contains another resin with 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 kneading machine used for melt-kneading is the same as the kneading machine used to obtain the unvulcanized epoxy rubber layer. Furthermore, molding methods include, for example, injection molding, vacuum molding, pressure molding, melt casting, etc.

[0067] 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 comes into contact with the unvulcanized epoxy rubber layer and the surface of the unvulcanized epoxy rubber layer that comes into contact with the resin layer are brought into contact 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.

[0068]

[0033] When a composite having an epoxy rubber layer, a resin layer, and a diene rubber layer is produced, the composite is produced, for example, through the steps 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 heating the laminate to vulcanize the unvulcanized epoxy rubber layer and the unvulcanized diene rubber layer. The unvulcanized diene rubber layer can be obtained in the same manner as the unvulcanized epoxy rubber layer.

[0069] <Uses of the composite> The composite according to this embodiment is applicable to various fields in which members including a resin layer and members 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, and bicycles.

[0070] When the composite is used in a tire, the following combinations may be mentioned as examples of the combination of the resin layer and the epoxy rubber layer in the composite. 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 component 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 that covers 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 coats 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).

[0071] Furthermore, when the composite 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.

[0072] [tire] The tire of the present invention comprises at least the composite described above. Hereinafter, embodiments of a tire having the above-described composite will be described with reference to the drawings, but the tire of the present invention is not limited to these examples.

[0073] First Embodiment A tire according to a first embodiment includes an annular tire frame member including a resin, a belt member provided radially outward of the tire frame member and including a plurality of reinforcing cords and a coating resin coating the reinforcing cords, a rubber sheet that is an epoxy rubber member provided on the radially outward surface of the belt member in direct contact with the coating resin of the belt member, and a tread provided on the radially outward surface of the rubber sheet in direct contact with the rubber sheet. In the first embodiment, the tire includes a composite including 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 multi-layer structure 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.

[0074] The first embodiment will be described below with reference to Figures 1 and 2. In Figure 2, arrow W indicates a direction parallel to the tire rotation axis (hereinafter, sometimes 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, sometimes referred to as the "tire radial direction"). Furthermore, dashed dotted line CL indicates the center line of the tire (hereinafter, sometimes referred to as the "tire equatorial plane").

[0075] FIG. 1 is a perspective view showing a cross section of a part of a tire according to a first embodiment, and FIG. 2 is a cross section taken along the tire width direction 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.

[0076] -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 in an annular shape in the tire circumferential direction. The tire case 17 is configured to include a pair of bead portions 14 spaced apart in the tire width direction, a pair of side portions 16 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 the 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 convex outward in the tire width direction.

[0077] 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 radially outward of the tire.

[0078] 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 have a curved shape that bulges outward in the tire radial direction. Note that 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.

[0079] 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. These tire halves 17H are arranged opposite each other and end portions of the half-width crown portions 18 are joined together at the tire equatorial plane CL. These end portions are joined together using, for example, a welding resin material 17A.

[0080] 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, or a hard resin. Note that if sufficient rigidity of the bead portion 14 can be ensured, the bead core 20 itself may be omitted.

[0081] The tire case 17 may be an integrally molded product, or may be manufactured as three or more separate resin members and then formed by joining them together. For example, the tire case 17 may be manufactured as separate parts (e.g., bead portion 14, side portion 16, crown portion 18) and then formed by joining them together. In this case, each part of the tire case 17 (e.g., bead portion 14, side portion 16, crown portion 18) may be formed from a resin material having different characteristics.

[0082] Further, the tire case 17 may be provided with a reinforcing material (polymer material, metal fiber, cord, nonwoven fabric, woven fabric, etc.) embedded therein.

[0083] Furthermore, a covering layer 21 may be formed on the surface of the bead portion 14 at a portion that comes into contact with the rim (not shown) to improve 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 bead portion 14 on the inner side in the tire width direction to the outer side in the tire width direction, pass through the outer surface of the side portion 16, and extend to the vicinity of the outer end of the belt member 12 in the tire width direction. Furthermore, the extending end of the covering layer may be covered by the tread 30, which will be 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, a composite may be used in which the tire case 17 corresponds to a resin layer containing a polyester-based thermoplastic elastomer and a phenolic resin, and the coating layer 21 corresponds to an epoxy rubber layer containing an epoxidized diene-based rubber, carbon black, and an organic phosphorus compound.

[0084] -Belt material- Next, the belt member 12 will be described. The belt member 12 is configured by a resin-coated cord 28 wound spirally around the outer periphery of the tire case 17 in the tire circumferential direction and joined to 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.

[0085] The reinforcing cord 24 is made of a monofilament (single wire) such as a metal fiber or an organic fiber, or a multifilament (twisted wire) made of twisted fibers, and the coating resin 26 is made 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 a single metal cord and a multifilament (twisted wire) made of multiple twisted metal cords, but from the viewpoint of further improving the durability of the tire, a multifilament is preferred. 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 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.

[0086] 1 and 2, the layer of the resin-coated cords 28 is a single layer, and the reinforcing cords 24 are arranged in a row in the tire width direction, but this is not limiting. The belt member 12 may be a belt member with a laminated structure in which the resin-coated cords 28 are wound spirally in the tire circumferential direction to form a layer, and then another resin-coated cord 28 is wound around the outer peripheral surface of the layer.

[0087] 1 and 2 is configured by spirally winding and joining a resin-coated cord 28 around the outer circumferential surface of the tire case 17, but is not limited to this. For example, the belt member may be configured by winding a sheet in which a plurality of reinforcing cords 24 and a coating resin 26 are integrated into one piece around the outer circumferential surface of the tire case 17.

[0088] -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 on the radially outer side of the belt member 12 in direct contact with the belt member 12, and a tread 30 is arranged on the radially outer side of the rubber sheet 11 in direct contact with the rubber sheet 11. The rubber sheet 11 is made of a rubber material containing rubber containing epoxidized diene rubber, carbon black, and an organic phosphorus compound, and the tread 30 is made of a rubber material containing diene rubber. The tread 30 may be a multi-layer body in which multiple layers of rubber material containing diene rubber are laminated. The rubber sheet 11 and the tread 30 are laminated in an unvulcanized state onto the belt member 12 on the tire case 17, for example, and then vulcanization bonded thereto. 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.

[0089] 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 limiting and more grooves 30A may be formed. Also, a known tread pattern may be used.

[0090] 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, carbon black, and an organic phosphorus compound may be provided in direct contact with the belt member 12.

[0091] - 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, an annular tire case 17 is formed.

[0092] Next, a description will be given of a process of winding the resin-coated cord 28 around the outer periphery of the tire case 17. Specifically, while the resin-coated cord 28 is fed 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. 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 bond the resin-coated cord 28 and the outer periphery 18A, which is also molten, and these are solidified by cooling. In this way, 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.

[0093] Next, the rubber sheet 11 and the tread 30 are formed on the outer peripheral surface of the belt member 12 . Specifically, first, an unvulcanized rubber sheet is wound around the outer peripheral surface of the belt member 12. Next, an unvulcanized tread is wound around the outer peripheral surface of the unvulcanized rubber sheet. 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 on which the belt member 12 is provided. 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 placed in a vulcanization can or a 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.

[0094] Second Embodiment A tire according to a second embodiment includes an annular tire frame member including rubber, a belt member provided radially outward of the tire frame member and including a plurality of reinforcing cords and a coating resin coating the reinforcing cords, a tread provided on the radially outward surface of the belt member, and rubber sheets that are epoxy rubber members 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. The second embodiment includes 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, too, 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 in between. Furthermore, a tire frame member having a rubber layer corresponding to another rubber layer may be used instead of a tire frame member having a rubber layer corresponding to the diene rubber layer, and a 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 in between.

[0095] 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, the tire 80 according to the second embodiment includes a tire case 94, which is an example of an annular tire frame member made up of 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 the same as those in the first embodiment, and therefore the description thereof will be omitted.

[0096] 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 bead cores 20 are embedded, and a carcass 86 consisting of one carcass ply 82 straddles 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.

[0097] 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 cords of the carcass ply 82 may be made of, for example, PET, but may be made of other conventionally known materials. The coating rubber is a rubber material containing diene rubber, and constitutes a coating layer (not shown) corresponding to the diene rubber layer.

[0098] The carcass ply 82 has end portions in the tire width direction folded back toward the tire radial direction outside 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.

[0099] A bead filler 88 whose thickness gradually decreases from the bead core 20 toward the tire radially outer side is disposed between the main body portion 82A and the turned-up portion 82B of the carcass ply 82. In the tire 80, the 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.

[0100] An inner liner 90 made of rubber is disposed on the tire inner side of the carcass 86, and a side rubber layer 92 made of a rubber material containing rubber is disposed on the tire width direction outer side of the carcass 86. 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.

[0101] 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 to this. For example, the belt member 12 may be provided in direct contact with a carcass consisting of a carcass ply formed by coating cords with a coating rubber containing a rubber containing an epoxidized diene rubber, carbon black, and an organic phosphorus compound. 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, carbon black, and an organic phosphorus compound 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 pattern that is conventionally known.

[0102] (Tire manufacturing method) Next, an example of a method for manufacturing the tire 80 of this embodiment will be described. First, an unvulcanized tire case 94 is formed on 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.

[0103] On the other hand, the belt member 12 is formed as follows. Specifically, the resin-coated cord 28 is fed toward the outer circumferential surface of a belt-forming drum (not shown). The resin-coated cord 28 is heated by hot air and, in a melted state, is pressed against the outer circumferential surface of the belt-forming drum, 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.

[0104] Next, the belt member 12, in which the resin-coated cords 28 have been cooled and the coating resin 26 has solidified, is removed from the belt building drum. Then, an unvulcanized rubber sheet 11 is attached to the inner circumferential surface of the removed belt member 12, and then the belt member 12 is placed radially outside the unvulcanized tire case 94 on the tire building drum. Thereafter, the tire case 94 is expanded, and the outer circumferential surface of the tire case 94, in other words the outer circumferential surface of the carcass 86, is pressed against the inner circumferential 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 to the unvulcanized rubber sheet 11, thereby completing a green tire. The green tire thus manufactured is vulcanized in a vulcanization mold to complete the tire 80.

[0105] <Third embodiment> A tire according to a third embodiment includes a composite including an annular tire frame member including a resin, a belt member provided radially outward 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 radially outer surface of the belt member in direct contact with the coating resin of the belt member, a tread provided on the 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 radially outer side of the tire frame member in the tire width direction. The third embodiment includes 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 the side rubber corresponding to the 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 this is not limitative. The tread may also be a multi-layer structure of multiple diene rubber layers.

[0106] Fig. 4 is a cross-sectional view taken along the tire width direction, showing the configuration of a tire according to the 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 and on the tire radially outer surface and tire widthwise 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 widthwise outer surface of the tire case 17. The tire case 17, the belt member 12, the rubber sheet 11, and the tread 30 are the same as those in the first embodiment, and therefore their description will be omitted. The side rubber 13 is made of a rubber material containing a rubber containing an epoxidized diene rubber, carbon black, and an organic phosphorus compound.

[0107] 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, but 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.

[0108] <Fourth embodiment> The fourth embodiment is an example of a configuration in which the composite is provided in the bead portion of an annular tire frame member containing rubber. Specifically, the tire frame member is composed of 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 turned-up portion folded from the inside to the outside around the bead core, a resin bead filler provided between the bead cores, the main portion, and the turned-up portion, a rubber sheet that 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 including the coating resin and bead filler on the bead core corresponding to the resin layer, the rubber sheet corresponding to the epoxy rubber layer, and the rubber member corresponding 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 it is sufficient that at least one of the bead core and the bead filler has a resin layer. For example, if 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, with a rubber sheet corresponding to the epoxy rubber layer interposed therebetween, 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.

[0109] Fig. 5 is an enlarged cross-sectional view of a bead portion of a tire according to Embodiment 4. In Fig. 5, members common to other figures are given the same reference numerals and descriptions 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, surrounded by a rubber sheet 11. However, the bead core 20 and the bead filler 89 may be separate bodies.

[0110] 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 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 making up the bead filler 89 may be different from that of the covering layer 65 of the bead core 20. Furthermore, the resin material making up the bead filler 89 may be different for each portion of the bead filler 89.

[0111] 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 that make up the bead core 20 appear when viewed in cross section in the tire width direction, and the actual number of bead wires that make up 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 by winding multiple bead wires each one time or multiple times in the tire circumferential direction. The bead wires may be made of any known material, such as a steel cord, which may be made of a steel monofilament or a stranded wire, or may be made of organic fiber or carbon fiber.

[0112] 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 when viewed in a cross section in the tire width direction so as to surround the entire circumference of the bead wire bundle 62 of the bead core 20. The covering layer 65 does not have to be annular in a portion of the tire circumferential direction when viewed in a cross section in the tire width direction, and may be, for example, C-shaped. In this example, when viewing the 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, if 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 if 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 viewing the 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.

[0113] The tire of this embodiment is manufactured in the same manner as the tire of the second embodiment described above. 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. A belt member and an unvulcanized tread are then provided as necessary to obtain a green tire, which is then vulcanized and molded to obtain a tire.

[0114] An example of a method for manufacturing the core filler member 50 will now be described. The manufacturing method of the core filler member 50 includes, for example, an annular body forming step, an injection molding step, and a cooling step.

[0115] In the annular body forming process, a strip member formed by coating one or more bead wires with the coating resin 63 is wound to form an annular body. In the bead core 20 shown in Fig. 5, for example, strip members formed by coating three bead wires with the coating resin 63 are spirally wound and stacked in three layers. In this example, in the annular body forming step, the outer periphery of the bead wire is coated with molten coating resin 63 and then 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 then solidifying the molten coating resin 63. Alternatively, the layers can be joined together by adhering them with an adhesive or the like.

[0116] Following the annular body forming process, in the injection molding process, the annular body formed in the annular body forming process is coated with a resin material to form a coating layer 65 and a bead filler 89 integral with the coating layer 65.

[0117] 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 has a configuration in which the periphery of the annular body is covered with the solidified covering layer 65. In addition, the bead filler 89 is integrally formed with the covering layer 65 on the outer side in the tire radial direction of the covering layer 65.

[0118] 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. [Example]

[0119] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" are by mass.

[0120] <Preparation of unvulcanized rubber layer> Of the ingredients shown in Table 1, the ingredients other than the vulcanization accelerator and vulcanizing agent were mixed and stirred in a Labo Plastomill (manufactured by Toyo Seiki Seisakusho, 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. The mixture was then rolled using a roll to obtain Rubber 1 to Rubber 6, each of which was an unvulcanized rubber sheet with a thickness of 2.5 mm.

[0121] <Preparation of resin layer> Among the components shown in Table 2, a polyester-based thermoplastic elastomer, polybutylene terephthalate (PBT), and a carbodiimide compound were mixed in the amounts (parts by mass) shown in Table 2 using a twin-screw extruder (manufactured by Technovel Corporation, product name: KZW31TW-45HG, screw diameter 30 mm, L / D = 45) at 230°C to 250°C, a shaft rotation speed of 100 rpm, and an extrusion rate of 10 kg / h. The resulting mixed resin was then mixed with the phenolic resin shown in Table 2 in the amount (parts by mass) shown in Table 2, and the mixture was fed into the twin-screw extruder. The mixture was further mixed at 230°C to 250°C, a shaft rotation speed of 100 rpm, and an extrusion rate of 10 kg / h. The resulting mixture was injection-molded to obtain 2 mm-thick resin sheets, Resin 1 and Resin 2, respectively.

[0122] [Table 1]

[0123] [Table 2]

[0124] The numbers in the tables indicate the “addition amount (parts by mass).” Furthermore, blank spaces in Tables 1 and 2 indicate that the corresponding component is not included. The details of each component shown in Tables 1 and 2 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, epoxidation ratio: 25%) Epoxy rubber 2: Epoxidized natural rubber (manufactured by Muang Mai Guthrie Company Limited, product name: ENR50, epoxidation ratio: 50%)

[0125] Carbon black: N330 carbon black (manufactured by Asahi Carbon Co., Ltd., product name: Asahi #70K, BET method) Nitrogen adsorption specific surface area: 71 m2 / g) Process oil (ENEOS, product name: Process oil) Fatty acid: stearic acid Tackifier: Butylphenol acetylene condensate resin (manufactured by BASF, product name: Koresin) Organophosphorus compounds 1: Tri-p-tolylphosphine (TPTP) Organophosphorus compounds 2: Triphenylphosphine (TPP) Metal oxide: zinc oxide Vulcanizing agent: sulfur Scorch inhibitor: N-cyclohexylthiophthalimide (manufactured by Toray Industries, Inc., product name: Retarder CTP) The antioxidants and vulcanization accelerators used were the above-mentioned known ones, used in appropriate combination.

[0126] TPC: Thermoplastic polyester elastomer (manufactured by Toray DuPont Co., Ltd., product name: Hytrel 5557) PBT: Polybutylene terephthalate (Toray Industries, Inc., product name: Toraycon 1401X06) Carbodiimide: Carbodiimide compound (manufactured by Nisshinbo Chemical Inc., product name: Carbodilite HMV-15CA) Phenolic resin: Unmodified solid straight novolac phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-50235)

[0127] [Examples 1 to 5, Comparative Examples 1 and 2] <Preparation of test specimens> Using the obtained resin sheet and unvulcanized rubber sheet, 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 were bonded together in this order, and vulcanized at a pressure of 2 MPa at the vulcanization temperature and for the vulcanization time shown in Tables 3 and 4 below to obtain test specimens. Tables 3 and 4 show the carbon black content ("CB content (parts by mass)" in the table) per 100 parts by mass of rubber in the rubber sheet of the obtained test specimen, the organic phosphorus compound content ("Phosphorus content (parts by mass)" in the table) per 100 parts by mass of rubber, and the epoxidation ratio of the rubber, as well as the polyester thermoplastic elastomer content ("TPC content (% by mass)" in the table), phenolic resin content ("PH content (% by mass)" in the table), and carbodiimide compound content ("CI content (% by mass)" in the table) relative to the entire resin sheet.

[0128] <Evaluation of adhesive strength> Using the test pieces obtained in each example, a peel test was performed using a precision universal testing machine (Autograph AG-X 5kN, manufactured by Shimadzu Corporation) in an environment of 150°C, in which one resin sheet was pulled 180 degrees from the other resin sheet at a tensile speed of 100 mm / min. The average value over a stroke range of 20 mm to 70 mm, where the peel resistance was relatively stable, was calculated as the peel resistance (unit: N / 25 mm). The results and the locations of failure are shown in Tables 3 and 4 below. In the tables, "Base material / interface" indicates that failure occurred in both the base material and the interface.

[0129] [Table 3]

[0130] [Table 4]

[0131] As can be seen from the evaluation results shown in Tables 3 and 4, the present examples have higher peel resistance at 150° C. than the comparative examples, and are excellent in adhesion between the rubber layer and the resin layer. [Explanation of symbols]

[0132] 10 Tires 11 Rubber sheet 12 Belt member 13 Side rubber 14 Bead section 16 Side part 17 Tire Case 17A Welding Resin Material 17H tire half 18 Crown part 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 containing a rubber containing an epoxidized diene-based rubber, carbon black, and an organic phosphorus compound; 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; A resin-rubber composite having the above structure.

2. 2. The resin-rubber composite according to claim 1, wherein the carbon black content is 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 content of the phenolic resin is 3% by mass or more with respect to the entire second layer.

5. The resin-rubber composite according to any one of claims 1 to 4, wherein the epoxidation ratio of the rubber is 30% to 60%.

6. The resin-rubber composite according to any one of claims 1 to 5, wherein the content of the organic phosphorus compound is 0.5 parts by mass or more per 100 parts by mass of the rubber.

7. The resin-rubber composite according to any one of claims 1 to 6, wherein the second layer contains a carbodiimide compound.

8. 8. The resin-rubber composite according to claim 1, further comprising a third layer that 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.

9. A tire comprising the resin-rubber composite according to any one of claims 1 to 8.

10. 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; 10. The tire of claim 9, having:

11. 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; 10. The tire of claim 9, having:

12. an annular tire frame member including the first layer; The tire according to claim 9 , wherein a bead portion of the tire frame member includes at least one of a bead core including the second layer and a bead filler including the second layer.

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