Laminate and tire

Abstract

To provide a laminate excellent in adhesion between a resin layer and a rubber layer in direct contact with the resin layer.SOLUTION: A laminate comprising: a rubber layer containing a rubber; and a polymer layer containing a polymer having a chlorine-reactive functional group, the polymer layer being in contact with the rubber layer, wherein the amount of chloride atoms present in the rubber layer is 1. 8wt% to 22wt% based on the weight of all atoms present in the rubber layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to laminates and tires. [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 a tire component has been considered from the viewpoints of weight reduction, ease of molding, recycling, etc. 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 comes into contact with a rubber layer of another component, but due to differences in materials, it is not easy to increase the adhesion between the resin layer and the rubber layer.

[0003] Therefore, methods have been proposed to improve the adhesion between a resin layer and a rubber layer by providing an adhesive layer between the resin layer and the rubber layer (see, for example, Patent Document 1). Also, a method has been disclosed in which a surface treatment layer of 1 to 15 μm is formed on the surface of a rubber layer containing a tackifier, thereby directly bonding the rubber layer to the resin layer without an adhesive layer (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-176989 [Patent Document 2] Patent Publication No. 2021-146544 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in a laminate in which a resin layer and a rubber layer are bonded via an adhesive layer, the manufacturing process becomes complicated, and depending on the properties of the adhesive, it may be difficult to obtain heat resistance for the entire laminate. Therefore, in a laminate in which a resin layer and a rubber layer are arranged so as to be in contact with each other, it is desired to obtain excellent adhesion between the two even when the two are in direct contact without an adhesive. Furthermore, even in a method in which a surface treatment layer is formed on the surface of the rubber layer and then directly bonded to the resin layer, it may be difficult to obtain sufficient adhesion depending on the surface condition of the rubber layer, and further improvement in adhesion is required.

[0006] In view of the above circumstances, the present disclosure has an object to provide a laminate having excellent adhesion between a resin layer and a rubber layer that is in direct contact with the resin layer, and a tire having the laminate. [Means for solving the problem]

[0007] The present disclosure includes the following aspects. <1> a rubber layer containing rubber; a resin layer in contact with a surface of the rubber layer and containing a resin having a functional group that reacts with chlorine; and A laminate, wherein the amount of chlorine atoms present on the surface of the rubber layer is 1.8 wt % to 22 wt % of the weight of all atoms present on the surface of the rubber layer. <2> the functional group reactive with chlorine includes at least one selected from the group consisting of an ester bond, an amide bond, and a urethane bond; <1> The laminate according to claim 1. <3> the resin having a functional group reactive with chlorine includes at least one selected from the group consisting of a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a polyester-based thermoplastic resin, a polyamide-based thermoplastic resin, a polyurethane-based thermoplastic elastomer, and a polyurethane-based thermoplastic resin; <1> or <2> The laminate according to claim 1. <4> The resin having a functional group reactive with chlorine contains an aromatic ring. <1> ~ <3> 10. The laminate according to claim 9, wherein the first and second layers are laminates. <5> The melting point of the resin layer is 150°C or higher. <1> ~ <4> 10. The laminate according to claim 9, wherein the first and second layers are laminates. <6> Storage modulus G' of the rubber layer at 50°C A Storage modulus G' of the resin layer at 50 ° C. B The ratio G' B / G' A is between 1 and 200, <1> ~ <5> The laminate according to any one of the above. <7> the surface of the rubber layer is a surface treated with a chlorination treating agent; <1> ~ <6> 10. The laminate according to claim 9, wherein the first and second layers are laminates. <8> <1> ~ <7> A tire having the laminate according to any one of the above. [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a laminate having excellent adhesion between a resin layer and a rubber layer that is in direct contact with the resin layer, and a tire having the laminate. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view of a tire according to an embodiment of the present disclosure taken along a tire rotation axis. [Figure 2] FIG. [Figure 3] FIG. 2 is an enlarged cross-sectional view showing the vicinity of a belt end. [Figure 4] FIG. 2 is a cross-sectional view showing a mold for molding a tire. [Figure 5] FIG. 2 is a cross-sectional view of a mold in which a tread rubber layer, a belt layer, and a rubber chafer are arranged as tire components. [Figure 6] FIG. 2 is a side view of a tire according to another embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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.

[0011] In the present disclosure, the term "resin" is a concept that includes thermoplastic resins, thermoplastic elastomers, and thermosetting resins, but does not include vulcanized rubber. In the present disclosure, 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 the present disclosure, 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 the present disclosure, 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.

[0012] In addition, in this disclosure, "thermoplastic resin" refers to a polymer compound that softens and flows as the temperature rises, and becomes relatively hard and strong when cooled, but does not have rubber-like elasticity. In this disclosure, 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.

[0013] [Laminate] A laminate according to one embodiment of the present disclosure comprises a rubber layer containing rubber, and a resin layer in contact with the surface of the rubber layer and containing a resin having a functional group that reacts with chlorine, wherein the amount of chlorine atoms present on the surface of the rubber layer is 1.8 wt % to 22 wt % of the weight of all atoms present on the surface of the rubber layer. Hereinafter, a functional group that reacts with chlorine will be referred to as a "specific functional group," a resin having a specific functional group will be referred to as a "specific resin," the surface of the rubber layer that comes into contact with the specific resin will be referred to as a "contact surface," and the amount of chlorine atoms present on the contact surface of the rubber layer relative to the weight of all atoms present on the contact surface of the rubber layer will be referred to as the "surface chlorine amount."

[0014] As described above, in a laminate in which a resin layer and a rubber layer are arranged 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. In this embodiment, it has been found that by setting the surface chlorine content at the contact surface of the rubber layer within the above range and arranging the resin layer containing the specific resin so as to be in contact with the contact surface, a laminate with excellent adhesion between the resin layer and the rubber layer can be obtained. The reason for this is not clear, but is presumed to be as follows.

[0015] It is believed that when chlorine atoms are present at the contact surface of the rubber layer, chemical bonds are formed at the interface between the resin layer and the rubber layer due to a reaction between the specific functional group of the resin layer and the chlorine atoms at the contact surface of the rubber layer. When the amount of surface chlorine at the contact surface of the rubber layer is within the above range, more chemical bonds are formed at the interface between the resin layer and the rubber layer than when the amount of surface chlorine is less than the above range, which is thought to result in excellent adhesion between the resin layer and the rubber layer. Here, an example of a method for adjusting the surface chlorine content at the contact surface of the rubber layer to the above range is to treat the surface of the rubber composition with a chlorination treatment agent to introduce chlorine atoms into the surface of the rubber composition. It is believed that treatment with a chlorination treatment agent not only introduces chlorine atoms into the surface of the rubber composition, but also promotes an oxidation reaction of the rubber composition. Therefore, when the surface chlorine content at the contact surface of the rubber layer is within the above range, it is believed that deterioration in adhesion caused by oxidation of the rubber composition is suppressed compared to when the surface chlorine content is greater than the above range, thereby resulting in excellent adhesion between the resin layer and the rubber layer. Furthermore, by having the amount of surface chlorine at the contact surface of the rubber layer within the above range, the movement of the main chain of the rubber contained in the rubber layer is less likely to be hindered by chlorine than when the amount is greater than the above range. Here, if the movement of the main chain of the rubber is hindered by chlorine, the contact surface of the rubber layer behaves hard, and the contact surface is more likely to be broken when the laminate is deformed, which may result in a decrease in adhesion between the resin layer and the rubber layer. Therefore, it is believed that by having the amount of surface chlorine at the contact surface of the rubber layer within the above range, the decrease in adhesion caused by the movement of the main chain of the rubber being hindered by chlorine is suppressed, resulting in excellent adhesion between the resin layer and the rubber layer. For the above reasons, it is presumed that the laminate of this embodiment has excellent adhesion between the resin layer and the rubber layer.

[0016] The rubber composition is a composition that becomes the rubber layer when subjected to a chlorination treatment step, or a composition that becomes the rubber layer when subjected to a chlorination treatment step and a vulcanization step. The composition that becomes the rubber layer after undergoing the chlorination treatment step has the same composition as the rubber layer except for the number of chlorine atoms at the contact surface being smaller. Also, the composition that becomes the rubber layer after undergoing the chlorination treatment step and the vulcanization step has the same composition as the rubber layer except for the number of chlorine atoms at the contact surface and the presence or absence of a crosslinked structure due to vulcanization.

[0017] As described above, the laminate of the present embodiment only needs to have a rubber layer having a contact surface with a surface chlorine content within the above range, and a resin layer in contact with the contact surface and containing a specific resin, and may further have other layers as necessary. Each layer constituting the laminate according to this embodiment will be described below.

[0018] <Rubber layer> The rubber layer is not particularly limited as long as it contains at least rubber and the amount of surface chlorine on the contact surface is within the above range. The surface chlorine content at the contact surface of the rubber layer is 1.8 wt% to 22 wt% as described above, and from the viewpoint of improving adhesion, it is preferably 2.7 wt% to 19 wt%, more preferably 3.5 wt% to 16 wt%.

[0019] The amount of surface chlorine is determined by energy dispersive X-ray analysis (EDX). Specifically, using a tabletop microscope (Hitachi High-Technologies, Miniscope TM3030Plus) equipped with the analytical equipment QUANTAX70 (BRUKER), the surface to be measured is irradiated with an electron beam at an accelerating voltage of 15 kV and a focal length (WD) of 9 mm, and analysis is performed under conditions of observation magnification of 600x, detection time of 60 seconds, and detection area of ​​200 μmΦ. In the obtained EDX scattered X-ray spectrum, the intensity of the Kα line of Cl (chlorine) at a detection energy of 2.621 keV is measured, and the amount of surface chlorine is determined by calculating the weight percentage of Cl (chlorine) atoms relative to the weight of all atoms present on the surface from analysis of the detected spectrum. When quantifying the amount of surface chlorine on the contact surface of the rubber layer in the laminate, for example, the laminate may be cut in a direction perpendicular to the contact surface and the above measurement may be carried out on the cross section.

[0020] (Surface treated with chlorinating agent) An example of a rubber layer having a contact surface with a surface chlorine content in the above range is a rubber layer whose contact surface is treated with a chlorination treatment agent. That is, a method for obtaining a rubber layer having a contact surface with a surface chlorine content in the above range can be, for example, the method of treating the surface of a rubber composition with a chlorination treatment agent to introduce chlorine atoms into the surface of the rubber composition, as described above.

[0021] In a rubber layer whose contact surface is treated with a chlorination treatment agent, chlorine atoms are introduced at the contact surface, so the amount of chlorine atoms present inside the rubber layer (specifically, at a position 50 μm or more away from the contact surface) is usually less than the amount of chlorine atoms present at the contact surface of the rubber layer. Furthermore, the amount of chlorine atoms present on the surface of the rubber layer that has not been treated with a chlorination treatment agent is also less than the amount of chlorine atoms present on the contact surface that has been treated with a chlorination treatment agent. The amount of chlorine atoms present inside the rubber layer and the amount of chlorine atoms present on the surface that has not been treated with a chlorination treatment agent may be 1.7 wt% or less of the weight of all atoms. The amount of chlorine atoms present inside the rubber layer can be determined by measuring the cross section of the rubber layer in the same manner as the amount of chlorine on the surface.

[0022] When the contact surface is a surface treated with a chlorination treatment agent, methods for controlling the surface chlorine content within the above range include a method of selecting the type of chlorination treatment agent, a method of adjusting the concentration of the chlorination treatment agent, the treatment time, the number of treatments, etc., and a combination of these.

[0023] Examples of the chlorination agent include solvent-based chlorination agents and aqueous chlorination agents. Examples of the solvent-based chlorination agent include a solution in which a chlorinating agent such as a chlorinated cyanuric acid, e.g., dichloroisocyanuric acid or trichloroisocyanuric acid, is dissolved in an organic solvent. Examples of the organic solvent include ethyl acetate and acetone. Among these, an ethyl acetate solution of trichloroisocyanuric acid is preferred as the solvent-based chlorination agent from the viewpoint of improving adhesion.

[0024] Examples of aqueous chlorination agents include aqueous solutions of chlorinating agents such as chlorinated cyanurates (e.g., sodium dichloroisocyanurate, sodium trichloroisocyanurate), chlorites (e.g., chlorous acid, sodium chlorite), hypochlorites (e.g., hypochlorous acid, sodium hypochlorite), chlorate (e.g., chloric acid, sodium chlorate), and perchlorates (e.g., sodium perchlorate) dissolved in water. Among these aqueous chlorination agents, an aqueous sodium hypochlorite solution is preferred from the viewpoints of solubility in water and ease of handling. The aqueous chlorination agent may further contain an acid (e.g., hydrochloric acid) to adjust the pH. The pH of the aqueous chlorination agent is preferably in the range of 1.8 to 6.0 from the viewpoints of the hypochlorous acid content and stability.

[0025] The chlorine concentration in the chlorination treatment agent is, for example, in the range of 1500 ppm by mass to 6500 ppm by mass, and preferably in the range of 2500 ppm by mass to 6000 ppm by mass. The chlorine concentration in the chlorination treatment agent can be measured using a commercially available water quality meter or residual chlorine meter after diluting it with the solvent or water used.

[0026] In the treatment with a chlorination treating agent, for example, the chlorination treating agent is applied to the surface of the rubber composition by immersion, wiping, dropping or the like, and then dried as necessary. The temperature at the time of application of the chlorination treatment agent is, for example, 18°C ​​to 25°C. When the chlorination treatment agent is applied by immersion, the immersion time varies depending on the chlorine concentration of the chlorination treatment agent, but is, for example, 30 seconds to 10 hours, and preferably 1 minute to 5 hours. When drying is carried out after application of the chlorination treatment agent, the drying temperature may be, for example, 15° C. to 40° C., and the drying time may be, for example, 3 minutes to 300 minutes. The components contained in the rubber layer will be described below.

[0027] (rubber) The rubber layer contains at least rubber, and may contain other components as necessary. The rubber content in the entire rubber layer (i.e., the rubber content in the entire rubber composition) is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more. The rubber content in the entire rubber layer may be 95% by mass or less, 85% by mass or less, or 75% by mass or less.

[0028] Examples of the rubber contained in the rubber layer include diene rubbers containing double bonds in the main chain of the rubber and non-diene rubbers containing almost no double bonds in the main chain of the rubber. The rubber may be unvulcanized or vulcanized. Examples of diene rubbers include natural rubber (NR) and synthetic rubbers such as polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), and acrylonitrile-butadiene copolymer rubber (NBR). Examples of non-diene rubbers include butyl rubbers (butyl rubber (IIR), etc.), ethylene-propylene rubbers (EPM, EPDM), urethane rubbers (U), silicone rubbers (Q), acrylic rubbers (ACM), and fluororubbers (FKM).

[0029] The rubber layer may contain one type of rubber alone or a mixture of two or more types. When the rubber layer contains two or more types of rubber, it may contain two or more types of diene rubbers, two or more types of non-diene rubbers, or a diene rubber and a non-diene rubber. From the viewpoint of ease of chlorination, the rubber contained in the rubber layer preferably contains a diene rubber among these, and more preferably contains at least one selected from the group consisting of natural rubber (NR) and polybutadiene rubber (BR).

[0030] (Other ingredients) Examples of other components include reinforcing materials such as carbon black, fillers (fillers, short fibers, resins, etc.), vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, and antioxidants. 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.

[0031] When the rubber layer contains carbon black as another component, the content of carbon black in the entire rubber layer (i.e., the content of carbon black in the entire rubber composition) is, for example, 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less. The content of carbon black in the entire rubber layer may be 5% by mass or more, 15% by mass or more, or 25% by mass or more.

[0032] <Resin layer> The resin layer contains at least a resin having a functional group that reacts with chlorine (that is, a specific resin), and may contain other resins as needed, or may contain other components other than resins. The content of the specific resin relative to the total resin contained in the resin layer is, for example, 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. The content of the specific resin in the entire resin layer is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 75% by mass or more. The total content of the resin in the entire resin layer is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 75% by mass or more.

[0033] -Specific resin- The specific functional group possessed by the specific resin, i.e., the functional group that reacts with chlorine, can be a functional group containing at least one group selected from the group consisting of a carbonyl group, a primary amino group, a secondary amino group, a hydroxyl group, and a thiol group. Specific examples of the specific functional group include an ester bond, an amide bond, a urethane bond, a carbonyl group, etc. From the viewpoint of improving adhesion to the rubber layer, the specific resin preferably has a functional group containing a carbonyl group as the specific functional group, more preferably has at least one selected from the group consisting of an ester bond, an amide bond, and a urethane bond, further preferably has at least one of an ester bond and an amide bond, and particularly preferably has an ester bond. The specific resin may have the specific functional group in its main chain, in its side chain, or in both the main chain and the side chain. From the viewpoint of improving adhesion to the rubber layer, it is preferable that the specific resin have the specific functional group in its main chain.

[0034] From the viewpoint of improving the heat resistance of the resin layer, the specific resin preferably contains an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. From the viewpoint of heat resistance, the specific resin preferably contains at least one of a benzene ring and a naphthalene ring as the aromatic ring, and more preferably contains a benzene ring. The specific resin may have an aromatic ring in its main chain, in its side chain, or in both its main chain and its side chain. From the viewpoint of heat resistance, the specific resin preferably has an aromatic ring in its main chain.

[0035] Examples of the specific resin include polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic resins, polyamide-based thermoplastic resins, polyurethane-based thermoplastic resins, etc. The resin layer may contain only one type of specific resin, or may contain two or more types. From the viewpoint of improving adhesiveness, the specific resin preferably contains at least one selected from the group consisting of polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic resins, and polyamide-based thermoplastic resins, more preferably contains at least one selected from the group consisting of polyester-based thermoplastic elastomers and polyester-based thermoplastic resins, and even more preferably contains a polyester-based thermoplastic elastomer. The content of the polyester-based thermoplastic elastomer relative to the entire specific resin is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0036] (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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] (Polyamide thermoplastic elastomer) A polyamide-based thermoplastic elastomer is a thermoplastic resin material made of a copolymer having a polymer that forms a crystalline hard segment with a high melting point and a polymer that forms an amorphous soft segment with a low glass transition temperature, and has an amide bond (-CONH-) in the main chain of the polymer that forms the hard segment. Examples of polyamide-based thermoplastic elastomers include materials in which at least polyamide forms crystalline hard segments with a high melting point and other polymers (e.g., polyester, polyether, etc.) form amorphous soft segments with a low glass transition temperature. Furthermore, polyamide-based thermoplastic elastomers may be formed using a chain extender such as dicarboxylic acid in addition to the hard and soft segments. Specific examples of the polyamide-based thermoplastic elastomer include thermoplastic amide elastomers (TPA) defined in JIS K6418:2007 and polyamide-based elastomers described in JP-A-2004-346273.

[0044] In the polyamide-based thermoplastic elastomer, examples of the polyamide that forms the hard segment include polyamides produced from monomers represented by the following general formula (1) or (2).

[0045] [ka]

[0046] In general formula (1), R 1 represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms).

[0047] [ka]

[0048] In general formula (2), R 2 represents a molecular chain of a hydrocarbon having 3 to 20 carbon atoms (for example, an alkylene group having 3 to 20 carbon atoms).

[0049] In general formula (1), R 1 As the alkylene group, a molecular chain of a hydrocarbon having 3 to 18 carbon atoms, for example, an alkylene group having 3 to 18 carbon atoms, is preferred, a molecular chain of a hydrocarbon having 4 to 15 carbon atoms, for example, an alkylene group having 4 to 15 carbon atoms, is more preferred, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, for example, an alkylene group having 10 to 15 carbon atoms, is particularly preferred. In addition, in the general formula (2), R 2 As the alkylene group, a molecular chain of a hydrocarbon having 3 to 18 carbon atoms, for example, an alkylene group having 3 to 18 carbon atoms, is preferred, a molecular chain of a hydrocarbon having 4 to 15 carbon atoms, for example, an alkylene group having 4 to 15 carbon atoms, is more preferred, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, for example, an alkylene group having 10 to 15 carbon atoms, is particularly preferred. Examples of the monomer represented by general formula (1) or (2) include ω-aminocarboxylic acids and lactams, and examples of the polyamide forming the hard segment include polycondensates of these ω-aminocarboxylic acids or lactams, and co-condensation polymers of diamines and dicarboxylic acids.

[0050] Examples of the ω-aminocarboxylic acid include aliphatic ω-aminocarboxylic acids having 5 to 20 carbon atoms, such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms, such as lauryllactam, ε-caprolactam, undecanelactam, ω-enantholactam, and 2-pyrrolidone. Examples of diamines include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine. Dicarboxylic acids are also represented by HOOC-(R 3 ) m -COOH(R 3 m: a hydrocarbon molecular chain having 3 to 20 carbon atoms, and m: 0 or 1), and examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. As the polyamide forming the hard segment, a polyamide obtained by ring-opening polycondensation of lauryllactam, ε-caprolactam, or udecanolactam can be preferably used.

[0051] Examples of polymers that form soft segments include polyesters and polyethers, specifically polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and ABA triblock polyethers. These may be used alone or in combination of two or more. Polyether diamines obtained by reacting ammonia or the like with the terminals of polyethers may also be used. Here, the term "ABA triblock polyether" refers to a polyether represented by the following general formula (3).

[0052] [ka]

[0053] In the general formula (3), x and z represent integers of 1 to 20. y represents an integer of 4 to 50.

[0054] In general formula (3), x and z each preferably represent an integer of 1 to 18, more preferably an integer of 1 to 16, still more preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12. In addition, in general formula (3), y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, still more preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.

[0055] The combination of the hard segment and the soft segment can be the combination of the hard segment and the soft segment mentioned above. Among these, the combination of the hard segment and the soft segment is preferably a combination of a ring-opening polycondensate of lauryllactam / polyethylene glycol, a combination of a ring-opening polycondensate of lauryllactam / polypropylene glycol, a combination of a ring-opening polycondensate of lauryllactam / polytetramethylene ether glycol, or a combination of a ring-opening polycondensate of lauryllactam / ABA triblock polyether, and more preferably a combination of a ring-opening polycondensate of lauryllactam / ABA triblock polyether.

[0056] From the viewpoint of melt moldability, the number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15,000. From the viewpoint of toughness and low-temperature flexibility, the number average molecular weight of the polymer forming the soft segment is preferably 200 to 6,000. Furthermore, from the viewpoint of moldability, the mass ratio (x:y) of the hard segment (x) to the soft segment (y) is preferably 50:50 to 90:10, more preferably 50:50 to 80:20.

[0057] The polyamide-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.

[0058] Examples of commercially available polyamide-based thermoplastic elastomers that can be used include the "UBESTA XPA" series from Ube Industries, Ltd. (e.g., XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2, XPA9044, etc.) and the "VESTAMID" series from Daicel-Eponic Co., Ltd. (e.g., E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.).

[0059] (Polyurethane-based thermoplastic elastomer) Examples of polyurethane-based thermoplastic elastomers include materials in which at least polyurethane forms hard segments that form pseudo-crosslinks through physical aggregation, and other polymers form soft segments that are amorphous and have a low glass transition temperature. Specific examples of polyurethane-based thermoplastic elastomers include polyurethane-based thermoplastic elastomers (TPU) defined in JIS K6418: 2007. The polyurethane-based thermoplastic elastomer can be expressed as a copolymer containing a soft segment containing a unit structure represented by the following formula A and a hard segment containing a unit structure represented by the following formula B:

[0060] [ka]

[0061] In the formula, P represents a long-chain aliphatic polyether or a long-chain aliphatic polyester, R represents an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon, and P' represents a short-chain aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon.

[0062] In Formula A, the long-chain aliphatic polyether or long-chain aliphatic polyester represented by P may have a molecular weight of, for example, 500 to 5,000. P is derived from a diol compound containing the long-chain aliphatic polyether or long-chain aliphatic polyester represented by P. Examples of such diol compounds include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly(butylene adipate)diol, poly-ε-caprolactone diol, poly(hexamethylene carbonate)diol, and ABA triblock polyether, all of which have molecular weights within the above ranges. These may be used alone or in combination of two or more.

[0063] In Formula A and Formula B, R is a partial structure introduced using a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by R. Examples of aliphatic diisocyanate compounds containing an aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, and 1,6-hexamethylene diisocyanate. Furthermore, examples of diisocyanate compounds containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate. Furthermore, examples of aromatic diisocyanate compounds containing an aromatic hydrocarbon represented by R include 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate. These may be used alone or in combination of two or more.

[0064] In Formula B, the short-chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon represented by P' may have a molecular weight of less than 500, for example. P' is derived from a diol compound containing the short-chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon represented by P'. Examples of aliphatic diol compounds containing the short-chain aliphatic hydrocarbon represented by P' include glycols and polyalkylene glycols, and specific examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol. Furthermore, examples of alicyclic diol compounds containing an alicyclic hydrocarbon represented by P' include cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, and cyclohexane-1,4-dimethanol. Furthermore, examples of aromatic diol compounds containing an aromatic hydrocarbon represented by P' include hydroquinone, resorcinol, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1,1-di(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)ethane, 1,4-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. These may be used alone or in combination of two or more.

[0065] From the viewpoint of melt moldability, the number average molecular weight of the polymer (polyurethane) forming the hard segment is preferably 300 to 1500. From the viewpoint of flexibility and thermal stability of the polyurethane-based thermoplastic elastomer, the number average molecular weight of the polymer forming the soft segment is preferably 500 to 20000, more preferably 500 to 5000, and particularly preferably 500 to 3000. From the viewpoint of moldability, the mass ratio (x:y) of the hard segment (x) to the soft segment (y) is preferably 15:85 to 90:10, more preferably 30:70 to 90:10.

[0066] The polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method. For example, the thermoplastic polyurethane described in JP-A-5-331256 can be used as the polyurethane-based thermoplastic elastomer.

[0067] Specifically, the polyurethane-based thermoplastic elastomer is preferably a combination of a hard segment made of an aromatic diol and an aromatic diisocyanate with a soft segment made of a polycarbonate ester, and more specifically, tolylene diisocyanate (TDI) / polyester-based polyol copolymer, TDI / polyether-based polyol copolymer, TDI / caprolactone-based polyol copolymer, TDI / polycarbonate-based polyol copolymer, 4,4'-diphenylmethane diisocyanate (MDI) / polyester-based polyol copolymer, MDI At least one selected from TDI / polyether-based polyol copolymer, MDI / caprolactone-based polyol copolymer, MDI / polycarbonate-based polyol copolymer, and MDI+hydroquinone / polyhexamethylene carbonate copolymer is preferred, and at least one selected from TDI / polyester-based polyol copolymer, TDI / polyether-based polyol copolymer, MDI / polyester polyol copolymer, MDI / polyether-based polyol copolymer, and MDI+hydroquinone / polyhexamethylene carbonate copolymer is more preferred.

[0068] In addition, examples of commercially available polyurethane-based thermoplastic elastomers that can be used include the "Elastollan" series manufactured by BASF (e.g., ET680, ET880, ET690, ET890, etc.), the "Kuramilon U" series manufactured by Kuraray Co., Ltd. (e.g., 2000 series, 3000 series, 8000 series, 9000 series, etc.), and the "Miractollan" series manufactured by Nippon Miractoran Co., Ltd. (e.g., XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc.).

[0069] (Polyester-based thermoplastic resin) 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.

[0070] 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.

[0071] (Polyamide thermoplastic resin) Examples of the polyamide-based thermoplastic resin include polyamides that form the hard segments of the above-mentioned polyamide-based thermoplastic elastomer. Specific examples of polyamide-based thermoplastic resins include polyamide (amide 6) obtained by ring-opening polycondensation of ε-caprolactam, polyamide (amide 11) obtained by ring-opening polycondensation of undecane lactam, polyamide (amide 12) obtained by ring-opening polycondensation of lauryllactam, polyamide (amide 66) obtained by polycondensation of diamine and dibasic acid, and polyamide having metaxylenediamine as a constituent unit (amide MX).

[0072] Amide 6 can be prepared, for example, by the reaction of {CO—(CH2)5—NH} n Amide 11 can be represented by, for example, {CO—(CH) 10 -NH} n Amide 12 can be represented by, for example, {CO—(CH) 11 -NH} n The amide 66 can be represented, for example, by {CO(CH2)4CONH(CH2)6NH} n Amide MX can be represented, for example, by the following structural formula (A-1): where n represents the number of repeating units.

[0073] [ka]

[0074] As a commercially available product of amide 6, for example, the "UBE Nylon" series (e.g., 1022B, 1011FB, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available product of amide 11, for example, the "Rilsan B" series manufactured by Arkema K.K. can be used. As a commercially available product of amide 12, for example, the "UBE Nylon" series (e.g., 3024U, 3020U, 3014U, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available product of amide 66, for example, the "Leona" series (e.g., 1300S, 1700S, etc.) manufactured by Asahi Kasei Corporation can be used. As a commercially available product of amide MX, for example, the "MX Nylon" series (e.g., S6001, S6021, S6011, etc.) manufactured by Mitsubishi Gas Chemical Company, Inc. can be used.

[0075] The thermoplastic polyamide resin may be a homopolymer formed solely of the above structural units, or a copolymer of the above structural units with other monomers. In the case of a copolymer, the content of the above structural units in each thermoplastic polyamide resin is preferably 40% by mass or more.

[0076] -Other resins- Examples of resins other than the specific resin include polystyrene-based thermoplastic elastomers, polystyrene-based thermoplastic resins, polyolefin-based thermoplastic elastomers, polyolefin-based thermoplastic resins, and phenolic resins.

[0077] -Other ingredients- In addition to the resin, the resin layer may contain other components such as additives, provided that the effects are not impaired. Examples of other components include rubber, various fillers (e.g., silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, colorants, and weather resistance agents.

[0078] <Characteristics of rubber layer and resin layer> (Melting Point) From the viewpoint of improving the heat resistance of the laminate, the melting point of the resin layer is preferably 150°C or higher, more preferably 165°C or higher, and even more preferably 180°C or higher. From the viewpoint of ease of production, the melting point of the resin layer is preferably 350°C or lower, more preferably 300°C or lower, and even more preferably 250°C or lower. The melting point of the resin layer is preferably 150°C to 350°C, more preferably 165°C to 300°C, and even more preferably 180°C to 250°C. The melting point of the resin layer is a value measured by differential scanning calorimetry (DSC) in accordance with JIS K 7121:2012. The measurement can be performed, for example, using a "DSC Q100" from TA Instruments, Inc., at a sweep rate of 10°C / min. When the resin layer has two or more melting points, the melting point of the component with the largest mass proportion in the resin layer is taken as the melting point of the resin layer.

[0079] (hardness) The durometer hardness (Type A) of the contact surface of the rubber layer is, for example, 20 to 100, and from the viewpoints of running stability, vibration, and ride comfort, it is preferably 30 to 90, and more preferably 40 to 80. Hereinafter, the durometer hardness (Type A) may also be simply referred to as "hardness." The durometer hardness (type A) inside the rubber layer (specifically, at a position 50 μm or more away from the contact surface) is, for example, 20 to 100, preferably 30 to 90, more preferably 40 to 80, in terms of running stability, vibration, and ride comfort. From the viewpoint of improving adhesion, the difference between the durometer hardness (Type A) at the contact surface of the rubber layer and the durometer hardness (Type A) inside the rubber layer (hereinafter also referred to as "hardness difference") is preferably 1.3 or less, more preferably 1.2 or less. When the contact surface of the rubber layer is a surface treated with a chlorination treatment agent, it is considered that the contact surface is oxidized by the chlorination treatment agent, resulting in a higher durometer hardness (Type A) than the inside of the rubber layer. Therefore, it is presumed that a rubber layer having a hardness difference equal to or less than the above upper limit has good adhesion to the resin layer due to a small degree of oxidation of the contact surface by the chlorination treatment agent. Durometer hardness (Type A) can be accurately measured using a digital rubber hardness meter (manufactured by Kobunshi Keiki, product name: Digital Rubber Hardness Meter DD4) and the rubber hardness meter auxiliary device CLE-150. When measuring durometer hardness (Type A) inside a rubber layer, the cut surface of the rubber layer is used as the measurement surface and the measurement is carried out in the same way.

[0080] (storage modulus G') Storage modulus G' of the rubber layer at 50°C A The pressure may be, for example, 0.5 MPa to 50 MPa, and from the viewpoint of tire running stability and vibration ride comfort, the pressure is preferably 0.75 MPa to 50 MPa, and more preferably 1 MPa to 50 MPa. Storage modulus G' of the resin layer at 50°C B The pressure is, for example, 10 MPa to 100 MPa, and from the viewpoint of running stability, 20 MPa to 80 MPa is preferable, and 30 MPa to 60 MPa is more preferable. Storage modulus G' at 50°C A Storage modulus G' at 50°C B The ratio G' B / G' A is preferably 1 to 200, more preferably 1 to 150, and even more preferably 1 to 100, from the viewpoint of suppressing peeling at the interface between the rubber layer and the resin layer. The storage modulus is the value measured for the layer to be measured using a dynamic viscoelasticity measuring tester ("ARESI" manufactured by TA Instruments Japan Co., Ltd.) under conditions of a temperature of -20°C to 145°C, a measurement frequency of 20 Hz, and a dynamic strain of 0.1%.

[0081] <Method of manufacturing laminate> An example of a method for producing the laminate of this embodiment (hereinafter also referred to as the "first method") includes a rubber composition preparation step of preparing a rubber composition containing rubber, a chlorine introduction step of introducing chlorine atoms into the surface of the rubber composition and adjusting the surface chlorine amount on the surface into which chlorine atoms have been introduced (hereinafter also referred to as the "chlorine-introduced surface") to fall within the above-mentioned range to obtain a rubber layer, and a resin molding step of molding a resin composition containing a specific resin so that it is in contact with the surface (i.e., the chlorine-introduced surface) to obtain a resin layer. The resin composition is a composition that will become the resin layer when molded, and has the same composition as the resin layer.

[0082] Another example of a method for producing the laminate of the present embodiment (hereinafter also referred to as the "second method") is a method that includes the rubber composition preparation step, the chlorine introduction step, a resin layer preparation step of separately preparing a resin layer containing a specific resin, and a joining step of arranging the resin layer obtained in the resin layer preparation step so as to be in contact with the chlorine-introduced surface of the rubber layer obtained in the chlorine introduction step, and joining the rubber layer and the resin layer.

[0083] (First method) In the first method, as described above, a laminate is obtained through a rubber composition preparation step, a chlorine introduction step, and a resin molding step. When the rubber composition prepared in the rubber composition preparation step contains unvulcanized rubber, the unvulcanized rubber may be vulcanized in the resin molding step, or a vulcanization step for vulcanizing the unvulcanized rubber may be further carried out after the resin molding step.

[0084] In the rubber composition preparation process, for example, the materials constituting the rubber layer (i.e., rubber and other components used as needed) are kneaded, molded into the desired shape, and, if necessary, vulcanized after molding to obtain the rubber composition. Examples of the kneader include ordinary kneaders such as a mixing roll, a Sigma-type rotary blade kneader, a Banbury mixer, a high-speed twin-screw continuous mixer, a single-screw, twin-screw, or multi-screw extruder-type kneader, etc. The kneading temperature may be, for example, in the range of 80°C to 180°C, from the viewpoint of maintaining the unvulcanized state. Examples of the molding method include extrusion molding and roll molding. The vulcanization temperature is set appropriately depending on the composition of the 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.

[0085] In the chlorine introduction step, for example, the surface of the rubber composition obtained in the rubber composition preparation step is treated with a chlorination treatment agent to introduce chlorine atoms into the surface of the rubber composition to form a chlorine-introduced surface, and the amount of surface chlorine on the chlorine-introduced surface is controlled within the above range. The details of the treatment method using the chlorination treatment agent and the method of controlling the amount of surface chlorine on the chlorine-introduced surface are as described above.

[0086] In the resin molding step, for example, first, the materials constituting the resin layer (i.e., the specific resin and other resins and other components used as needed) are melt-kneaded to obtain a resin composition. The obtained resin composition is then molded into a desired shape so as to be in contact with the chlorine-introduced surface of the rubber layer, thereby obtaining a resin layer in contact with the chlorine-introduced surface of the rubber layer. The kneader used for melt kneading is the same as the kneader used to obtain the rubber composition. The kneading temperature is, for example, in the range of Tm°C to (Tm+80)°C, where Tm°C is the melting point of the specific resin. When the resin layer contains another resin having a melting point higher than that of the specific resin, the kneading temperature is preferably higher than the melting point of the other resin. Examples of molding methods include injection molding, vacuum molding, pressure molding, melt casting, etc., and injection molding is preferred from the viewpoint of productivity. When molding the resin composition by injection molding, for example, a rubber layer is placed in a mold, and the molten resin composition is injected so as to contact the chlorine-introduced surface of the rubber layer.

[0087] (Second method) In the second method, as described above, a laminate is obtained through a rubber composition preparation step, a chlorine introduction step, a resin layer preparation step, and a joining step. When the rubber composition prepared in the rubber composition preparation step contains unvulcanized rubber, the unvulcanized rubber may be vulcanized in the joining step, or a vulcanization step for vulcanizing the unvulcanized rubber may be further carried out after the joining step. The details of the rubber composition preparation step and the chlorine introduction step are the same as those of the rubber composition preparation step and the chlorine introduction step in the first method.

[0088] In the resin layer preparation step, for example, a resin composition is obtained in the same manner as in the resin molding step in the first method, and the resin composition is molded in the same manner as in the resin molding step in the first method, except that the resin composition does not come into contact with the rubber layer, to obtain a resin layer. Details of the melt-kneading and molding are as described above.

[0089] In the bonding step, for example, the resin layer is brought into contact with the chlorine-introduced surface of the rubber layer, and the rubber layer and the resin layer are bonded together by applying heat and pressure. The heating temperature is, for example, 110° C. to 190° C. The pressure applied to the contacted rubber layer and resin layer is, for example, 1 MPa to 20 MPa. The heating and pressure application time is, for example, 2 minutes to 100 minutes.

[0090] <Applications of laminates> The laminate 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.

[0091] When the laminate is used in a tire, the following combinations may be mentioned as examples of the combination of the resin layer and the rubber layer in the laminate. A combination of a belt member as a resin layer and at least one member selected from the group consisting of a tread as a 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 a 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 a rubber layer. A combination of a belt cord as a resin layer, a cord covering layer that covers the belt cord as a 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 laminate). A combination of a ply cord as a resin layer, a cord covering layer that covers the ply cord as a 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 laminate). A combination of a bead wire as a resin layer, a wire coating layer that coats the bead wire as a 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 laminate).

[0092] [tire] A tire according to one embodiment of the present disclosure includes at least the laminate described above. Hereinafter, embodiments of a tire having the above-described laminate will be described with reference to the drawings, but the tire of the present disclosure is not limited to these examples.

[0093] FIG. 1 is a cross-sectional view of a tire according to one embodiment of the present disclosure taken along the tire rotation axis. As shown in FIG. 1, a tire 10 of this embodiment is, as an example, a so-called pneumatic tire that is mounted on a rim and filled with air, and has a cross-sectional shape substantially similar to that of a conventional pneumatic tire.

[0094] The tire 10 includes a tire frame member 18 made of resin, which includes a pair of bead portions 12, side portions 14 extending radially outward from the bead portions 12, and a crown portion 16 connecting one side portion 14 to the other side portion 14. The tire frame member 18 is formed from a thermoplastic resin 19, which is an example of the specific resin of the present disclosure, and details of the thermoplastic resin 19 are as described above.

[0095] The bead portion 12 is a portion that fits onto a rim (not shown). The side portion 14 is a portion that constitutes the side of the tire 10, and is gently curved so as to be convex outward in the tire width direction from the bead portion 12 toward the crown portion 16. The crown portion 16 is a portion that supports a tread rubber layer 34, which is an example of a rubber layer described below, that is disposed on the outer side in the tire radial direction, and in this embodiment, the outer peripheral surface is formed flat along the tire width direction.

[0096] An annular bead core 20 is embedded inside the bead portion 12. As shown in Fig. 2, the bead core 20 has a cord 22 wound in an annular shape and made of a metal (e.g., steel), organic fiber, or the like, coated with a resin, specifically a thermoplastic resin 24, which is an example of a specific resin in this embodiment.

[0097] 1, rubber chafers 26, which are an example of a rubber layer made of vulcanized rubber, are provided on the axially outer surface and radially inner surface of the bead portion 12 in contact with the rim (not shown). The rubber chafers 26 are welded to the tire frame member 18 and are integrated with the tire frame member 18.

[0098] A belt layer 28 is provided on the inner circumferential portion of the crown portion 16. As shown in Fig. 3, the belt layer 28 includes, for example, spirally wound cords 30 made of metal (e.g., steel), organic fiber, or the like, coated with a resin, and in this embodiment, a thermoplastic resin 32 that is the same type of resin as the thermoplastic resin 24. The belt layer 28 in this embodiment has, for example, a cylindrical shape with a constant diameter. As shown in Figs. 1 and 3, the outer circumferential surface and widthwise end faces of the belt layer 28 are bonded to the tire frame member 18.

[0099] As shown in FIG. 1, a tread rubber layer 34 made of vulcanized rubber that forms the tread portion of the tire 10 is bonded to the outer periphery of the crown portion 16 of the tire frame member 18.

[0100] The tread rubber layer 34 has a flat inner peripheral surface and an outer peripheral surface that is gently curved so as to be convex radially outward. A tread pattern (not shown) is formed on the outer peripheral surface of the tread rubber layer 34.

[0101] A plurality of protrusions 34A formed at a constant height are provided at intervals on the inner peripheral surface of the tread rubber layer 34 so as to maintain a constant distance from the belt layer 28. The tips of the protrusions 34A abut against the outer peripheral surface of the belt layer 28.

[0102] As shown in FIG. 3, a resin thickness t1 between the tread rubber layer 34 and the cords 30 of the belt layer 28 may be thicker than a resin thickness t2 on the opposite side of the cords 30 from the tread rubber layer 34.

[0103] (Tire manufacturing method) 4 shows a cross-sectional view of a mold 40 for molding the tire 10 of this embodiment. The mold 40 includes an outer mold 42 for molding the outer surface of the tire, and an inner mold (core) 44 for molding the inner surface of the tire. A cavity S (space) for molding the tire 10 is formed between the outer mold 42 and the inner mold 44.

[0104] The outer mold 42 is provided with gates 46 at positions facing both widthwise ends of the crown portion 16 of the tire frame member 18. The inner mold 44 is formed with protruding holding portions 44A that hold the bead cores 20.

[0105] Next, a manufacturing process of the tire 10 of this embodiment will be described. (1) First, as shown in FIG. 5, the tread rubber layer 34, the belt layer 28, and the rubber chafer 26 are placed in predetermined positions in the cavity S of the mold 40. A plurality of protruding supports 26A are formed along the circumferential direction on the inner periphery of the rubber chafer 26 to sandwich and support the bead core 20 between the rubber chafer 26 and the holding portion 44A of the inner mold 44.

[0106] In the tread rubber layer 34 and the rubber chafer 26, the portions that come into contact with the thermoplastic resin that forms the tire frame member 18 are, for example, treated with the above-mentioned chlorination treatment agent, and the surface chlorine content is controlled within the above-mentioned range.

[0107] (2) Molten thermoplastic resin 19 for forming the tire frame member 18 is injected into the cavity S in which the tread rubber layer 34, the belt layer 28, the rubber chafer 26, and the bead core 20 are arranged.

[0108] In the tire 10 of this embodiment, the rubber surfaces of the tread rubber layer 34 in contact with the thermoplastic resin 19 and the rubber chafer 26 in contact with the thermoplastic resin 19 and the thermoplastic resin 24 are surfaces treated with a chlorination treatment agent, and the amount of surface chlorine is controlled within the above range. In other words, the combination of the tire frame member 18 as a resin layer and the tread rubber layer 34 as a rubber layer, the combination of the tire frame member 18 as a resin layer and the rubber chafer 26 as a rubber layer, and the combination of the layer of thermoplastic resin 24 as a resin layer and the rubber chafer 26 as a rubber layer each correspond to the above-mentioned laminate. Therefore, compared to when the surface chlorine content is outside the above range, the tread rubber layer 34 and rubber chafer 26, which are vulcanized rubber, can be directly and firmly bonded (joined) to the thermoplastic resin 19 that forms the tire frame member 18, and the rubber chafer 26 and the thermoplastic resin 24 that is part of the bead core 20. Here, "directly bonded" means that the rubber member and the thermoplastic resin are in direct contact with each other and are joined without any adhesive or the like interposed between them.

[0109] In this embodiment, the belt layer 28, the rubber chafer 26, and the bead core 20 are brought into contact with the molten thermoplastic resin 19 that forms the tire frame member 18, thereby bonding the belt layer 28, the rubber chafer 26, and the bead core 20 to the thermoplastic resin 19. This improves productivity compared to the case where the belt layer 28, the rubber chafer 26, and the bead core 20 are bonded to the tire frame member 18 that has been molded in advance (hardened thermoplastic resin) using an adhesive.

[0110] As shown in FIG. 3, in the tire 10 of this embodiment, the resin thickness dimension t1 between the tread rubber layer 34 and the cords 30 of the belt layer 28 is set to be thicker than the resin thickness dimension t2 of the cords 30 on the side opposite to the tread rubber layer 34. This increases the distance from the tread rubber layer 34 to the ends of the cords 30 of the belt layer 28 (ends in the longitudinal direction of the cords; cut ends of the cords). This makes it difficult for forces acting from the tread surface side of the tread rubber layer 34 to act near the ends of the cords 30, thereby suppressing peeling and damage to the resin (thermoplastic resin 19, thermoplastic resin 32) around the ends of the cords 30.

[0111] From the viewpoint of bonding strength, it is preferable that the thermoplastic resin 24 used in the bead cores 20 and the thermoplastic resin 32 used in the belt layers 28 be the same type of thermoplastic resin as the thermoplastic resin 19 used in the tire frame member 18. However, the present disclosure is not limited to this configuration, and the thermoplastic resin 24 used in the bead cores 20 and the thermoplastic resin 32 used in the belt layers 28 may be a resin material different from the thermoplastic resin 19 used in the tire frame member 18.

[0112] [Other embodiments] The above describes one embodiment of the present disclosure, but the present disclosure is not limited to the above, and it goes without saying that various modifications can be made to the present disclosure without departing from the spirit of the present disclosure.

[0113] The tire 10 in the above embodiment is a so-called pneumatic tire that is filled with air when used, but the tire 10 may also be a tire that is not filled with air. An example of a tire that is not filled with air inside is a type in which the crown portion is supported on the rim via spokes instead of the tire side portions and bead portions.

[0114] FIG. 6 is a side view of a tire according to another embodiment of the present disclosure. As shown in Fig. 6, the tire 110 of this embodiment is a non-pneumatic tire including an inner cylindrical body 121, an outer cylindrical body 122 surrounding the inner cylindrical body 121 from the outside in the tire radial direction, and a plurality of elastically deformable connecting members 123 connecting the inner cylindrical body 121 and the outer cylindrical body 122 to each other. In this embodiment, the inner cylindrical body 121, the outer cylindrical body 122, and the connecting members 123 are integrally formed from a thermoplastic resin, which is an example of the specific resin of the present disclosure. This allows the tire 110 to be formed by injection molding. Details of the thermoplastic resin are as described above. As shown in FIG. 6, the tire 110 has a tread rubber layer 124 made of vulcanized rubber that forms the tread portion of the tire 110 adhered to the outer periphery of the outer cylinder body 122.

[0115] In the manufacturing process of the tire 110 of this embodiment, similarly to the tire 10, the tread rubber layer 124 is placed at a predetermined position in the cavity of a mold, and then molten thermoplastic resin is injected into the cavity to form the inner cylindrical body 121, the outer cylindrical body 122, and the connecting member 123. Note that the portion of the tread rubber layer 124 that comes into contact with the thermoplastic resin is treated with, for example, the above-mentioned chlorination treatment agent, and the surface chlorine content is controlled within the above-mentioned range. [Example]

[0116] 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.

[0117] <Preparation of rubber layer for test specimen> (Preparation of rubber composition for test specimen) Of the ingredients listed below, all ingredients except the vulcanization accelerator and vulcanizing agent were mixed and stirred in a Laboplastomill (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 an unvulcanized rubber sheet with a thickness of 3.0 mm. Diene rubber 1 (natural rubber, product name: TSR20): 85 parts by weight Diene rubber 2 (polybutadiene rubber, manufactured by ENEOS Materials, product name: BR01): 15 parts by weight Carbon black (N550 carbon black, manufactured by Asahi Carbon Co., Ltd., product name: Asahi #65, BET method) Nitrogen adsorption specific surface area: 42 m 2 / g):43 parts by mass Vulcanizing agent (sulfur): 3.3 parts by weight Vulcanization accelerator (Noccela DM, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.): 0.5 parts by mass

[0118] The resulting unvulcanized rubber sheet was sandwiched between two iron plates and vulcanized for 15 minutes at a pressure of 2 MPa and a vulcanization temperature of 160°C to obtain a vulcanized rubber sheet 2.5 mm thick. The resulting vulcanized rubber sheet was cut into a size of 75 mm x 25 mm, and both sides were wiped with hexane, an organic solvent, to degrease the sheet, which was then used as a rubber composition for test specimens. The obtained rubber composition for test specimens is composed of rubber that does not contain chlorine atoms. Therefore, in the rubber layer for test specimens obtained by treating the surface of the obtained rubber composition for test specimens with a chlorination treatment agent, the amount of chlorine atoms present inside and on the surface not treated with the chlorination treatment agent are both 0 wt %. The durometer hardness (Type A) of the surface of the obtained rubber composition for test specimens was measured by the above-mentioned method and was found to be 60.1. Hereinafter, the durometer hardness (Type A) of the surface of the rubber composition for test specimens will be referred to as the durometer hardness (Type A) of the interior of the rubber layer for test specimens described below.

[0119] (Preparation of rubber layers 1 to 7 for test specimens) At room temperature of 25°C, both surfaces of the obtained rubber composition for test specimens were coated with the chlorination treatment agent shown in Table 1 below using the coating method and conditions shown in Table 1 below, and the resulting mixture was left to dry for 1 hour in an environment of 23°C, thereby obtaining rubber layers 1 to 7 for test specimens, respectively. The surface chlorine content and durometer hardness (Type A) of the treated surface (i.e., the chlorine-introduced surface) of the obtained rubber layer for test specimen were determined by the above-mentioned methods. The surface chlorine content, hardness (i.e., durometer hardness (Type A)), and hardness difference (i.e., durometer hardness (Type A) of the treated surface of the rubber layer for test specimen - durometer hardness (Type A) of the surface of the rubber composition for test specimen) are also shown in Table 1. In addition, the storage modulus G' of the obtained rubber layer for test specimen A The results obtained by the above-mentioned method are also shown in Table 1. In Table 1, chlorination treating agents A to C refer to the following chlorination treating agents. Chlorination treatment agent A: A solution prepared by adding hydrochloric acid to an aqueous solution of sodium hypochlorite to adjust the pH to 4 to 6 (chlorine concentration: 4500 mass ppm) Chlorination agent B: Trichloroisocyanuric acid in ethyl acetate (manufactured by Lord Japan Inc., product name "Chemlock 7701") Chlorination treatment agent C: Hypochlorous acid aqueous solution (manufactured by Trust Chemical Co., Ltd., product name "Corona Killer", pH 6.0, chlorine concentration 4000 mass ppm) In Table 1, "immersion" means that the rubber composition for the test piece was submerged in the chlorination treatment agent and kept in contact with the surface of the rubber composition, and "wiping" means that the rubber composition was wiped with a nonwoven fabric (trade name: Bemcot (registered trademark), manufactured by Ozu Sangyo Co., Ltd.) impregnated with the chlorination treatment agent.

[0120] (Rubber layers 1 to 8 for test specimens) The above-mentioned rubber composition for test specimen was used as it was to form the rubber layer 8 for test specimen.

[0121] <Preparation of resin layer> A polyester-based thermoplastic elastomer containing benzene rings in its main chain (manufactured by Toyobo MC Co., Ltd., product name "Pelprene P Type P-90B," melting point 203°C) was fed into a twin-screw extruder (manufactured by Technovel Co., Ltd., product name: KZW31TW-45HG, screw diameter 30 mm, L / D = 45), mixed at 230°C to 250°C, with a shaft rotation speed of 100 rpm and an extrusion rate of 10 kg / h, and injection molded to obtain a 3.0 mm thick resin sheet. The resulting resin sheet was cut into a size of 150 mm x 25 mm, and the contact surface with the rubber layer was degreased by wiping with an organic solvent, ethanol, to prepare the resin layer for the test specimen. The melting point and storage modulus G' of the obtained resin layer for the test piece B As a result of the above-mentioned method, the melting point was 200°C, the storage modulus G' B was 50 MPa.

[0122] [Examples 1 to 3, Comparative Example 4, Example 5, Comparative Examples 6 to 8] <Preparation of laminate (test piece)> Using the obtained rubber layer for test specimen and resin layer for test specimen, the resin layer for test specimen, the rubber layer for test specimen ("Rubber layers for test specimen 1 to 8" in the table), and the resin layer for test specimen were bonded together in this order so that they were in contact with each other, and heated at a pressure of 2 MPa and a temperature of 160°C for 15 minutes to obtain test specimens which were laminates of Examples 1 to 3, Comparative Example 4, Example 5, and Comparative Examples 6 to 8, respectively.

[0123] <Peel test of test piece (80℃)> Using the test specimens obtained in each example, a T-peel test was performed using a precision universal testing machine (Autograph AG-X 5kN, manufactured by Shimadzu Corporation) in an environment of 80°C, in which one test specimen resin layer and the other test specimen resin layer were pulled at an angle of 180 degrees at a tensile speed of 100 mm / min. After the peel test, the surface of the test specimen resin layer was observed, and the area of ​​the region where a portion of the test specimen rubber layer was adhered was determined. For each example, the percentage (%) of the area where a portion of the test specimen rubber layer was adhered after the peel test relative to the total area of ​​the region where the test specimen rubber layer was adhered is shown in Table 1 ("Peel Test" in the table).

[0124] <Production of laminate (tire)> Using the mold 40 of FIG. 4, the pneumatic tire shown in FIG. 1 was manufactured in accordance with the tire manufacturing method described above. Specifically, the tread rubber layer 34 and the rubber chafer 26 in each example were made of a rubber composition having the same composition as the rubber composition for the test specimen, with the surface (contact surface) treated with a chlorination treatment agent using the same method and conditions as those for the rubber layers 1 to 7 for the test specimens described above. A resin composition having the same composition as the resin layer for the test specimen was injected as the thermoplastic resin 19 into the cavity S of the mold 40 in which the tread rubber layer 34, the rubber chafer 26, and the belt layer 28 were arranged, and the tire frame member 18 was formed, thereby obtaining the tires of each example.

[0125] In addition, in the same manner as the pneumatic tire, the non-pneumatic tire shown in Fig. 6 was manufactured as each example. Specifically, the tread rubber layer 124 in each example was a rubber composition having the same composition as the rubber composition for test specimens, with the surface (contact surface) treated with a chlorination treatment agent using the same method and conditions as the rubber layers 1 to 7 for test specimens described above. Then, a resin composition having the same composition as the resin layer for test specimens was injected as a thermoplastic resin into the cavity of a mold in which the tread rubber layer 124 was placed, and an inner cylindrical body 121, an outer cylindrical body 122, and a connecting member 123 were integrally formed to obtain a tire for each example.

[0126] <Drum tire testing> Of the tires obtained, non-pneumatic tires (size 145 / 80 R12) of Examples 2 and 5 were left in a room at 25±2°C for 24 hours. Then, in an environment of 25±2°C, a load twice the JIS load was applied to the tires, and the tires were run on a drum with a diameter of 3 m at a speed of 60 km / h for a maximum of 20,000 km. The distance traveled until the tire failed was measured. A tire was deemed to have "failed" if it became unable to run due to peeling of the tread rubber layer. A longer running distance indicates better adhesion between the tread rubber layer 124 and the outer cylindrical body 122, and thus better tire durability. The results are shown in Table 1. In Table 1, "-" indicates that the test was omitted.

[0127] [Table 1]

[0128] As can be seen from the evaluation results shown in Table 1, the present example has a higher peel resistance at 80° C. than the comparative example, and is superior in adhesion between the rubber layer and the resin layer.

[0129] [Contribution to the United Nations-led Sustainable Development Goals (SDGs)] The SDGs have been proposed to realize a sustainable society. One embodiment of the present invention is expected to be a technology that contributes to goals such as "Responsible Consumption and Production" and "Responsible Consumption and Production" and "Responsible Contribution to Climate Change." [Explanation of symbols]

[0130] 10 Tires 12 Bead section 14 Side section 16 Crown part 18 Tire frame members 19, 24, 32 Thermoplastic resin 20 bead core 22 Code 26 Rubber Chafer 26A Support 28 Belt Layer 30 Code 34 Tread rubber layer 34A protrusion 40 molds 42 Outer mold 44 Inner mold 44A Holding part Gate 46 110 Tires 121 Inner cylinder 122 outer cylinder 123 Connecting member 124 Tread rubber layer S cavity

Claims

1. a rubber layer containing rubber; a resin layer in contact with a surface of the rubber layer and containing a resin having a functional group that reacts with chlorine; and A laminate, wherein the amount of chlorine atoms present on the surface of the rubber layer is 1.8 wt % to 22 wt % based on the weight of all atoms present on the surface of the rubber layer.

2. The laminate according to claim 1 , wherein the functional group that reacts with chlorine includes at least one selected from the group consisting of an ester bond, an amide bond, and a urethane bond.

3. 2. The laminate according to claim 1, wherein the resin having a functional group reactive with chlorine comprises at least one selected from the group consisting of a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a polyester-based thermoplastic resin, a polyamide-based thermoplastic resin, a polyurethane-based thermoplastic elastomer, and a polyurethane-based thermoplastic resin.

4. The laminate according to claim 1 , wherein the resin having a functional group that reacts with chlorine contains an aromatic ring.

5. The laminate according to claim 1 , wherein the resin layer has a melting point of 150° C. or higher.

6. Storage modulus G' of the rubber layer at 50°C Ａ Storage modulus G' at 50 ° C. in the resin layer Ｂ The ratio G' Ｂ / G' Ａ The laminate according to claim 1, wherein is 1 to 200.

7. The laminate according to claim 1 , wherein the surface of the rubber layer is a surface treated with a chlorinating agent.

8. A tire comprising the laminate according to any one of claims 1 to 7.

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