Resin composition, resin-metal composite member, and tire

Abstract

A resin composition contains a thermoplastic elastomer and an epoxy resin as resins, and zinc cyanurate.

Description

Technical Field

[0001] The present disclosure relates to a resin composition, a resin-metal composite member, and a tire. Background Art

[0002] Conventionally, as an attempt to improve tire durability (stress resistance, internal pressure resistance, and rigidity), attempts have been made to provide a reinforcement belt member formed by spirally winding reinforcement cords including metal wires around the outer circumference of the tire.

[0003] Furthermore, generally, a bead member having the function of fixing the tire to the rim is provided at a position of the tire in contact with the rim, and a reinforcing cord is also used in the bead member.

[0004] As a reinforcing cord, for example, Japanese Patent Application Publication No. 2019-1359 describes a resin-metal composite member for a tire, which has a metal member, an adhesive layer and a covering resin layer in this order, and the adhesive layer contains a polyester-based thermoplastic elastomer having a polar functional group. Summary of the invention

[0005] Problems to be solved by the invention

[0006] In the resin-metal composite member described in Japanese Patent Application Publication No. 2019-1359, a polyester-based thermoplastic elastomer having a polar functional group is used to form an adhesive layer provided between the metal member and the coating resin layer, thereby improving the adhesion to the metal member. On the other hand, it is known that the adhesive layer formed using the polyester-based thermoplastic elastomer having a polar functional group still has room for improvement in crack resistance.

[0007] As described above, it is desirable to provide a resin composition having excellent adhesion to metal members and crack resistance. It is further desirable to provide a resin-metal composite member and a tire obtained by using a resin composition having excellent adhesion to metal members and crack resistance.

[0008] Methods for solving problems

[0009] A resin composition contains a thermoplastic elastomer and an epoxy resin as resins, and zinc cyanurate.

[0010] Effects of the Invention

[0011] According to the present disclosure, a resin composition having excellent adhesion to metal members and crack resistance, and a resin-metal composite member and a tire obtained using the resin composition can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1A It is a perspective view showing a partial cross section of the tire according to the first embodiment.

[0013] Figure 1B It is a cross-sectional view of the bead portion mounted on the rim.

[0014] Figure 2 It is a cross-sectional view along the tire rotation axis showing a state in which a reinforcing cord member is embedded in a crown portion of a tire frame in the tire of the first embodiment.

[0015] Figure 3 This is an explanatory diagram for explaining the operation of installing a reinforcing cord member on the crown portion of a tire frame using a reinforcing cord member heating device and rollers.

[0016] Figure 4 It is a perspective view showing a partial cross section of a tire according to the second embodiment. DETAILED DESCRIPTION

[0017] Specific embodiments of the present disclosure are described in detail below, but the present disclosure is not limited to the following embodiments and can be implemented with appropriate changes within the scope of the purpose of the present disclosure.

[0018] In this specification, "resin" is a concept including thermoplastic resins, thermoplastic elastomers and thermosetting resins, and does not include vulcanized rubber. In addition, in the following description of resins, "same type" means that ester-based resins, styrene-based resins, etc. have a common skeleton with the skeleton constituting the main chain of the resin.

[0019] In the present specification, a numerical range expressed with "to" means a range including the numerical values ​​described before and after "to" as a lower limit and an upper limit.

[0020] In the present 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 purpose can be achieved.

[0021] In the present specification, "thermoplastic resin" means a polymer compound which softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubber-like elasticity.

[0022] In this specification, "thermoplastic elastomer" means a copolymer having a hard segment and a soft segment. As thermoplastic elastomers, the following substances can be cited: the material softens and flows as the temperature rises, and becomes a relatively hard state with strength when cooled, and has rubber-like elasticity. As thermoplastic elastomers, for example, copolymers of polymers constituting crystalline hard segments with high melting points or hard segments with high cohesive force and polymers constituting amorphous soft segments with low glass transition temperatures can be cited.

[0023] The hard segment is a relatively harder component than the soft segment. The hard segment is preferably a molecular constraint component that functions as a crosslinking point of a crosslinked rubber to prevent plastic deformation. For example, the hard segment may include a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure that allows for intermolecular stacking through intermolecular hydrogen bonds or π-π interactions.

[0024] In addition, the soft segment refers to a relatively soft component compared to the hard segment. The soft segment is preferably a soft component showing rubber elasticity. For example, as the soft segment, a segment having a main chain with a long chain group (such as a long chain alkylene group, etc.), a high degree of freedom of molecular rotation, and a stretchable structure can be cited.

[0025] <Resin composition>

[0026] The resin composition according to the present embodiment contains a thermoplastic elastomer and an epoxy resin as resins, and zinc cyanurate.

[0027] The resin composition having the above-mentioned structure has excellent adhesiveness to metal members and is more excellent in crack resistance than thermoplastic elastomers having polar functional groups.

[0028] Although the reason why the resin composition exhibits excellent adhesive strength is not necessarily clear, it is firstly believed that a certain interaction that improves the adhesive strength occurs between the epoxy group present in the resin composition and the surface of the metal component. Furthermore, according to the research of the present inventors, it is known that if the resin composition contains zinc cyanurate in addition to the epoxy resin, the adhesive strength to the metal component is further improved. Such a view has not been reported so far.

[0029] Although the reason why the resin composition shows better crack resistance than the thermoplastic elastomer having a polar functional group is not necessarily clear, it is considered that the thermoplastic elastomer having a polar functional group has a tendency for the molecule to be cut and the molecular weight to decrease in the process of introducing the polar functional group into the molecule, while by mixing the epoxy resin as a component different from the thermoplastic elastomer, the decrease in the molecular weight of the thermoplastic elastomer is suppressed.

[0030] The components contained in the resin composition are described below.

[0031] In the present disclosure, the "epoxy resin" does not include a resin that is either a thermoplastic elastomer or a thermoplastic resin (for example, a thermoplastic elastomer or a thermoplastic resin having an epoxy group in a molecule).

[0032] (Epoxy resin)

[0033] There is no particular limitation on the type of epoxy resin. Examples thereof include novolac epoxy resins, dicyclopentadiene epoxy resins, triphenylmethane epoxy resins, bisphenol epoxy resins, biphenyl epoxy resins, glycidylamine epoxy resins, naphthalene epoxy resins, linear aliphatic epoxy resins, etc. The epoxy resins contained in the resin composition may be only one type or two or more types.

[0034] From the viewpoint of miscibility with the thermoplastic elastomer, the epoxy resin is preferably solid at room temperature. For example, an epoxy resin having a softening point of 50° C. to 100° C. as measured by a ring and ball method is preferred.

[0035] From the viewpoint of moisture resistance, it is preferred to use low water-absorbing epoxy resins, for example, epoxy resins containing alicyclic structures or naphthalene structures in the preferred molecules. As alicyclic structures, specifically cyclopropane structures, cyclobutane structures, cyclopentane structures, cyclohexane structures, cycloheptane structures, cyclooctane structures, cubane structures, norbornane structures, tetrahydrodicyclopentadiene structures, adamantane structures, diadamantane structures, bicyclo[2.2.2]octane structures, decalin structures, spiro[5.5]undecane structures and other spirocyclic structures can be listed. Among them, epoxy resins (dicyclopentadiene type epoxy resins) with tetrahydrodicyclopentadiene structures are preferred.

[0036] From the viewpoint of obtaining a sufficient crack resistance improvement effect, the content of the epoxy resin in the entire resin composition is preferably 15% by mass or less, more preferably 12.5% ​​by mass or less, and even more preferably 10% by mass or less.

[0037] From the viewpoint of obtaining a sufficient effect of improving adhesion, the content of the epoxy resin in the entire resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more.

[0038] The epoxy equivalent of the epoxy resin is preferably 100 g / eq to 300 g / eq. If the epoxy equivalent is 100 g / eq or more, sufficient epoxy groups can be present in the resin layer at a certain mixing amount, and the adhesion to metal components can be effectively improved; if it is 300 g / eq or less, even if the ratio of the epoxy resin is small, sufficient epoxy groups can be present in the resin without significantly damaging the physical properties of the added resin, and the adhesion to metal components can be effectively improved.

[0039] From the viewpoint of optimizing the number of epoxy groups present in the resin composition, when the content of the epoxy resin in the entire resin is set to A (mass %) and the epoxy equivalent is set to B (g / eq), the value of A / B is preferably 0.003 to 0.15, more preferably 0.017 to 0.1, and further preferably 0.04 to 0.06.

[0040] (Thermoplastic Elastomer)

[0041] The type of thermoplastic elastomer contained in the resin composition is not particularly limited. Examples thereof include polyester thermoplastic elastomers, polyamide thermoplastic elastomers, polystyrene thermoplastic elastomers, polyurethane thermoplastic elastomers, olefin thermoplastic elastomers, thermoplastic rubber crosslinked bodies, and other thermoplastic elastomers specified in JIS K6418. The thermoplastic elastomer contained in the resin composition may be only one type or may be two or more types.

[0042] From the viewpoint of improving crack resistance, it is preferred that the thermoplastic elastomer contained in the resin composition does not have a polar functional group (epoxy group, carboxyl group, acid anhydride group, amino group, etc.). However, the resin composition may also contain a thermoplastic elastomer having a polar functional group as long as it does not impair the above-mentioned effect.

[0043] From the viewpoint of suppressing the reaction with the epoxy group contained in the epoxy resin, it is preferable that the thermoplastic elastomer contains a polyester-based thermoplastic elastomer.

[0044] -Polyester thermoplastic elastomer-

[0045] Examples of the polyester-based thermoplastic elastomer include a material in which at least polyester forms a crystalline hard segment with a high melting point, and another polymer (such as polyester or polyether) forms an amorphous soft segment with a low glass transition temperature.

[0046] As the polyester forming the hard segment, an aromatic polyester can be used. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or its ester-forming derivative and an aliphatic diol. The aromatic polyester is preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Furthermore, it can also be 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, diphenoxyethane dicarboxylic acid, 5-sulfonic isophthalic acid, or their ester-forming derivatives and a diol with a molecular weight of 300 or less, such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc. Polyesters derived from aliphatic diols such as methyl glycol, alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecane dimethanol, benzyl alcohol, bis(p-hydroxy)biphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-p-terphenyl, 4,4'-dihydroxy-p-quaterphenyl, or copolyesters using two or more of these dicarboxylic acid components and diol components. In addition, a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxyl component, etc. may be copolymerized in an amount of 5 mol% or less.

[0047] Examples of the polyester forming the hard segment include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, and polybutylene terephthalate is preferred.

[0048] In addition, examples of the polymer forming the soft segment include aliphatic polyesters and aliphatic polyethers.

[0049] Examples of the aliphatic polyether include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(butylene oxide) glycol, poly(hexylene 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.

[0050] Examples of the aliphatic polyester include poly(ε-caprolactone), polyenantholactone, polycapryllactone, polybutylene adipate, and polyethylene adipate.

[0051] From the viewpoint of the elastic properties of the obtained polyester block copolymer, among these aliphatic polyethers and aliphatic polyesters, preferred polymers for forming the soft segment include poly(oxybutylene) glycol, ethylene oxide adducts of poly(oxypropylene) glycol, poly(ε-caprolactone), polybutylene adipate, polyethylene adipate, and the like.

[0052] In addition, from the viewpoint of toughness and low-temperature flexibility, the number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000. Furthermore, 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, and more preferably 98:2 to 30:70.

[0053] As the combination of the hard segment and the soft segment, for example, each combination of the hard segment and the soft segment listed above can be cited. Among them, as the combination of the hard segment and the soft segment, preferably, the combination of the hard segment is polybutylene terephthalate and the soft segment is aliphatic polyether, and more preferably, the combination of the hard segment is polybutylene terephthalate and the soft segment is poly(ethylene oxide) glycol.

[0054] As commercially available products of polyester-based thermoplastic elastomers, for example, the "Hytrel" series manufactured by Toray-DuPont Co., Ltd. (for example, 3046, 4047, 4767, 5557, 6347, 6377, 7247, etc.) and the "Pelprene" series manufactured by Toyobo Co., Ltd. (for example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.

[0055] The polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.

[0056] -Polyamide-based thermoplastic elastomer-

[0057] The polyamide-based thermoplastic elastomer refers to a thermoplastic resin material composed of a copolymer of a polymer forming a crystalline hard segment with a high melting point and a polymer forming an amorphous soft segment with a low glass transition temperature, wherein the main chain of the polymer forming the hard segment has an amide bond (-CONH-).

[0058] Examples of polyamide-based thermoplastic elastomers include materials in which at least polyamide forms a crystalline hard segment with a high melting point, and other polymers (e.g., polyester, polyether, etc.) form a non-crystalline soft segment with a low glass transition temperature. In addition, the polyamide-based thermoplastic elastomer may be formed using a chain extender such as a dicarboxylic acid in addition to the hard segment and the soft segment.

[0059] Specific examples of the polyamide-based thermoplastic elastomer include amide-based thermoplastic elastomers (TPA) specified in JIS K6418:2007 and the polyamide-based elastomers described in JP-A-2004-346273.

[0060] Examples of the polyamide forming the hard segment in the polyamide-based thermoplastic elastomer include polyamides produced from monomers represented by the following general formula (1) or (2).

[0061] [Chemistry 1]

[0062] H2N-R 1 -COOH (1)

[0063] [In the general formula (1), R 1 It represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms (e.g., an alkylene group having 2 to 20 carbon atoms).]

[0064] [Chemistry 2]

[0065]

[0066] [In general formula (2), R 2 It represents a molecular chain of a hydrocarbon having 3 to 20 carbon atoms (e.g., an alkylene group having 3 to 20 carbon atoms).]

[0067] In the general formula (1), R 1 , preferably a molecular chain of a hydrocarbon having 3 to 18 carbon atoms, such as an alkylene group having 3 to 18 carbon atoms, further preferably a molecular chain of a hydrocarbon having 4 to 15 carbon atoms, such as an alkylene group having 4 to 15 carbon atoms, and particularly preferably a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, such as an alkylene group having 10 to 15 carbon atoms.

[0068] In the general formula (2), R 2 , preferably a molecular chain of a hydrocarbon having 3 to 18 carbon atoms, such as an alkylene group having 3 to 18 carbon atoms, further preferably a molecular chain of a hydrocarbon having 4 to 15 carbon atoms, such as an alkylene group having 4 to 15 carbon atoms, and particularly preferably a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, such as an alkylene group having 10 to 15 carbon atoms.

[0069] Examples of the monomer represented by the general formula (1) or (2) include ω-aminocarboxylic acids and lactams. Examples of the polyamide forming the hard segment include polycondensates of these ω-aminocarboxylic acids and lactams, and cocondensates of diamines and dicarboxylic acids.

[0070] 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-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms, such as lauryl lactam, ε-caprolactam, undecanoic acid, ω-enantholactam, and 2-pyrrolidone.

[0071] Examples of the diamine 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 m-phenylenediamine.

[0072] In addition, dicarboxylic acids can be prepared from HOOC-(R 3 )m-COOH(R 3 : a molecular chain of a hydrocarbon having 3 to 20 carbon atoms, 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.

[0073] As the polyamide forming the hard segment, a polyamide obtained by ring-opening polycondensation of lauryl lactam, ε-caprolactam or undecanolactam can be preferably used.

[0074] In addition, as the polymer forming the soft segment, for example, polyester, polyether, etc. can be cited, specifically polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ABA type triblock polyether, etc. can be cited. These can be used alone or in combination of two or more. In addition, polyether diamines obtained by reacting ammonia, etc. with the polyether terminal can also be used.

[0075] Here, "ABA type triblock polyether" means a polyether represented by the following general formula (3).

[0076] [Chemistry 3]

[0077]

[0078] [In the general formula (3), x and z represent integers of 1 to 20. y represents an integer of 4 to 50.]

[0079] In the general formula (3), x and z are each preferably an integer of 1 to 18, more preferably an integer of 1 to 16, further preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12. In the general formula (3), y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, further preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.

[0080] As the combination of the hard segment and the soft segment, the combinations of the hard segment and the soft segment listed above can be cited. Among them, as the combination of the hard segment and the soft segment, preferably the combination of the ring-opening polycondensate of lauryl lactam / polyethylene glycol, the combination of the ring-opening polycondensate of lauryl lactam / polypropylene glycol, the combination of the ring-opening polycondensate of lauryl lactam / polytetramethylene ether glycol, or the combination of the ring-opening polycondensate of lauryl lactam / ABA type triblock polyether, more preferably the combination of the ring-opening polycondensate of lauryl lactam / ABA type triblock polyether.

[0081] From the viewpoint of melt moldability, the number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15000. In addition, 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 6000. 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, and more preferably 50:50 to 80:20.

[0082] 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.

[0083] As commercially available products of polyamide-based thermoplastic elastomers, for example, Ube Industries, Ltd.'s "UBESTAXPA" series (for example, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.) and Daicel Evonik Co., Ltd.'s "VESTAMID" series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) can be used.

[0084] -Polystyrene thermoplastic elastomer-

[0085] As polystyrene-based thermoplastic elastomers, for example, at least polystyrene forms a hard segment, and other polymers (such as polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) form amorphous and low glass transition temperature soft segments. As polystyrene forming a hard segment, for example, polystyrene obtained by known free radical polymerization, ionic polymerization, etc. is preferably used, and specifically polystyrene with anionic living polymerization can be cited. In addition, as a polymer forming a soft segment, for example, polybutadiene, polyisoprene, poly (2,3-dimethyl-butadiene) and the like can be cited.

[0086] As the combination of the hard segment and the soft segment, each combination of the hard segment and the soft segment listed above can be cited. Among them, as the combination of the hard segment and the soft segment, a combination of polystyrene / polybutadiene or a combination of polystyrene / polyisoprene is preferred. In addition, in order to suppress the unintended crosslinking reaction of the thermoplastic elastomer, the soft segment is preferably hydrogenated.

[0087] The number average molecular weight of the polymer (polystyrene) forming the hard segment is preferably 5,000 to 500,000, more preferably 10,000 to 200,000.

[0088] The number average molecular weight of the polymer forming the soft segment is preferably 5000 to 1000000, more preferably 10000 to 800000, and even more preferably 30000 to 500000. Furthermore, from the viewpoint of moldability, the volume ratio (x:y) of the hard segment (x) to the soft segment (y) is preferably 5:95 to 80:20, and more preferably 10:90 to 70:30.

[0089] The polystyrene-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.

[0090] Examples of polystyrene-based thermoplastic elastomers include styrene-butadiene copolymers [SBS (polystyrene-poly(butylene) block-polystyrene), SEBS (polystyrene-poly(ethylene / butylene) block-polystyrene)], styrene-isoprene copolymers (polystyrene-polyisoprene block-polystyrene), styrene-propylene copolymers [SEP (polystyrene-(ethylene / propylene) block), SEPS (polystyrene-poly(ethylene / propylene) block-polystyrene), SEEPS (polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene), SEB (polystyrene (ethylene / butylene) block)], and the like.

[0091] As commercially available products of polystyrene-based thermoplastic elastomers, for example, the "Tuftec" series manufactured by Asahi Kasei Corporation (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.), the "SEBS" series manufactured by Kuraray Co., Ltd. (8007, 8076, etc.), and the "SEPS" series (2002, 2063, etc.) can be used.

[0092] -Polyurethane thermoplastic elastomer-

[0093] Examples of the polyurethane-based thermoplastic elastomer include a material in which at least polyurethane forms a hard segment that is pseudo-crosslinked by physical aggregation, and other polymers form a non-crystalline soft segment that has a low glass transition temperature.

[0094] Specific examples of polyurethane thermoplastic elastomers include polyurethane thermoplastic elastomers (TPU) specified in JIS K6418: 2007. Polyurethane thermoplastic elastomers can be represented by copolymers containing a soft segment having a unit structure represented by the following formula A and a hard segment having a unit structure represented by the following formula B.

[0095] [Chemistry 4]

[0096]

[0097]

[0098] [Wherein, P represents a long-chain aliphatic polyether or a long-chain aliphatic polyester. R represents an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon. P' represents a short-chain aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon.]

[0099] In formula A, as the long-chain aliphatic polyether or long-chain aliphatic polyester represented by P, for example, a substance having a molecular weight of 500 to 5000 can be used. P is derived from a diol compound containing the long-chain aliphatic polyether and the long-chain aliphatic polyester represented by P. Examples of such a diol compound include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly(butylene adipate) glycol, poly-ε-caprolactone glycol, poly(hexamethylene carbonate) glycol, and ABA-type triblock polyether, etc., having a molecular weight within the aforementioned range.

[0100] These can be used alone or in combination of two or more.

[0101] In Formula A and Formula B, R is derived from a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by R. Examples of the aliphatic diisocyanate compound 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.

[0102] Examples of diisocyanate compounds containing alicyclic hydrocarbons represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate. Examples of aromatic diisocyanate compounds containing aromatic hydrocarbons represented by R include 4,4'-diphenylmethane diisocyanate and toluene diisocyanate.

[0103] These can be used alone or in combination of two or more.

[0104] In formula B, as the short-chain aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by P', for example, a substance having a molecular weight of less than 500 can be used. In addition, P' is derived from a diol compound containing a short-chain aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by P'. As the aliphatic diol compound containing the short-chain aliphatic hydrocarbon represented by P', for example, diols and polyalkylene glycols can be listed, and specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc. can be listed.

[0105] Examples of the alicyclic diol compound 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.

[0106] Furthermore, examples of the aromatic diol compound 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-bis(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)ethane, 1,4-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

[0107] These can be used alone or in combination of two or more.

[0108] From the viewpoint of melt moldability, the number average molecular weight of the polymer (polyurethane) forming the hard segment is preferably 300 to 1500. In addition, 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 20,000, more preferably 500 to 5,000, and particularly preferably 500 to 3,000. In addition, 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, and more preferably 30:70 to 90:10.

[0109] The polyurethane thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method. As the polyurethane thermoplastic elastomer, for example, thermoplastic polyurethane described in Japanese Unexamined Patent Publication No. 5-331256 can be used.

[0110] As the polyurethane thermoplastic elastomer, specifically, a combination of a hard segment composed of an aromatic diol and an aromatic diisocyanate and a soft segment composed of a polycarbonate is preferred. More specifically, at least one selected from the group consisting of toluene diisocyanate (TDI) / polyester polyol copolymers, TDI / polyether polyol copolymers, TDI / caprolactone polyol copolymers, TDI / polycarbonate polyol copolymers, 4,4'-diphenylmethane diisocyanate (MDI) / polyester polyol copolymers, MDI / polyether polyol copolymers, MDI / caprolactone polyol copolymers, MDI / polycarbonate polyol copolymers and MDI+hydroquinone / polyhexamethylene carbonate copolymers is preferred. Further preferred is at least one selected from the group consisting of TDI / polyester polyol copolymers, TDI / polyether polyol copolymers, MDI / polyester polyol copolymers, MDI / polyether polyol copolymers and MDI+hydroquinone / polyhexamethylene carbonate copolymers.

[0111] In addition, as commercially available products of polyurethane-based thermoplastic elastomers, for example, the "Elastollan" series manufactured by BASF (for example, ET680, ET880, ET690, ET890, etc.), the "Kuramiron U" series manufactured by Kuraray Co., Ltd. (for example, 2000 series, 3000 series, 8000 series, 9000 series, etc.), and the "Miractran" series manufactured by Nippon Miralon Co., Ltd. (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc.) can be used.

[0112] -Olefin thermoplastic elastomer-

[0113] As the olefin-based thermoplastic elastomer, for example, a material in which at least a polyolefin forms a crystalline hard segment with a high melting point, and another polymer (for example, a polyolefin, another polyolefin, a polyvinyl compound, etc.) forms an amorphous soft segment with a low glass transition temperature can be cited. As the polyolefin forming the hard segment, for example, polyethylene, polypropylene, isotactic polypropylene, polybutene, etc. can be cited.

[0114] Examples of the olefin-based thermoplastic elastomer include olefin-α-olefin random copolymers and olefin block copolymers. Specifically, propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-pentene copolymers, ethylene-1-butene copolymers, 1-butene-1-hexene copolymers, 1-butene-4-methyl-pentene, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-butyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, propylene-methacrylic acid copolymers, propylene-methyl methacrylate copolymers, propylene-ethyl methacrylate copolymers, propylene-butyl methacrylate copolymers, propylene-methyl acrylate copolymers, propylene-ethyl acrylate copolymers, propylene-butyl acrylate copolymers, ethylene-vinyl acetate copolymers, and propylene-vinyl acetate copolymers.

[0115] Among them, the olefin-based thermoplastic elastomer is preferably selected from propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-pentene copolymers, ethylene-1-butene copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-butyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, propylene-methyl acrylate copolymers, The present invention is preferably at least one of propylene acid copolymers, propylene-methyl methacrylate copolymers, propylene-ethyl methacrylate copolymers, propylene-butyl methacrylate copolymers, propylene-methyl acrylate copolymers, propylene-ethyl acrylate copolymers, propylene-butyl acrylate copolymers, ethylene-vinyl acetate copolymers and propylene-vinyl acetate copolymers, and is further preferably at least one selected from ethylene-propylene copolymers, propylene-1-butene copolymers, ethylene-1-butene copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers and ethylene-butyl acrylate copolymers.

[0116] In addition, two or more olefin resins may be used in combination as in the case of ethylene and propylene. In addition, the content of the olefin resin in the olefin-based thermoplastic elastomer is preferably 50% by mass or more and 100% by mass or less.

[0117] The number average molecular weight of the olefin-based thermoplastic elastomer is preferably 5000 to 10000000. If the number average molecular weight of the olefin-based thermoplastic elastomer is 5000 to 10000000, the mechanical properties of the thermoplastic resin material are sufficient and the processability is also excellent. From the same viewpoint, the number average molecular weight of the olefin-based thermoplastic elastomer is further preferably 7000 to 1000000, and particularly preferably 10000 to 1000000. As a result, the mechanical properties and processability of the thermoplastic resin material can be further improved. In addition, as the number average molecular weight of the polymer forming the soft segment, from the viewpoint of toughness and low-temperature flexibility, it is preferably 200 to 6000. 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 95:15, and more preferably 50:50 to 90:10.

[0118] The olefin-based thermoplastic elastomer can be synthesized by copolymerization according to a known method.

[0119] As commercially available products of olefin-based thermoplastic elastomers, for example, the "Tafmer" series manufactured by Mitsui Chemicals, Inc. (e.g., A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010, XM-7070, XM-7080, BL4000, BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-018 0, P-0280, P-0480, P-0680, etc.), "Nucrel" series manufactured by Mitsui-DuPont Polychemicals (for example, AN4214C, AN4225C, AN42115C, N0903HC, N0908C, AN42012C, N410, N1050H, N1108C, N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN4228C, AN4213C, N035C), etc., "ELVALOY AC" series (e.g., 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715AC, 3117AC, 3427AC, 3717AC, etc.), Sumitomo Chemical's "Acryft" series, "EVATATE" series, etc., Tosoh Corporation's "Ultrathen" series, etc. e" series, PrimeTPO series made by Prime polymer (e.g. E-2900H, F-3900H, E-2900, F-3900, J-5900, E-2910, F-3910, J-5910, E-2710, F-3710, J-5910, E-2740, F-3740, R110MP, R110E, T310E, M142E, etc.), etc.

[0120] (Thermoplastic resin)

[0121] The resin composition may further contain a thermoplastic resin. By containing a thermoplastic resin, for example, the elastic modulus of the resin composition can be adjusted to a desired range. The elastic modulus of a thermoplastic resin is generally higher than that of a thermoplastic elastomer, so there is a tendency to improve the elastic modulus of the resin composition by mixing a thermoplastic resin.

[0122] The thermoplastic resin contained in the resin composition is preferably the same type as the thermoplastic elastomer contained in the resin composition. For example, when the thermoplastic elastomer contained in the resin composition is a polyester-based thermoplastic elastomer, the polyester-based thermoplastic resin is preferred.

[0123] Examples of the thermoplastic resin contained in the resin composition include polyester thermoplastic resins, polyamide thermoplastic resins, olefin thermoplastic resins, polyurethane thermoplastic resins, vinyl chloride thermoplastic resins, polystyrene thermoplastic resins, etc. These may be used alone or in combination of two or more.

[0124] -Polyester thermoplastic resin-

[0125] Examples of the polyester thermoplastic resin include polylactic acid, poly(hydroxy-3-butylbutyric acid), poly(hydroxy-3-hexylbutyric acid), poly(ε-caprolactone), polyenantholactone, polyoctalactone, aliphatic polyesters such as polybutylene adipate and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene naphthalate. Among them, polybutylene terephthalate is preferred as the polyester thermoplastic resin from the viewpoint of heat resistance and processability.

[0126] As commercially available products of polyester-based thermoplastic resins, for example, the "Duranex" series manufactured by Polyplastics Co., Ltd. (for example, 2000, 2002, etc.), the "Novaduran" series manufactured by Mitsubishi Engineering-Plastics Co., Ltd. (for example, 5010R5, 5010R3-2, etc.), and the "Toraycon" series manufactured by Toray Industries, Ltd. (for example, 1401X06, 1401X31, etc.) can be used.

[0127] -Polyamide-based thermoplastic resin-

[0128] Examples of polyamide-based thermoplastic resins include polyamides obtained by ring-opening polycondensation of ε-caprolactam (amide 6), polyamides obtained by ring-opening polycondensation of undecanolactam (amide 11), polyamides obtained by ring-opening polycondensation of lauryl lactam (amide 12), polyamides obtained by polycondensation of diamines and dibasic acids (amide 66), and polyamides having meta-phenylenediamine as a structural unit (amide MX).

[0129] Amide 6 can be prepared, for example, using {CO-(CH2)5-NH} n Amide 11 can be represented by {CO-(CH2) 10 -NH} n Amide 12 can be represented by {CO-(CH2) 11 -NH} n Amide 66 can be represented by {CO(CH2)4CONH(CH2)6NH} n Amide MX can be represented by, for example, the following structural formula (A-1): Here, n represents the number of repeating units.

[0130] As a commercial product of amide 6, for example, the "UBE Nylon" series (for example, 1022B, 1011FB, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercial product of amide 11, for example, the "Rilsan B" series manufactured by Arkema Co., Ltd. can be used. As a commercial product of amide 12, for example, the "UBE Nylon" series (for example, 3024U, 3020U, 3014U, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercial product of amide 66, for example, the "UBE Nylon" series (for example, 2020B, 2015B, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercial product of amide MX, for example, the "MX Nylon" series (for example, S6001, S6021, S6011, etc.) manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used.

[0131] [Chemistry 5]

[0132]

[0133] The polyamide-based thermoplastic resin may be a homopolymer consisting of the above-mentioned structural unit alone, or a copolymer of the above-mentioned structural unit and other monomers. In the case of a copolymer, the content of the above-mentioned structural unit in each polyamide-based thermoplastic resin is preferably 40% by mass or more.

[0134] -Polyolefin-based thermoplastic resin-

[0135] Examples of the polyolefin-based thermoplastic resin include polyethylene-based thermoplastic resins, polypropylene-based thermoplastic resins, polybutadiene-based thermoplastic resins, etc. Among them, polypropylene-based thermoplastic resins are preferred as the polyolefin-based thermoplastic resin from the viewpoint of heat resistance and processability.

[0136] Specific examples of polypropylene-based thermoplastic resins include propylene homopolymers, propylene-α-olefin random copolymers, propylene-α-olefin block copolymers, etc. Examples of α-olefins include α-olefins having about 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0137] (Zinc Cyanurate)

[0138] The content of zinc cyanurate in the resin composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 2% by mass, based on the entire resin composition, from the viewpoint of the adhesion improvement effect and the balance with other components.

[0139] (Other ingredients)

[0140] The resin composition may contain components other than the resin and zinc cyanurate as required. Examples of such components include rubber, fillers (silicon dioxide, calcium carbonate, clay, etc.), antioxidants, plasticizers, colorants, weathering agents, reinforcing materials, and the like.

[0141] When the resin composition contains components other than the resin and zinc cyanurate, the total proportion of the resin and zinc cyanurate in the resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0142] From the viewpoint of crack resistance, the weight average molecular weight of the resin contained in the resin composition is preferably 35,000 or more, more preferably 37,500 or more, and further preferably 40,000 or more.

[0143] The upper limit of the weight average molecular weight of the resin contained in the resin composition is not particularly limited, but may be 100,000 or less.

[0144] In the present disclosure, the weight average molecular weight of the resin contained in the resin composition is the weight average molecular weight of the entire resin contained in the resin composition. The weight average molecular weight of the resin can be measured by the method described in the Examples described below.

[0145] From the viewpoint of ensuring the necessary rigidity, the tensile modulus of the resin composition is preferably 500 MPa or more, more preferably 550 MPa or more, and further preferably 600 MPa or more. The upper limit of the tensile modulus of the resin composition is not particularly limited, but may be 1,000 MPa or less.

[0146] In the present disclosure, the tensile modulus of the resin composition can be measured by the method described in the examples described later.

[0147] The resin composition is preferably solid from the viewpoint of workability. Specifically, it is preferred that the melting point or glass transition temperature appears at 20° C. or higher in differential scanning calorimetry (DSC).

[0148] (Application of resin composition)

[0149] The use of the resin composition is not particularly limited. As described above, since the resin composition exhibits excellent adhesion to metal components, it can be suitably used as an adhesive for bonding metal components to each other or metal components to non-metallic components (resin components, etc.). Furthermore, since the resin composition exhibits excellent crack resistance, it can also be suitably used in situations where physical force is applied.

[0150] In one embodiment, the resin composition is used to form a resin layer of a resin-metal composite member described below.

[0151] <Resin-metal composite parts>

[0152] The resin-metal composite member according to the present embodiment includes a metal member and a resin layer disposed around the metal member, and the resin layer is composed of the above-mentioned resin composition.

[0153] The shape of the resin-metal composite member is not particularly limited, and examples thereof include a cord shape, a sheet shape, a plate shape, etc. The resin-metal composite member may include only one metal member or may include a plurality of metal members.

[0154] The use of the resin-metal composite member is not particularly limited, and examples thereof include a tire frame constituting a tire, a reinforcing belt member disposed on the outer periphery of the tire, and a bead member disposed at a position of the tire in contact with a rim.

[0155] The thickness of the resin layer is not particularly limited, but is, for example, preferably 0.5 μm to 500 μm, more preferably 1 μm to 150 μm, and further preferably 1 μm to 100 μm.

[0156] The average thickness of the resin layer is defined as the arithmetic mean value of the thickness of the adhesive layer measured from the SEM images obtained by cutting the resin-metal composite member along the lamination direction of the metal member and the resin layer at five arbitrary positions. The thickness of the resin layer in each SEM image is defined as the value measured at the portion with the smallest thickness.

[0157] The resin-metal composite member may further include a coating resin layer disposed around the resin layer. In this case, the resin layer functions as, for example, an adhesive layer disposed between the metal member and the coating resin layer.

[0158] That is, the resin-metal composite component involved in this embodiment has a metal component, an adhesive layer arranged around the aforementioned metal component, and a coating resin layer arranged around the aforementioned adhesive layer. The aforementioned adhesive layer can also be a material containing a thermoplastic elastomer and an epoxy resin as resin.

[0159] The material constituting the coating resin layer is not particularly limited, and can be selected from, for example, the thermoplastic elastomers and thermoplastic resins described above as the thermoplastic elastomers and thermoplastic resins that can be contained in the resin layer.

[0160] From the viewpoint of affinity to the resin layer, the coating resin layer preferably contains the same resin as the resin contained in the adhesive layer. For example, when the resin layer contains a polyester thermoplastic elastomer, it preferably contains a polyester thermoplastic elastomer or a polyester thermoplastic resin.

[0161] The coating resin layer may contain components other than the resin as required, such as rubber, fillers (silicon dioxide, calcium carbonate, clay, etc.), antioxidants, plasticizers, colorants, weathering agents, reinforcing materials, etc.

[0162] When the covering resin layer contains components other than the resin, the proportion of the entire resin in the covering resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0163] The thickness of the coating resin layer is not particularly limited, and may be, for example, in the range of 10 μm to 1000 μm, or in the range of 50 μm to 700 μm.

[0164] The average thickness of the coating resin layer can be measured in the same manner as the thickness of the resin layer.

[0165] The metal member used for the resin-metal composite member is not particularly limited, and for example, a metal cord, a metal plate, etc. can be used appropriately.

[0166] Examples of the metal cord include a monofilament (single wire) consisting of one metal cord, a multifilament (twisted wire) consisting of a plurality of metal cords twisted together, etc. From the viewpoint of improving the durability of the tire, the metal member is more preferably a multifilament.

[0167] The cross-sectional shape, size (diameter), etc. of the metal member are not particularly limited, and appropriate parameters can be used depending on the application.

[0168] When the metal member is a multifilament composed of a plurality of cords, the number of the plurality of cords may be, for example, 2 to 10, preferably 5 to 9.

[0169] When a resin-metal composite member is used to reinforce a tire, the thickness of the metal member is preferably 0.2 mm to 2 mm, more preferably 0.8 mm to 1.6 mm, from the viewpoint of achieving both the tire's internal pressure resistance and weight reduction. The thickness of the metal member is the arithmetic mean of the thicknesses measured at 5 randomly selected locations.

[0170] The tensile modulus of the metal member itself is generally about 100,000 MPa to 300,000 MPa, preferably 120,000 MPa to 270,000 MPa, and more preferably 150,000 MPa to 250,000 MPa. The tensile modulus of the metal member is calculated from the slope of a stress-strain curve drawn using a tensile tester and a ZWICK chuck.

[0171] The elongation at break (tensile elongation at break) of the metal component itself is usually about 0.1% to 15%, preferably 1% to 15%, and more preferably 1% to 10%. The tensile elongation at break of the metal component can be obtained from the strain by using a tensile tester and a ZWICK-type chuck to draw a stress-strain curve.

[0172] <Tires>

[0173] A tire according to the present embodiment includes the above-mentioned resin-metal composite member.

[0174] The resin metal composite member can be used as, for example, a tire frame constituting a tire or a reinforcing belt member or a bead member wound circumferentially around the outer periphery of the carcass.

[0175] Tire frame or carcass

[0176] In the present disclosure, the term "carcass" includes a so-called radial carcass, bias carcass, semi-radial carcass, etc. in conventional rubber tires. The carcass generally has a structure in which reinforcing materials such as cords and fibers are covered with a rubber material.

[0177] In the present disclosure, the term "tire frame" refers to a frame member formed of a resin material (a so-called tire frame for a resin tire).

[0178] Examples of the elastic material forming the carcass include the rubber material described below, and examples of the elastic material forming the tire frame include the resin material described below.

[0179] (Elastic material: rubber material)

[0180] The rubber material may contain at least rubber (rubber component), and may contain other components such as additives within the range that does not impair the effect of the present embodiment. The content of the rubber (rubber component) in the rubber material is preferably 50% by mass or more, and more preferably 90% by mass or more relative to the total amount of the rubber material.

[0181] The rubber component is not particularly limited, and natural rubber and various synthetic rubbers used in conventionally known rubber formulations may be used alone or in combination of two or more. For example, the following rubbers or a mixture of two or more thereof may be used.

[0182] The natural rubber may be in the form of a sheet or a block, and any of RSS#1 to #5 may be used.

[0183] As the synthetic rubber, various diene synthetic rubbers, diene copolymer rubbers, special rubbers, modified rubbers, etc. can be used. Specifically, for example, butadiene polymers such as polybutadiene (BR), copolymers of butadiene and aromatic vinyl compounds (such as SBR, NBR, etc.), copolymers of butadiene and other diene compounds, isoprene polymers such as polyisoprene (IR), copolymers of isoprene and aromatic vinyl compounds, copolymers of isoprene and other diene compounds, chloroprene rubber (CR), butyl rubber (IIR), halogenated butyl rubber (X-IIR), ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), and any mixtures thereof can be cited.

[0184] The rubber material may contain other components such as additives according to the purpose.

[0185] Examples of additives include reinforcing materials such as carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, antioxidants, and the like, and these may be appropriately blended.

[0186] The carcass formed of a rubber material can be obtained by heating an unvulcanized rubber material to vulcanize the rubber.

[0187] (Elastic material: resin material)

[0188] The resin material contains at least resin (resin component), and may contain other components such as additives within the scope of not damaging the effect of the present embodiment. Wherein, the content of the resin (resin component) in the aforementioned resin material is preferably 50% by mass or more relative to the total amount of the resin material, and more preferably 90% by mass or more.

[0189] Examples of the resin (resin component) contained in the resin material include thermoplastic resins, thermoplastic elastomers, and thermosetting resins. From the viewpoint of ride comfort during driving, the resin material preferably contains a thermoplastic elastomer.

[0190] Examples of the thermoplastic resin and thermoplastic elastomer include those described above as the thermoplastic resin and thermoplastic elastomer that can be contained in the resin composition. Examples of the thermosetting resin include phenolic resin, urea resin, melamine resin, epoxy resin, and the like.

[0191] From the viewpoint of adhesion, as the resin material forming the tire frame, it is preferred to use a material containing the same type of resin as the coating resin layer contained in the resin-metal composite component. For example, when the coating resin layer contains a polyester thermoplastic resin or a polyester thermoplastic elastomer, the tire frame is also preferably made of a polyester thermoplastic resin or a polyester thermoplastic elastomer.

[0192] The elastic material (rubber material or resin material) may contain other components other than rubber or resin as desired. Other components include fillers (silicon dioxide, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, colorants, weathering agents, reinforcing materials, etc.

[0193] <Tire Structure>

[0194] Hereinafter, a tire according to an embodiment of the present disclosure will be described with reference to the drawings.

[0195] The following figures are schematic diagrams, and the size and shape of each part are appropriately exaggerated for easy understanding. In addition, in the following embodiments, the resin metal composite member is applied to the belt portion, but in addition to the belt portion, the resin metal composite member can also be applied to other parts such as the tire bead portion.

[0196] (First Embodiment)

[0197] The tire according to the first embodiment includes a tire frame made of resin.

[0198] Figure 1A It is a perspective view showing a partial cross section of the tire according to the first embodiment. Figure 1B This is a cross-sectional view showing a state in which the bead portion of the tire is mounted on the rim (separated from the tire).

[0199] like Figure 1A As shown, the tire 10 according to the first embodiment is a pneumatic tire and has substantially the same cross-sectional shape as a conventional general rubber pneumatic tire.

[0200] The tire 10 includes a tire frame 17, which is composed of a pair of bead portions 12 in contact with a bead seat 21 and a rim flange 22 of a rim 20, a sidewall portion 14 extending radially outward from the bead portion 12, and a crown portion (outer peripheral portion) 16 connecting the radially outer end of one sidewall portion 14 and the radially outer end of the other sidewall portion 14. The tire frame 17 is formed of a resin material.

[0201] The tire frame 17 is formed by placing annular tire frame halves (tire frame pieces) 17A of the same shape obtained by injection molding one bead portion 12, one sidewall portion 14 and a crown portion 16 of half width face to face and joining them at the tire equatorial plane.

[0202] An annular bead core 18 composed of a steel cord is embedded in the bead portion 12. In addition, an annular sealing layer 24 is formed in the portion of the bead portion 12 that contacts the rim 20, at least in the portion that contacts the rim flange 22 of the rim 20. The annular sealing layer 24 is made of rubber, which is a material with better sealing properties than the resin material constituting the tire frame 17.

[0203] In the crown portion 16, when the cross section along the axial direction of the tire frame 17 is observed, the resin metal composite member 26 as a reinforcing cord is spirally wound in the circumferential direction of the tire frame 17 in a state where at least a part is buried in the crown portion 16. In addition, a tread 30 is arranged on the radially outer peripheral side of the resin metal composite member 26, and the tread 30 is composed of rubber as a material having better wear resistance than the resin material constituting the tire frame 17. The details of the resin metal composite member 26 are as follows.

[0204] In the tire 10 of the first embodiment, the tire frame 17 is formed of a resin material. The tire frame half 17A is bilaterally symmetrical, that is, one tire frame half 17A has the same shape as the other tire frame 17A, so there is an advantage that only one mold is required to mold the tire frame half 17A.

[0205] Among them, in the tire 10 involved in the first embodiment, the tire frame 17 is formed of a single resin material, but it is not limited to this method. For example, similar to a rubber pneumatic tire, resin materials with different characteristics can be used in various parts of the tire frame 17 (such as the sidewall 14, the crown 16, the bead 12, etc.). In addition, reinforcing materials (polymer materials, metal fibers, cords, non-woven fabrics, fabrics, etc.) can be embedded in various parts of the tire frame 17 (such as the sidewall 14, the crown 16, the bead 12, etc.), and the tire frame 17 can be reinforced with the reinforcing materials. It is also possible not to embed the reinforcing materials.

[0206] In the tire 10 involved in the first embodiment, the tire frame half 17A is formed by injection molding, but not limited to this, and can also be formed by, for example, vacuum molding, compressed air molding, casting, etc. In addition, in the tire 10 involved in the first embodiment, the tire frame 17 is formed by joining two components (tire frame half 17A), but not limited to this, and the tire frame can also be made into one component by using a molten core method, a split core method or blow molding using a low melting point metal, or can be formed by joining more than three components.

[0207] An annular bead core 18 made of a metal cord such as a steel cord is embedded in the bead portion 12 of the tire 10. The resin metal composite member according to the present embodiment described above can be used as a member including the bead core 18, and for example, the bead portion 12 can be formed of a resin metal composite member.

[0208] In addition, the bead core 18 can be formed by organic fiber cords, organic fiber cords coated with resin, or hard resin in addition to being formed by steel cords. If the rigidity of the bead portion 12 can be ensured and there is no problem in fitting with the rim 20, the bead core 18 can also be omitted.

[0209] An annular sealing layer 24 made of rubber is formed at the portion of the bead portion 12 that contacts the rim 20, or at least at the portion that contacts the rim flange 22 of the rim 20. The sealing layer 24 can also be formed at the portion where the tire frame 17 (bead portion 12) contacts the bead seat 21. When rubber is used as the material for forming the sealing layer 24, it is preferred to use the same type of rubber as that used on the outer surface of the bead portion of conventional ordinary rubber pneumatic tires. In particular, when the tire frame 17 is formed of a resin material, if the sealing between the tire frame 17 and the rim 20 can be ensured only by the resin material forming the tire frame 17, the rubber sealing layer 24 can also be omitted.

[0210] The sealant layer 24 may be formed using other thermoplastic resin or thermoplastic elastomer having a sealing property superior to that of the resin material forming the tire frame 17 .

[0211] Next, refer to Figure 2 The reinforcement belt member formed of the resin cord member 26 will be described. However, the resin metal composite member according to the present embodiment described above can be used for the resin cord member 26 .

[0212] Figure 2 It is a cross-sectional view along the tire rotation axis of the tire 10 according to the first embodiment, and shows a state in which the resin cord member 26 is embedded in the crown portion of the tire frame 17 .

[0213] like Figure 2 As shown, when observing the cross section along the axial direction of the tire frame 17, the resin cord member 26 is spirally wound in a state where at least a portion is buried in the crown portion 16. Moreover, the portion of the resin cord member 26 buried in the crown portion 16 is in a state of being closely attached to the resin material constituting the crown portion 16 (tire frame 17). Figure 2 Here, L represents the embedding depth of the resin cord member 26 in the crown portion 16 (tire frame 17 ) in the tire rotation axis direction. In one embodiment, the embedding depth L of the resin cord member 26 in the crown portion 16 is 1 / 2 of the diameter D of the resin cord member 26 .

[0214] The resin cord member 26 has a structure in which a metal member 27 (for example, a steel cord formed by twisting steel fibers) is used as a core, and the outer periphery of the metal member 27 is covered with a coating resin layer 28 via an adhesive layer 25 .

[0215] A rubber tread 30 is disposed on the tire radial direction outer peripheral side of the resin cord member 26. Also, the tread 30 has a tread pattern composed of a plurality of grooves formed on the surface in contact with the road surface, similarly to a conventional rubber pneumatic tire.

[0216] In one embodiment, in the tire 10, the resin cord member 26 coated with the coating resin layer 28 containing a thermoplastic elastomer is embedded in a state of being closely attached to the tire frame 17 formed of a resin material containing the same thermoplastic elastomer. Therefore, the contact area between the coating resin layer 28 of the coated metal member 27 and the tire frame 17 is increased, the durability of the resin cord member 26 and the tire frame 17 is improved, and as a result, the durability of the tire becomes excellent.

[0217] When the resin cord member 26 is buried in the crown portion 16, the buried depth L of the resin cord member 26 relative to the crown portion 16 is preferably 1 / 5 or more of the diameter D of the resin cord member 26, and more preferably more than 1 / 2. Moreover, it is further preferred that the resin cord member 26 is buried in the crown portion 16 as a whole. If the buried depth L of the resin cord member 26 exceeds 1 / 2 of the diameter D of the resin cord member 26, it is difficult for the resin cord member 26 to protrude from the buried portion in consideration of the size of the resin cord member 26. Moreover, if the resin cord member 26 is buried in the crown portion 16 as a whole, the surface (peripheral surface) becomes flat, and even when a member is placed on the crown portion 16 in which the resin cord member 26 is buried, it is possible to suppress the air from entering the peripheral portion of the resin cord member 26.

[0218] In the tire 10 according to the first embodiment, the tread 30 is formed of rubber, but a tread formed of a thermoplastic resin material having excellent wear resistance may be used instead of rubber.

[0219] Next, a method for manufacturing a tire according to the first embodiment will be described.

[0220] [Tire frame molding process]

[0221] First, the tire frame halves supported by thin metal support rings are made to face each other. Then, a joining mold is set in a manner to contact the outer peripheral surface of the abutment portion of the tire frame halves. Here, the above-mentioned joining mold is configured to press the periphery of the joining portion (abutment portion) of the tire frame halves with a predetermined pressure (not shown in the figure). Then, the periphery of the joining portion of the tire frame halves is pressed at a temperature above the melting point (or softening point) of the resin material forming the tire frame. If the joining portion of the tire frame halves is heated and pressurized by the joining mold, the above-mentioned joining portion melts, the tire frame halves fuse to each other, and these components become one to form the tire frame 17.

[0222] [Resin cord member molding process]

[0223] Next, a description will be given of a step of molding a resin cord member as the resin metal composite member according to the present embodiment.

[0224] First, for example, the metal member 27 is unwound from a reel and its surface is washed. Then, the outer periphery of the metal member 27 is coated with a material for forming an adhesive layer extruded from an extruder to form an adhesive layer 25. Further, the resin extruded from an extruder is coated thereon to form a coating resin layer 28. Then, the obtained resin cord member 26 is wound on a reel 58.

[0225] [Resin cord member winding step]

[0226] Next, refer to Figure 3 The resin cord member winding step will be described. Figure 3 This is an explanatory diagram for explaining the operation of installing the resin cord member on the crown portion of the tire frame using the resin cord member heating device and rollers. Figure 3 In the embodiment, the resin cord member supply device 56 comprises: a reel 58 wound with the resin cord member 26, a resin cord member heating device 59 arranged on the downstream side of the reel 58 in the cord conveying direction, a first roller 60 arranged on the downstream side of the resin cord member 26 conveying direction, a first cylinder device 62 that moves the first roller 60 in the direction of contacting and leaving the outer peripheral surface of the tire, a second roller 64 arranged on the downstream side of the resin cord member 26 conveying direction of the first roller 60, and a second cylinder device 66 that moves the second roller 64 in the direction of contacting and leaving the outer peripheral surface of the tire. The second roller 64 can be used as a metal cooling roller. In addition, in order to prevent the adhesion of the molten or softened resin material, the surface of the first roller 60 or the second roller 64 is coated with a fluororesin (for example, Teflon (registered trademark)). Through the above operation, the heated resin cord member is firmly integrated with the outer shell resin of the tire frame body.

[0227] The resin cord member heating device 59 includes a heater 70 for generating hot air and a fan 72. The resin cord member heating device 59 also includes a heating box 74 in which hot air is supplied and through which the resin cord member 26 passes, and an outlet 76 through which the heated resin cord member 26 is discharged.

[0228] In this process, the temperature of the heater 70 of the resin cord component heating device 59 is first raised, and the surrounding air heated by the heater 70 is transported to the heating box 74 by the wind generated by the rotation of the fan 72. Then, the resin cord component 26 rolled out from the reel 58 is sent to the heating box 74 where the internal space is heated by hot air, and is heated (for example, the temperature of the resin cord component 26 is heated to about 100°C to 250°C). The heated resin cord component 26 passes through the discharge port 76, maintains a certain tension, and is spirally wound along the Figure 3 The outer circumference of the crown portion 16 of the tire frame 17 rotating in the direction of the arrow R. Here, if the coated resin layer of the heated resin cord member 26 contacts the outer circumference of the crown portion 16, the resin material of the contact portion melts or softens, and melts and joins with the resin of the tire frame, thereby integrating with the outer circumference of the crown portion 16. At this time, the resin cord member will also melt and join with the adjacent resin cord member, so it is wound in a state without a gap. As a result, air can be suppressed from entering the portion where the resin cord member 26 is buried.

[0229] The embedding depth L of the resin cord member 26 can be adjusted by the heating temperature of the resin cord member 26, the tension acting on the resin cord member 26, the pressing force of the first roller 60, etc. In one embodiment, the embedding depth L of the resin cord member 26 is set to 1 / 5 of the diameter D of the resin cord member 26 or more.

[0230] Next, the belt-shaped tread 30 is wound around the outer peripheral surface of the tire frame 17 in which the resin cord member 26 is embedded, and is placed in a vulcanizer or mold to be heated (vulcanized). The tread 30 may be unvulcanized rubber or vulcanized rubber.

[0231] Then, when the sealant layer 24 made of vulcanized rubber is bonded to the bead portion 12 of the tire frame 17 using an adhesive or the like, the tire 10 can be manufactured.

[0232] In the tire manufacturing method involved in the first embodiment, the joining portion of the tire frame half 17A is heated using a joining mold, but the present embodiment is not limited to this method. For example, the above-mentioned joining portion can also be heated using a separately arranged high-frequency heating machine, or it can be softened or melted in advance using hot air, infrared irradiation, etc., and pressurized using a joining mold to join the tire frame half 17A.

[0233] In the tire manufacturing method according to the first embodiment, the resin cord member supply device 56 includes two rollers, the first roller 60 and the second roller 64 . However, the present embodiment is not limited to this configuration and may include only one of the rollers (ie, one roller).

[0234] The first embodiment involves a tire manufacturing method in which the resin cord member 26 is heated to melt or soften the surface of the tire frame 17 in contact with the heated resin cord member 26. However, the present embodiment is not limited to this method and the resin cord member 26 may not be heated. Instead, a hot air generating device may be used to heat the outer peripheral surface of the crown portion 16 in which the resin cord member 26 is embedded and then the resin cord member 26 is embedded in the crown portion 16.

[0235] In addition, in the tire manufacturing method involved in the first embodiment, a method is adopted in which the heat source of the resin cord component heating device 59 is set as a heater and a fan, but this embodiment is not limited to this method, and it can also be set as a method of directly heating the resin cord component 26 with radiant heat (such as infrared rays, etc.).

[0236] Furthermore, in the tire manufacturing method involved in the first embodiment, a method of forcibly cooling the melted or softened portion of the thermoplastic resin material of the embedded resin cord component 26 using a metal second roller 64 is adopted, but the present embodiment is not limited to this method, and a method of directly blowing cold air on the melted or softened portion of the thermoplastic resin material to forcibly cool and solidify the melted or softened portion of the thermoplastic resin material may also be adopted.

[0237] It is easy to manufacture by spirally winding the resin cord member 26 , but a method of discontinuously arranging the resin cord member 26 in the width direction is also conceivable.

[0238] In the tire of the present embodiment, the resin cord member 26 is formed of only one layer, but may be formed of two or more layers.

[0239] In the manufacturing method of the tire involved in the first embodiment, a method of winding the belt-shaped tread 30 on the outer peripheral surface of the tire frame 17 in which the resin cord member 26 is embedded and then heating (vulcanizing) is adopted, but the present embodiment is not limited to this method, and a method of bonding the vulcanized belt-shaped tread to the outer peripheral surface of the tire frame 17 with an adhesive or the like may be adopted. Examples of the vulcanized belt-shaped tread include, for example, pre-cured treads used in retreaded tires.

[0240] The tire 10 according to the first embodiment is a so-called tubeless tire in which an air chamber is formed between the tire 10 and the rim 20 by attaching the bead portion 12 to the rim 20 , but the present embodiment is not limited to this form and may be a complete tube shape.

[0241] (Second Embodiment)

[0242] A tire according to a second embodiment includes a carcass instead of a tire frame.

[0243] Figure 4 It is a cross-sectional view in the tire width direction schematically showing the structure of the tire 11 according to the present embodiment. Figure 4 , for convenience, the rim R on which the tire 11 is assembled is shown by a dotted line.

[0244] like Figure 4 As shown, the tire 11 includes a pair of bead portions 112 disposed on both sides of the tire equatorial plane CL, a pair of sidewall portions 111 extending radially outward from the pair of bead portions 112, and a tread portion 110 connecting the pair of sidewall portions 111. The pair of bead portions 112 each include a bead core 160.

[0245] Figure 4 In the example of the embodiment, a carcass 120 including at least one carcass ply (one in the example shown) extends in a toroidal shape between the bead cores 160 included in a pair of bead portions 112. The carcass ply of the carcass 120 has a structure in which a cord made of steel or organic fiber is covered with rubber, for example.

[0246] Figure 4 In the example, the carcass 120 includes: a main body portion 120a extending in a ring shape between a pair of bead cores 160, and a pair of folded portions 120b folded from the innermost end of the main body portion 120a in the tire radial direction to the outer side in the tire width direction on both sides relative to the tire equatorial plane CL and around the bead core 160.

[0247] Figure 4 In the example of the tire, an airtight layer 180 for preventing tire leakage is arranged inside the tread portion 110 and the sidewall portion 111. Furthermore, a belt 130 composed of at least one layer (one layer in the example shown) of belt layers is arranged at a position closer to the tire radial direction outer side than the crown region of the carcass 120 in the tread portion 110. The belt layer is formed by winding a resin-coated reinforcing cord around a portion forming the belt layer, for example.

[0248] Figure 4 In the example of , a bead member 150 including a bead filler 170 and a bead core 160 located inside the bead filler 170 in the tire radial direction and including a metal cord such as a steel cord is arranged on the bead portion 112 . Figure 4 In the example of FIG. 1 , the bead member 150 is buried in the rubber 140 .

[0249] Figure 4In the example of the embodiment, the belt 130 and the bead core 160 can be formed using the resin metal composite member of the above embodiment. In this case, either the belt 130 or the bead core 160 can be formed using the resin metal composite member of the above embodiment, or both can be formed using the resin metal composite member of the above embodiment.

[0250] Various embodiments have been described above, but these embodiments are only examples, and the present disclosure can be implemented with various modifications without departing from the spirit thereof. In addition, it goes without saying that the scope of rights of the present disclosure is not limited to these embodiments.

[0251] The present disclosure includes tires in the following forms.

[0252] <1> A resin composition comprising a thermoplastic elastomer and an epoxy resin as resins, and zinc cyanurate.

[0253] <2> The resin composition according to <1>, wherein a content of the zinc cyanurate in the entire resin composition is 0.1% by mass to 5% by mass.

[0254] <3> The resin composition according to <1> or <2>, wherein a content of the epoxy resin in the entire resin composition is 15% by mass or less.

[0255] <4> The resin composition according to any one of <1> to <3>, wherein a content of the epoxy resin in the entire resin composition is 1% by mass or more.

[0256] <5> The resin composition according to any one of <1> to <4>, wherein an epoxy equivalent of the epoxy resin is 100 g / eq to 300 g / eq.

[0257] <6> The resin composition according to any one of <1> to <5>, wherein, when A (mass %) is the content of the epoxy resin in the entire resin composition and B (g / eq) is the epoxy equivalent of the epoxy resin, the value of A / B is 0.003 to 0.15.

[0258] <7> The resin composition according to any one of <1> to <6>, wherein the thermoplastic elastomer contains a polyester-based thermoplastic elastomer.

[0259] <8> The resin composition according to any one of <1> to <7>, further comprising a thermoplastic resin as a resin.

[0260] <9> The resin composition according to any one of <1> to <8>, wherein a weight average molecular weight of the entire resin is 40,000 or more.

[0261] <10> A resin-metal composite member comprising a metal member and a resin layer disposed around the metal member, wherein the resin layer is composed of the resin composition according to any one of <1> to <9>.

[0262] <11> A tire comprising the resin-metal composite member according to <10>.

[0263] <12> The tire according to <11>, wherein at least one of a reinforcement belt member and a bead member of the tire includes the resin-metal composite member.

[0264] Example

[0265] The present disclosure will be specifically described below by way of examples, but the present disclosure is not limited to these descriptions at all.

[0266] <Preparation of resin composition>

[0267] The materials described in Table 1 were mixed in the amounts (parts by mass) shown in Table 1 to prepare a resin composition. The details of the materials shown in Table 1 are as follows. The obtained resin composition was evaluated in (1) to (3). The results are shown in Table 1.

[0268] TPC1...Polyester thermoplastic elastomer (Toray-DuPont, "Hytrel 6367")

[0269] TPC2...Polyester thermoplastic elastomer (manufactured by Toray-DuPont, "Hytrel 7247")

[0270] TPC3...Polyester thermoplastic elastomer (Toray-DuPont, "Hytrel 6377")

[0271] TPC4: a polyester thermoplastic elastomer containing a maleic anhydride group (manufactured by Mitsubishi Chemical Corporation, "Primalloy GQ741", maleic anhydride group equivalent: about 9.5 × 10 -5 eq / g)

[0272] PBT: Polybutylene terephthalate (Toray Industries, Inc., “Toraycon 1401X06”)

[0273] Epoxy resin 1: an epoxy resin represented by the following formula (A) (manufactured by Nippon Kayaku Co., Ltd., "XD-1000", epoxy equivalent 245 g / eq to 260 g / eq, softening point 68° C. to 78° C.)

[0274] Epoxy resin 2: an epoxy resin represented by the following formula (B) (manufactured by Nippon Kayaku Co., Ltd., "NC-7000L", epoxy equivalent 223 g / eq to 238 g / eq, softening point 83° C. to 93° C.)

[0275] Additives: Zinc cyanurate (Nissan Chemical Co., Ltd., "Star Fine F-10")

[0276] [Chemistry 6]

[0277]

[0278]

[0279] The tensile modulus, brass peel strength, and weight average molecular weight of the prepared resin composition were measured by the following methods.

[0280] (1) Tensile modulus

[0281] The tensile modulus is measured in accordance with JIS K7113: 1995. Specifically, for example, using Tensilon RTF-1210 (1 KN) manufactured by A&D Corporation, the tensile modulus (unit: MPa) of the resin composition is measured at a tensile speed of 100 mm / min.

[0282] The tensile modulus of the resin composition can also be measured by preparing a test specimen of the same material as the resin composition. Specifically, a plate of 2 mm in thickness formed by the resin composition can be made by injection molding, and a test specimen punched into a dumbbell test piece of JIS3 can be prepared to measure the tensile modulus.

[0283] (2) Brass peeling force

[0284] The adhesion of the resin composition to the metal component is tested by a peel test. Specifically, a resin plate composed of the resin composition and a test piece with a width of 20 mm composed of brass (Cu / Zn=65 / 35) are prepared, and the resin plate is melted with a press at 230°C, and pressed with the test piece to make a laminate. Using the laminate, and using a Shimadzu Autograph AGS-J (5KN) made by Shimadzu Corporation as a tensile testing machine, a 180° peel test is performed at a tensile speed of 100 mm / min at room temperature (25°C) to measure the peel force (unit: N). The measured value of Example 1 is set to 100, and the obtained measured value is converted into an index.

[0285] (3) Weight average molecular weight

[0286] The weight average molecular weight (Mw) is calculated by polystyrene conversion in gel permeation chromatography (GPC). Specifically, after the resin composition is dissolved in a solvent such as hexafluoroisopropanol (HFIP), the insoluble matter is filtered with a filter, and the relative molecular weight relative to the reference substance is derived by GPC. ECOSEC (HLC-8320GPC) manufactured by Tosoh Corporation is used as a measuring instrument, and HFIP is used as a solvent.

[0287] (4) Cracking resistance

[0288] Resin-metal composite members having an adhesive layer formed using the resin compositions obtained in Example 1 and Comparative Example 1 and tires having the resin-metal composite members arranged in the crown portion were prepared, and the crack resistance of the adhesive layer was evaluated.

[0289] Specifically, using the average diameter Multifilament (7 strands A cord-shaped resin metal composite member having an adhesive layer and a coating resin layer formed in sequence around the multifilament was prepared by extrusion molding of a stranded wire formed by twisting a single filament (steel, strength: 280N, elongation: 3%) of 1000 Nm), a resin composition for forming an adhesive layer, and a polyester-based thermoplastic elastomer (Toray-DuPont, "Hytrel5557") for forming a coating resin layer. The thickness of the adhesive layer was adjusted to 1 μm to 500 μm, and the thickness of the coating resin layer was adjusted to 10 μm to 1000 μm.

[0290] The produced resin-metal composite member was wound around the crown portion to produce a rubber tire (size: 225 / 40R18), and the internal pressure was adjusted to 3.0 kg / cm in a room at 25±2°C. 2 After that, the tire was left for 24 hours. Then, the air pressure was adjusted again, the tire was subjected to a load of 1010 kg, and the tire was driven for 6000 km at a speed of 60 km / h on a roller with a diameter of about 3 m. The tire after driving was cut in the radial direction, and the cross section of the adhesive layer was observed with an optical microscope to investigate the occurrence of cracks.

[0291] As a result of the test, in Comparative Example 1, the number of cracks in the adhesive layer after the running test was 5 or more per cross section, whereas in Example 1, the number of cracks in the adhesive layer after the running test was less than 5 per cross section.

[0292] [Table 1]

[0293]

[0294] In Table 1, the weight average molecular weight of Example 2 is a predicted value.

[0295] As shown in the above results, the resin composition of the example containing epoxy resin and zinc cyanurate exhibited excellent brass peeling strength compared with the resin compositions of Comparative Examples 1 and 2 containing neither epoxy resin nor zinc cyanurate, and the resin composition of Comparative Example 3 containing epoxy resin but not zinc cyanurate. In addition, when used as an adhesive layer of a resin-metal composite of a tire, it exhibited excellent crack resistance.

[0296] The disclosure of Japanese Patent Application No. 2019-224542 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each document, patent application, and technical standard were specifically and separately described as being incorporated by reference.

Claims

1. A resin composition comprising a thermoplastic elastomer and an epoxy resin as resins, and zinc cyanurate, The thermoplastic elastomer contains a polyester-based thermoplastic elastomer, The content of the zinc cyanurate in the entire resin composition is 0.1% by mass to 5% by mass. 2 . The resin composition according to claim 1 , wherein the content of the epoxy resin in the entire resin composition is 15% by mass or less. 3 . The resin composition according to claim 1 , wherein the content of the epoxy resin in the entire resin composition is 1% by mass or more. 4 . The resin composition according to claim 1 , wherein the epoxy equivalent of the epoxy resin is 100 g / eq to 300 g / eq. 5 . The resin composition according to claim 1 , wherein, when the content of the epoxy resin in the entire resin composition is A mass %, and the epoxy equivalent of the epoxy resin is B g / eq, the value of A / B is 0.003 to 0.

15. 6 . The resin composition according to claim 1 , further comprising a thermoplastic resin as a resin. 7 . The resin composition according to claim 1 , wherein the weight average molecular weight of the entire resin is 40,000 or more. 8 . A resin-metal composite member comprising a metal member and a resin layer disposed around the metal member, wherein the resin layer is composed of the resin composition according to claim 1 . 9 . A tire comprising the resin-metal composite member according to claim 8 . 10 . The tire according to claim 9 , wherein at least one of a reinforcement belt member and a bead member of the tire includes the resin-metal composite member.

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