Reinforced thermoplastic elastomer composition and molded article

Abstract

The present invention is a reinforced thermoplastic elastomer composition obtained by blending a thermoplastic resin (A) having a melting point of 200°C or higher by differential scanning calorimetry (DSC), a thermoplastic elastomer (B), and a filler (C), wherein the loss tangent at a frequency of 100 Hz and a temperature of 23°C is 0.10 or more, the storage modulus at a frequency of 100 Hz and a temperature of 160°C is 30 MPa or more, and the melting point by differential scanning calorimetry (DSC) is 200°C or more. Provided is a reinforced thermoplastic elastomer composition that can be easily molded, is excellent in vibration damping property, heat resistance, and high temperature rigidity, is excellent in vibration damping property at normal temperature, and can be used as a sound absorbing member or a vibration control member capable of maintaining shape even alone in a harsh temperature environment.

Description

Reinforced thermoplastic elastomer composition and molded article

[0001] The present invention relates to a reinforced thermoplastic elastomer composition obtained by blending a thermoplastic resin, a thermoplastic elastomer and a filler, and to a molded article using the same.

[0002] Conventionally, flexible polymeric materials have been widely used in which rubbers, such as natural rubber or synthetic rubber, are crosslinked under high temperature and pressure by blending them with crosslinking agents and reinforcing agents. However, such rubbers require long-term crosslinking and molding processes under high temperature and pressure, resulting in poor processability. Furthermore, crosslinked rubbers do not exhibit thermoplasticity, and therefore generally cannot be recycled like thermoplastic resins. Therefore, various thermoplastic elastomers have been developed in recent years that can be easily manufactured into molded products using general-purpose melt molding techniques, such as injection molding, hot press molding, and extrusion molding, in the same way as conventional thermoplastic resins. Furthermore, in recent years, there has been an increasing demand for quieter vehicle interiors, and efforts are being made to reduce the vibration of various interior components and improve quietness.

[0003] Patent Document 1 discloses a thermoplastic resin composition having a good balance between rigidity and impact resistance, the thermoplastic resin composition comprising, as main components, a modified conjugated diene polymer having at least one group selected from the group consisting of an alkoxysilyl group, an amino group, an acid anhydride group, and a carboxyl group, and a polar resin.

[0004] Japanese Patent Application Laid-Open No. 2006-291117

[0005] The specific example disclosed in Patent Document 1 is a resin composition comprising a diene copolymer having a reactive functional group and polyamide 6. However, the loss tangent used as an indicator of vibration damping properties (the larger the value, the better the vibration damping properties) was low in this resin composition, making it impossible to obtain excellent vibration damping properties and insufficient for use as a sound-absorbing or vibration-damping material. Furthermore, the high-temperature rigidity was low, making it difficult to apply to automotive, aircraft, industrial equipment, etc.

[0006] An object of the present invention is to provide a reinforced thermoplastic elastomer composition that can be easily molded, can retain its shape even when used alone in severe temperature environments, and is applicable to automobiles, aircraft, industrial equipment, etc.

[0007] In order to solve the above problems, the present invention has the following configuration: (1) A reinforced thermoplastic elastomer composition comprising a thermoplastic resin (A) having a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC), a thermoplastic elastomer (B), and a filler (C), wherein the reinforced thermoplastic elastomer composition has a loss tangent of 0.10 or higher at a frequency of 100 Hz and a temperature of 23°C, a storage modulus of 30 MPa or higher at a frequency of 100 Hz and a temperature of 160°C, and a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC). (2) The reinforced thermoplastic elastomer composition according to (1), wherein the thermoplastic resin (A) having a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC) and the thermoplastic elastomer (B) contained in the reinforced thermoplastic elastomer composition are in a mass ratio of (A):(B) = 40:60 to 70:30, and the amount of filler (C) blended is 10 to 200 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A) and the thermoplastic elastomer (B). (3) The reinforced thermoplastic elastomer composition according to (1) or (2), wherein the thermoplastic resin (A) is at least one selected from the group consisting of polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, and polyphenylene sulfide resin. (4) The reinforced thermoplastic elastomer composition according to any one of (1) to (3), wherein the thermoplastic elastomer (B) is at least one selected from the group consisting of a copolymer (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and having a reactive functional group, and a copolymer (B2) other than the component (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof. (5) The reinforced thermoplastic elastomer composition according to (4), wherein the polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof is a polymer block derived from at least one selected from isoprene, butadiene, ethylene-butylene, and ethylene-propylene.(6) The reinforced thermoplastic elastomer composition is a reinforced thermoplastic elastomer composition comprising: (A) a thermoplastic resin having a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC); (B1) a copolymer having a reactive functional group, which contains a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof; (B2) a copolymer other than the component (B1), which contains a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof; and (C) a filler. A thermoplastic elastomer composition according to any one of (1) to (5), wherein the mass ratios of the thermoplastic resin (A), the copolymer (B1), and the copolymer (B2) contained in the reinforced thermoplastic elastomer composition are (A):(B1)=45:55 to 95:5, (B1):(B2)=90:10 to 5:95, and (A):((B1)+(B2))=40:60 to 70:30, and the amount of the filler (C) blended is 10 to 200 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A), the copolymer (B1), and the copolymer (B2). (7) The reinforced thermoplastic elastomer composition according to any one of (1) to (6), wherein the copolymer (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof and having a reactive functional group is a copolymer (B1-1) having a glass transition temperature in the range of -20°C to 60°C. (8) The reinforced thermoplastic elastomer composition according to any one of (1) to (6), wherein the copolymer (B2) other than the component (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof is a copolymer (B2-1) having a glass transition temperature in the range of -20°C to 60°C. (9) The reinforced thermoplastic elastomer composition according to any one of (1) to (6), further comprising a hydrogenated petroleum resin (D), wherein the amount of the hydrogenated petroleum resin (D) is 0.01 to 20 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A), the copolymer (B1), and the copolymer (B2). (10) A molded article made of the reinforced thermoplastic elastomer composition according to any one of (1) to (9).(11) A molded product, wherein the molded product according to (10) is a sound-absorbing material. (12) A molded product, wherein the molded product according to (10) is a vibration-damping material. (13) An electric / electronic device, an automobile, an electric vehicle, a fuel cell vehicle, an aircraft, a drone, an electric vertical take-off and landing unpiloted aircraft, a railway vehicle component, an industrial machine, a construction component, an office product, an optical device, a precision machine, or an artificial satellite, in which the molded product according to any one of (10) to (12) is used.

[0008] The reinforced thermoplastic elastomer composition of the present invention has excellent vibration damping properties, heat resistance, and high-temperature rigidity. Furthermore, the reinforced thermoplastic elastomer composition of the present invention can be easily molded using general-purpose melt molding techniques such as injection molding, hot press molding, and extrusion molding, just like ordinary thermoplastic resins. The reinforced thermoplastic elastomer composition of the present invention can be used in, for example, automobiles, aircraft, drones, and vertical takeoff and landing unpiloted aircraft, electrical and electronic applications, railway vehicles, building materials, industrial equipment, and the like.

[0009] The present invention will now be described in further detail.

[0010] The present invention provides a reinforced thermoplastic elastomer composition comprising a thermoplastic resin (A) having a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC), a thermoplastic elastomer (B), and a filler (C), the reinforced thermoplastic elastomer composition having a loss tangent of 0.10 or higher at a frequency of 100 Hz and a temperature of 23°C, a storage modulus of 30 MPa or higher at a frequency of 100 Hz and a temperature of 160°C, and a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC).

[0011] In the present invention, the thermoplastic resin (A) having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC) (hereinafter, sometimes abbreviated as thermoplastic resin (A)) is a resin that has a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC) and can be molded by heating and melting.

[0012] The thermoplastic resin (A) preferably used in the present invention is at least one selected from polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, and polyphenylene sulfide resin, since it can give molded articles excellent in physical properties such as heat resistance and strength, and more preferably polyamide resin.

[0013] The melting point of the thermoplastic resin (A) in the present invention by DSC can be determined by the following method. First, a differential scanning calorimeter (DSC-7 manufactured by PerkinElmer) is used, and two-point calibration (indium, lead) and baseline correction are performed. 8 to 10 mg of a sample of the thermoplastic resin (A) is weighed, and the sample is heated at a heating rate of 20°C / min. The melting endothermic peak observed during the heating process is taken as the melting point.

[0014] The melting point of the thermoplastic resin (A) is 200° C. or higher. If the melting point is lower than 200° C., the heat resistance of the reinforced thermoplastic elastomer composition of the present invention will decrease. The melting point of the thermoplastic resin (A) is more preferably 205° C. or higher, and even more preferably 210° C. or higher.

[0015] On the other hand, the upper limit of the melting point of the thermoplastic resin (A) is not particularly limited, but is preferably 400°C or lower, since this tends to suppress decomposition of the thermoplastic elastomer (B) and prevent a decrease in mechanical properties, more preferably 370°C or lower, and even more preferably 350°C or lower.

[0016] Examples of means for adjusting the melting point of the thermoplastic resin (A) to fall within the above range include a method of selecting one having the desired melting point from thermoplastic resins with different melting points, and a method of adjusting the degree of polymerization or copolymerization ratio of the thermoplastic resin.

[0017] The polyamide resin is not particularly limited, but is generally a polymer obtained from amino acids, lactams, or diamines and dicarboxylic acids as main raw materials. Typical examples of such raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid; lactams such as ε-caprolactam and ω-laurolactam; aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, and 5-methylnonamethylenediamine; aromatic diamines such as metaxylylenediamine and paraxylylenediamine; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(aminomethyl) ... Alicyclic diamines such as (4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperazine; aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. In the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used. Two or more of these polyamide resins may be used.

[0018] Specific examples of polyamide resins preferably used in the present invention include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene terephthalamide / polycaproamide copolymer (polyamide 6T / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene terephthalamide / polycaproamide copolymer (polyamide 6T / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene sebacamide (polyamide 610), polyhexamethylene sebacamide / polyhexamethylene sebacamide (polyamide 610), polyhexamethylene sebacamide / polyhexamethylene sebacamide copolymer (polyamide 66 / 6T), polyhexamethylene adip ... Examples of the polyamide include methylene isophthalamide copolymer (polyamide 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyhexamethylene terephthalamide / poly(2-methylpentamethylene) terephthalamide copolymer (polyamide 6T / M5T), polyxylylene adipamide (polyamide XD6), and mixtures or copolymers thereof. Particularly preferred are polyamide 6, polyamide 610, and polyamide 66, and more preferred is polyamide 6.

[0019] Although there are no particular restrictions on the degree of polymerization of the polyamide resin, it is preferable that the relative viscosity, measured at 25°C in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml, be in the range of 1.5 to 7.0. If the relative viscosity is 1.5 or higher, the melt viscosity of the reinforced thermoplastic elastomer composition during molding will be appropriately high, which will suppress air entrapment during molding and further improve moldability. On the other hand, if the relative viscosity is 7.0 or lower, the melt viscosity of the reinforced thermoplastic elastomer composition during molding will be appropriately low, which will further improve moldability.

[0020] There is no particular limitation on the amount of amino terminal groups in the polyamide resin, but it is preferably 1.0×10 －５ ~12.0 x 10 －５ The amount of amino terminal groups is preferably in the range of 1.0×10 mol / g. －５~12.0 x 10 －５ Within this range, a sufficient degree of polymerization can be obtained, and the mechanical strength of the molded product can be improved. Here, the amount of amino terminal groups in the polyamide resin can be determined by dissolving the polyamide resin in a phenol / ethanol mixed solvent (83.5:16.5 (volume ratio)) and titrating the solution with a 0.02 N hydrochloric acid solution.

[0021] The polybutylene terephthalate resin is not particularly limited, but is generally a polymer obtained by a polycondensation reaction using terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative as the main raw materials. Copolymerization components may be included to the extent that the properties are not impaired. The copolymerization amount of the copolymerization components is preferably 20 mol% or less based on the total monomer components. Preferred examples of these polymers and copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene (terephthalate / naphthalate), and poly(butylene / ethylene) terephthalate. These may be used alone or in combination of two or more. Polybutylene terephthalate is particularly preferred.

[0022] From the viewpoint of moldability and mechanical properties, these polymers and copolymers preferably have an intrinsic viscosity (dl / g) measured in o-chlorophenol solution at 25°C in the range of 0.10 to 2.00, particularly 0.30 to 1.60, and most preferably 0.45 to 1.35.

[0023] The polyethylene terephthalate resin is not particularly limited, but is generally a polymer obtained by a polycondensation reaction using terephthalic acid or its ester-forming derivative and ethylene glycol or its ester-forming derivative as the main raw materials. It may contain a copolymerization component within a range that does not impair its properties. The copolymerization amount of the copolymerization component is preferably 20 mol % or less based on the total monomer components.

[0024] From the viewpoint of moldability and mechanical properties, these polymers and copolymers preferably have an intrinsic viscosity (dl / g) measured in o-chlorophenol solution at 25°C in the range of 0.10 to 2.00, particularly 0.30 to 1.60, and most preferably 0.45 to 1.35.

[0025] The polyphenylene sulfide resin is not particularly limited, but a polymer having a repeating unit represented by the following structural formula can be preferably used.

[0026]

[0027] From the viewpoint of heat resistance, a polymer containing 70 mol % or more, and even 90 mol % or more, of the repeating units represented by the structural formula above is preferred. Furthermore, the polyphenylene sulfide resin may be composed of repeating units having any of the following structures, with less than 30 mol % of the repeating units being of that structure. Among these, a p-phenylene sulfide / m-phenylene sulfide copolymer (a copolymer containing 20 mol % or less of m-phenylene sulfide units) is preferably used because it combines moldability and barrier properties.

[0028]

[0029] Polyphenylene sulfide resins can be produced in high yields by reacting a polyhalogenated aromatic compound with a sulfidizing agent in a polar organic solvent, followed by recovery and post-treatment of the resulting polyphenylene sulfide resin. Specifically, they can be produced by a method for obtaining a polymer with a relatively low molecular weight, as described in Japanese Patent Publication No. 45-3368, or by a method for obtaining a polymer with a relatively high molecular weight, as described in Japanese Patent Publication No. 52-12240 or Japanese Patent Laid-Open Publication No. 61-7332. The polyphenylene sulfide resins obtained as described above can also be used after various treatments, such as crosslinking / polymerization by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvents, hot water, or acid aqueous solutions, or activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, or functional group-containing disulfide compounds.

[0030] The melt viscosity of the polyphenylene sulfide resin used in the present invention is 1 to 2000 Pa·s (300°C, shear rate 1000 sec) from the viewpoint of improving chemical resistance and imparting properties such as fluidity during processing. －１ ) is preferably in the range of 1 to 200 Pa·s, more preferably in the range of 1 to 50 Pa·s. －１ The values ​​were measured using a high-speed flow tester under the conditions of 1) above, using a nozzle with a nozzle diameter of 0.5 mm and a nozzle length of 10 mm.

[0031] The thermoplastic elastomer (B) referred to in the present invention is an organic resin that behaves as a rubbery elastic body at room temperature but undergoes plastic deformation as the temperature rises (see pages 180 to 207 of Practical Plastics Encyclopedia, published by Sangyo Chosakai Co., Ltd. on May 1, 1993). Examples of the thermoplastic elastomer (B) used in the present invention include styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers. Two or more of these may be blended together.

[0032] Among these, a styrene-based thermoplastic elastomer is preferably used because it has excellent compatibility with the thermoplastic resin (A) and a high vibration-damping improving effect. The styrene-based thermoplastic elastomer is preferably at least one selected from a copolymer (B1) (hereinafter sometimes abbreviated as copolymer (B1)) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and having a reactive functional group, and a copolymer (B2) (hereinafter sometimes abbreviated as copolymer (B2)) other than the component (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof.

[0033] The copolymer (B1) used in the present invention is a copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and having a reactive functional group.

[0034] The polymer block mainly composed of an aromatic vinyl compound in the copolymer (B1) is a polymer block in which, of the units constituting the polymer block, units derived from an aromatic vinyl compound account for 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more.

[0035] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α Examples of suitable styrene derivatives include 2,4,6-trichlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, and vinylnaphthalene. Among these, styrene, α-methylstyrene, or a mixture thereof is preferred from the viewpoints of industrial availability and glass transition temperature.

[0036] A polymer block mainly composed of a conjugated diene compound is a polymer block in which, among the units constituting the polymer block, units derived from a conjugated diene compound account for 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more.

[0037] Examples of conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and hydrogenated products thereof, among which one or more may be selected and used.

[0038] Preferably, it is at least one selected from the group consisting of isoprene, butadiene, ethylene-butylene which is a hydrogenated product of butadiene, and ethylene-propylene which is a hydrogenated product of isoprene.

[0039] The ratio of the polymer block mainly composed of an aromatic vinyl compound to the polymer block mainly composed of a conjugated diene compound constituting the copolymer (B1) is not particularly limited, but from the viewpoint of loss tangent, the content of the polymer block mainly composed of an aromatic vinyl compound in the copolymer (B1) is preferably 10 to 75 mass%. When the content of the polymer block mainly composed of an aromatic vinyl compound is 10 mass% or more, sufficient mechanical properties are exhibited, and when it is 75 mass% or less, the loss tangent can be increased.

[0040] The molecular weight of the copolymer (B1) is not particularly limited, but from the viewpoints of moldability, fluidity, rubber elasticity, etc., the weight average molecular weight measured by GPC is preferably 5,000 to 800,000, more preferably 10,000 to 600,000, and even more preferably 13,000 to 400,000. When the weight average molecular weight is 5,000 or more, sufficient mechanical properties are exhibited. On the other hand, when the weight average molecular weight is 800,000 or less, the molded article has excellent processability and fluidity.

[0041] The reactive functional group in the copolymer (B1) is not particularly limited, and examples thereof include at least one selected from an amino group, a carboxyl group, a carboxyl metal salt, a hydroxyl group, an acid anhydride group, an epoxy group, an isocyanate group, a mercapto group, an oxazoline group, a sulfonic acid group, etc. Among these, at least one selected from an amino group, a carboxyl group, a carboxyl metal salt, an epoxy group, an acid anhydride group, and an oxazoline group is preferably used because it has high reactivity and is less likely to undergo side reactions such as decomposition and crosslinking.

[0042] Examples of acid anhydrides constituting the above-described acid anhydride group include maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, and 1-butene-3,4-dicarboxylic anhydride. Two or more of these may be used in combination. Of these, maleic anhydride or itaconic anhydride is preferably used.

[0043] The amount of reactive functional groups introduced into the copolymer (B1) is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 3% by mass, based on 100% by mass of the entire copolymer (B1). By introducing the reactive functional groups in an amount of 0.1% by mass or more, the reactivity with the thermoplastic resin (A) can be enhanced. On the other hand, by setting the amount of reactive functional groups to 20% by mass or less, the reaction between the thermoplastic resin (A) and the copolymer (B1) can be prevented from proceeding excessively, and the heat resistance of the reinforced thermoplastic elastomer composition can be maintained.

[0044] The copolymer (B2) used in the present invention is a copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and is a copolymer other than the copolymer (B1). That is, the copolymer (B2) is a copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and having no reactive functional groups.

[0045] The polymer block mainly composed of an aromatic vinyl compound in the copolymer (B2) is preferably the same as the polymer block mainly composed of an aromatic vinyl compound described above for the copolymer (B1).

[0046] The polymer block mainly composed of a conjugated diene compound and / or its hydrogenated product in the copolymer (B2) is preferably the same as the polymer block mainly composed of a conjugated diene compound and / or its hydrogenated product described above for the copolymer (B1).

[0047] The block copolymer (B2) of the present invention is not particularly limited in structure, so long as it is composed of a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and any of a linear, branched, star-shaped structure, etc. may be selected.

[0048] The ratio of the polymer block mainly composed of an aromatic vinyl compound to the polymer block mainly composed of a conjugated diene compound constituting the copolymer (B2) is not particularly limited, but from the viewpoint of loss tangent, the content of the polymer block mainly composed of an aromatic vinyl compound in the copolymer (B2) is preferably 10 to 75 mass%. When the content of the polymer block mainly composed of an aromatic vinyl compound is 10 mass% or more, sufficient mechanical properties are exhibited. When the content of the polymer block mainly composed of an aromatic vinyl compound is 75 mass% or less, the loss tangent can be increased.

[0049] The molecular weight of copolymer (B2) is not particularly limited, but from the viewpoints of moldability, fluidity, rubber elasticity, etc., the weight average molecular weight measured by GPC is preferably 5,000 to 800,000, more preferably 10,000 to 600,000, and even more preferably 13,000 to 400,000. When the weight average molecular weight is 5,000 or more, sufficient mechanical properties are exhibited. On the other hand, when the weight average molecular weight is 800,000 or less, the molded article has excellent processability and fluidity.

[0050] In the present invention, a compound that corresponds to both the copolymer (B1) and the copolymer (B2) and has a reactive functional group is treated as the copolymer (B1).

[0051] The filler (C) used in the present invention may be any of fibrous, plate-like, powdery, granular, etc. Among these, fibrous fillers such as glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, and metal fiber are preferred from the viewpoint of improving the physical properties of the reinforced thermoplastic elastomer composition.

[0052] Examples of the filler (C) other than the fibrous filler include silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, and alumina silicate; metal oxides such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, and iron oxide; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; sulfates such as calcium sulfate and barium sulfate; glass beads, ceramic beads, boron nitride, silicon carbide, and calcium phosphate; calcium hydroxide, magnesium hydroxide, Hydroxides such as aluminum hydroxide; non-fibrous fillers such as glass flakes, glass powder, carbon black, silica, and graphite; smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and sauconite; various clay minerals such as vermiculite, halloysite, kanemite, kenyaite, zirconium phosphate, and titanium phosphate; and layered silicates represented by swellable micas such as Li-type fluorine taeniolite, Na-type fluorine taeniolite, Na-type tetrasilicic fluorine mica, and Li-type tetrasilicic fluorine mica.

[0053] Among these fillers (C), glass fiber, carbon fiber, talc, wollastonite, and layered silicates such as montmorillonite and synthetic mica are preferred, and those selected from glass fiber and carbon fiber are particularly preferred.

[0054] The type of glass fiber is not particularly limited as long as it is generally used to reinforce resins, and can be selected from, for example, long fiber type or short fiber type chopped strands, milled fiber, etc. Furthermore, two or more types of the above filler (C) can also be used in combination.

[0055] The filler (C) used in the present invention may be surface-treated with a known coupling agent (e.g., a silane coupling agent, a titanate coupling agent, etc.), a sizing agent (e.g., an epoxy resin, a phenolic resin), or other surface treatment agent. The filler (C) may also be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

[0056] The type of carbon fiber may be either a PAN-based or pitch-based carbon fiber, and may be selected from, for example, a long fiber type roving or a short fiber type chopped strand.

[0057] The amounts of the thermoplastic resin (A), thermoplastic elastomer (B), and filler (C) contained in the reinforced thermoplastic elastomer composition of the present invention are preferably such that the ratio (mass ratio) of the thermoplastic resin (A) to the thermoplastic elastomer (B) (A):(B) is 40:60 to 70:30, and the amount of the filler (C) is 10 to 200 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A) and the thermoplastic elastomer (B).

[0058] When the ratio of thermoplastic resin (A) is greater than 40:60, the storage modulus of the reinforced thermoplastic elastomer composition at 160°C can be increased, resulting in higher heat resistance. When the ratio of thermoplastic elastomer (B) is greater than 70:30, the loss tangent of the reinforced thermoplastic elastomer composition can be increased, resulting in better vibration damping. A mass ratio of (A):(B) of 45:55 to 65:35 is more preferred.

[0059] In addition, by incorporating 10 parts by mass or more of filler (C), the storage modulus of the reinforced thermoplastic elastomer composition at 160°C can be increased, resulting in higher high-temperature rigidity. In addition, by incorporating 200 parts by mass or less, the toughness of the reinforced thermoplastic elastomer composition can be increased. The amount of filler (C) is more preferably 15 to 180 parts by mass.

[0060] The reinforced thermoplastic elastomer composition of the present invention has a loss tangent of 0.10 or more at a frequency of 100 Hz and a temperature of 23°C, a storage modulus of 30 MPa or more at a frequency of 100 Hz and a temperature of 160°C, and a melting point measured by differential scanning calorimetry (DSC) of 200°C or more. By achieving a loss tangent of 0.10 or more at a frequency of 100 Hz and a temperature of 23°C, it is possible to impart vibration damping properties and sound absorption properties to a molded article made from the reinforced thermoplastic elastomer composition.

[0061] The loss tangent of a reinforced thermoplastic elastomer composition at a frequency of 100 Hz and a temperature of 23°C can be determined by the following method. A rectangular molded article is prepared using the reinforced thermoplastic elastomer composition of the present invention as described below. The molded article, kept in an absolutely dry state, is measured using a viscoelasticity measuring device (Seiko Instruments, DMS6100) under conditions of a nitrogen atmosphere, a heating rate of 2°C / min, and a frequency of 100 Hz to determine the storage modulus and loss modulus. The loss tangent at 23°C is determined by dividing the loss modulus at 23°C by the storage modulus.

[0062] The loss tangent of the reinforced thermoplastic elastomer composition of the present invention at a frequency of 100 Hz and a temperature of 23° C. is preferably 0.15 or more, more preferably 0.18 or more.

[0063] There is no particular upper limit to the loss tangent at a frequency of 100 Hz and a temperature of 23° C., but from the viewpoint of maintaining the shape of the molded product, it is preferably 5.0 or less.

[0064] Furthermore, since the storage modulus of the reinforced thermoplastic elastomer composition is 30 MPa or more at a frequency of 100 Hz and a temperature of 160°C, high-temperature rigidity is imparted to a molded article made of the reinforced thermoplastic elastomer composition, and the shape of the molded article can be maintained even at high temperatures.

[0065] The storage modulus of a reinforced thermoplastic elastomer composition at a frequency of 100 Hz and a temperature of 160°C can be determined by the following method. A rectangular molded article is prepared using the reinforced thermoplastic elastomer composition of the present invention as described below. The molded article, kept in an absolutely dry state, is measured using a viscoelasticity measuring device (Seiko Instruments, DMS6100) under conditions of a nitrogen atmosphere, a heating rate of 2°C / min, and a frequency of 100 Hz, to determine the storage modulus at a temperature of 160°C.

[0066] The storage modulus of the reinforced thermoplastic elastomer composition of the present invention at a frequency of 100 Hz and a temperature of 160°C is preferably 40 MPa or more, more preferably 50 MPa or more.

[0067] There is no particular upper limit to the storage modulus at a frequency of 100 Hz and a temperature of 160° C., but from the viewpoint of toughness of the molded product, it is preferably 10,000 MPa or less.

[0068] Furthermore, the reinforced thermoplastic elastomer composition of the present invention has a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC), thereby imparting heat resistance to a molded article made of the reinforced thermoplastic elastomer composition, allowing the molded article to be used at high temperatures.

[0069] The melting point of the reinforced thermoplastic elastomer composition by DSC can be determined by the following method. First, a differential scanning calorimeter (PerkinElmer DSC-7) is used, and two-point calibration (indium, lead) and baseline correction are performed. A sample of the reinforced thermoplastic elastomer composition (8 to 10 mg) is weighed, and the sample is heated at a heating rate of 20°C / min. The melting endothermic peak observed during the heating process is taken as the melting point.

[0070] The melting point of the reinforced thermoplastic elastomer composition of the present invention is preferably 205°C or higher, more preferably 210°C or higher.

[0071] On the other hand, the upper limit of the melting point of the reinforced thermoplastic elastomer composition is not particularly limited, but is preferably 400°C or less, since this tends to suppress decomposition of the thermoplastic elastomer (B) in the reinforced thermoplastic elastomer composition and prevent a decrease in mechanical properties, more preferably 370°C or less, and even more preferably 350°C or less.

[0072] There are no particular limitations on the method for making the reinforced thermoplastic elastomer composition have a loss tangent of 0.10 or more at a frequency of 100 Hz and a temperature of 23°C, a storage modulus of 30 MPa or more at a frequency of 100 Hz and a temperature of 160°C, and a melting point as measured by differential scanning calorimetry (DSC) of 200°C or more, as long as such reinforced thermoplastic elastomer composition can be obtained, but the reinforced thermoplastic elastomer composition of the following embodiment is preferably used.

[0073] A preferred embodiment of the reinforced thermoplastic elastomer composition of the present invention comprises a thermoplastic resin (A) having a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC), a copolymer (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof and having a reactive functional group, a copolymer (B2) other than the component (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and a filler (C). and (B2)) = 40:60 to 70:30, and the amount of filler (C) blended is 10 to 200 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A), copolymer (B1), and copolymer (B2).

[0074] By blending a thermoplastic resin (A) having excellent heat resistance and moldability with a copolymer (B1) having a reactive functional group in a specific ratio, the thermoplastic resin (A) and the copolymer (B1) react appropriately, improving the compatibility between the thermoplastic resin (A) and the copolymer (B2). Furthermore, blending the copolymer (B1) and the copolymer (B2) in a specific ratio allows the copolymer (B1) and the copolymer (B2) to interact appropriately, improving the compatibility between the thermoplastic resin (A) and the copolymer (B2), and improving the loss tangent of the reinforced thermoplastic elastomer composition. The high loss tangent of the reinforced thermoplastic elastomer composition results in a reinforced thermoplastic elastomer composition with excellent vibration damping properties. Furthermore, blending the copolymer (B2) in a specific ratio with the thermoplastic resin (A) and the copolymer (B1) improves the loss tangent of the reinforced thermoplastic elastomer composition while maintaining the heat resistance of the thermoplastic resin (A). Furthermore, by blending the thermoplastic resin (A), the copolymer (B1), the copolymer (B2), and the filler (C) in a specific ratio, a reinforced thermoplastic elastomer composition having excellent heat resistance, vibration damping properties, and high-temperature rigidity can be obtained.

[0075] The thermoplastic resin (A) used in this embodiment is a thermoplastic resin having a melting point measured by DSC of 200° C. or higher. The thermoplastic resin (A) used in this embodiment is preferably the same as the above-described thermoplastic resin (A).

[0076] The copolymer (B1) used in this embodiment is preferably the same as the above-mentioned copolymer (B1).

[0077] Although there is no particular limitation on the glass transition temperature of the copolymer (B1) in this embodiment, it is preferable that the copolymer (B1-1) has a glass transition temperature in the range of −20° C. to 60° C. When the copolymer (B1-1) has a glass transition temperature in the range of −20° C. to 60° C., the loss tangent of the reinforced thermoplastic elastomer composition at a frequency of 100 Hz and a temperature of 23° C. can be further increased.

[0078] The glass transition temperature of the copolymer (B1-1) is more preferably in the range of -20°C to 50°C, and even more preferably in the range of -20°C to 40°C.

[0079] The glass transition temperature of copolymer (B1-1) can be determined by the following method. A sample kept in an absolutely dry state is measured using a viscoelasticity measuring device (Seiko Instruments, DMS6100) under a nitrogen atmosphere at a frequency of 100 Hz and a temperature increase rate of 2°C / min to determine the storage modulus and loss modulus. The loss modulus is calculated by dividing the loss modulus by the storage modulus. The temperature at the peak of the loss tangent obtained here is taken as the glass transition temperature.

[0080] The glass transition temperature of the copolymer (B1-1) can be adjusted to fall within the above range by, for example, adjusting the structure or copolymerization ratio of the copolymer components of the copolymer (B1-1).

[0081] The copolymer (B2) used in this embodiment is preferably the same as the above-mentioned copolymer (B2).

[0082] Although there is no particular limitation on the glass transition temperature of the copolymer (B2) in this embodiment, it is preferable that the copolymer (B2-1) has a glass transition temperature in the range of −20° C. to 60° C. When the copolymer (B2-1) has a glass transition temperature in the range of −20° C. to 60° C., the loss tangent of the reinforced thermoplastic elastomer composition at a frequency of 100 Hz and a temperature of 23° C. can be further increased.

[0083] The glass transition temperature of the copolymer (B2-1) is more preferably in the range of -20°C to 50°C, and even more preferably in the range of -20°C to 40°C.

[0084] The glass transition temperature of copolymer (B2-1) can be determined by the following method. A sample kept in an absolutely dry state is measured using a viscoelasticity measuring device (Seiko Instruments, DMS6100) under a nitrogen atmosphere at a frequency of 100 Hz and a temperature increase rate of 2°C / min to determine the storage modulus and loss modulus. The loss modulus is calculated by dividing the loss modulus by the storage modulus. The temperature at the peak of the loss tangent obtained here is taken as the glass transition temperature.

[0085] The glass transition temperature of the copolymer (B2-1) can be adjusted to fall within the above range by, for example, adjusting the structure or copolymerization ratio of the copolymer components of the copolymer (B2-1).

[0086] The amounts of the thermoplastic resin (A), copolymer (B1), copolymer (B2), and filler (C) contained in the reinforced thermoplastic elastomer composition of this embodiment are preferably such that the ratio (mass ratio) (A):(B1) of the thermoplastic resin (A) to the copolymer (B1) is 45:55 to 95:5, the ratio (mass ratio) (B1):(B2) of the copolymer (B1) to the copolymer (B2) is 90:10 to 5:95, and the ratio (mass ratio) (A):((B1)+(B2)) of the thermoplastic resin (A) to the total of the copolymer (B1) and the copolymer (B2) is 40:60 to 70:30, and the amount of the filler (C) is 10 to 200 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A), copolymer (B1), and copolymer (B2).

[0087] By reducing the amount of copolymer (B1) below a mass ratio (A):(B1) of 45:55, the reaction between the thermoplastic resin (A) and the copolymer (B1) proceeds appropriately, making it easier for the thermoplastic resin to exhibit its heat resistance, and thereby improving the heat resistance of the reinforced thermoplastic elastomer composition. Furthermore, by increasing the amount of copolymer (B1) above a mass ratio (A):(B1) of 95:5, the compatibility between the thermoplastic resin (A) and the copolymer (B2) improves, thereby increasing the loss tangent of the reinforced thermoplastic elastomer composition. A mass ratio (A):(B1) of 50:50 to 95:5 is more preferred, with a mass ratio of 55:45 to 95:5 being even more preferred.

[0088] Furthermore, by increasing the amount of copolymer (B2) in the (B1):(B2) ratio (mass ratio) above 90:10, the excellent loss tangent of copolymer (B2) is more preferably achieved. Furthermore, by increasing the amount of copolymer (B1) in the (B1):(B2) ratio (mass ratio) above 5:95, the reactivity between thermoplastic resin (A) and copolymer (B1) is improved, and compatibility with copolymer (B2) is improved, resulting in a higher loss tangent of the reinforced thermoplastic elastomer composition. The (B1):(B2) ratio (mass ratio) is more preferably 80:20 to 5:95, even more preferably 70:30 to 5:95, and particularly preferably 60:40 to 10:90.

[0089] Furthermore, when the ratio (mass ratio) of (A):((B1) + (B2)) is less than 40:60, the heat resistance of the thermoplastic resin (A) is more easily exhibited, and the heat resistance of the reinforced thermoplastic elastomer composition is increased, which is preferable. Furthermore, when the ratio (mass ratio) of (A):((B1) + (B2)) is greater than 70:30, the loss tangent of the reinforced thermoplastic elastomer composition is increased, and better vibration-damping properties can be imparted, which is preferable. The ratio (mass ratio) of (A):((B1) + (B2)) is more preferably 40:60 to 68:32, and even more preferably 45:55 to 65:35.

[0090] Furthermore, if the amount of filler (C) is less than 10 parts by mass per 100 parts by mass of the total of thermoplastic resin (A), copolymer (B1), and copolymer (B2), the high-temperature rigidity of the reinforced thermoplastic elastomer composition will be reduced. On the other hand, if the amount of filler (C) is more than 200 parts by mass, the toughness of the reinforced thermoplastic elastomer composition will be reduced. The amount of filler (C) is preferably 10 to 200 parts by mass, more preferably 15 to 180 parts by mass.

[0091] The reinforced thermoplastic elastomer composition of this embodiment preferably further contains a hydrogenated petroleum resin (D).

[0092] The hydrogenated petroleum resin (D) is a resin obtained by hydrogenating a petroleum resin solidified with an acid catalyst from mainly the C5 fraction and the C9 fraction, which are the remaining fractions obtained after the necessary fractions are extracted by thermal cracking of petroleum naphtha, without isolating unsaturated hydrocarbons.

[0093] Examples of the hydrogenated petroleum resin (D) include hydrogenated dicyclopentadiene resins and partially hydrogenated aromatic-modified dicyclopentadiene resins, which are hydrogenated resins of C5 petroleum resins obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene produced by thermal decomposition of petroleum naphtha; C9 hydrogenated petroleum resins obtained by copolymerizing C9 fractions such as indene, vinyltoluene, and α- or β-methylstyrene produced by thermal decomposition of petroleum naphtha; and copolymerized hydrogenated petroleum resins of the C5 fraction and the C9 fraction.

[0094] Commercially available hydrogenated dicyclopentadiene resins include, for example, the "ESCOLETZ" (registered trademark) 5300 and 5400 series manufactured by Tonex Corporation; and the "Eastotac" (registered trademark) H series manufactured by Eastman Chemical Japan Co., Ltd.

[0095] Commercially available partially hydrogenated aromatic modified dicyclopentadiene resins include, for example, the "ESCOLETZ" (registered trademark) 5600 series manufactured by Tonex Corporation.

[0096] Commercially available C9 hydrogenated petroleum resins include, for example, "Arcon" (registered trademark) P and M series manufactured by Arakawa Chemical Industries, Ltd.; and Polystolyn manufactured by Eastman Chemical Company.

[0097] Examples of copolymerized hydrogenated petroleum resins of C5 fraction and C9 fraction include the "Imarv" (registered trademark) series manufactured by Idemitsu Kosan Co., Ltd.

[0098] From the viewpoint of compatibility with the copolymer (B1) and the copolymer (B2), the hydrogenated petroleum resin (D) is preferably a C9 hydrogenated petroleum resin.

[0099] The amount of hydrogenated petroleum resin (D) contained in the reinforced thermoplastic elastomer composition of the present invention is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total of thermoplastic resin (A), copolymer (B1), and copolymer (B2). By setting the amount to 0.01 parts by mass or more, the loss tangent of the reinforced thermoplastic elastomer composition at a temperature of 23°C when measured at a frequency of 100 Hz can be further increased. On the other hand, setting the amount to 20 parts by mass or less is preferred because it can suppress surface tack due to bleed-out. The amount of hydrogenated petroleum resin is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1.5 to 15 parts by mass.

[0100] The reinforced thermoplastic elastomer composition of the present invention may optionally contain 0 to 10 parts by mass of other components than those described above per 100 parts by mass of the total of the thermoplastic resin (A) and the thermoplastic elastomer (B), provided that the properties of the composition are not impaired. Examples of such other components include copper compounds, potassium compounds, and various additives.

[0101] Examples of copper compounds include copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper carbonate, copper fluoroborate, copper citrate, copper hydroxide, copper nitrate, copper sulfate, and copper oxalate. Two or more of these compounds may be contained as copper compounds. Among these copper compounds, those that are industrially available are preferred, and copper halides are preferred. Examples of copper halides include copper iodide, copper (I) bromide, copper (II) bromide, and copper (I) chloride. Copper iodide is more preferred as the copper compound.

[0102] Examples of potassium compounds include potassium iodide, potassium bromide, potassium chloride, potassium fluoride, potassium acetate, potassium hydroxide, potassium carbonate, and potassium nitrate. Two or more of these potassium compounds may be contained. Among these potassium compounds, potassium iodide is preferred. By including a potassium compound, the surface appearance, weather resistance, and mold corrosion resistance of the molded article can be improved.

[0103] The potassium compound inhibits the liberation and precipitation of copper, and therefore, it is believed that the combined use of a copper compound and a potassium compound has the effect of promoting the reaction between the copper compound and the thermoplastic resin (A).

[0104] Examples of the various additives include color inhibitors, antioxidants such as hindered phenols and hindered amines, mold release agents such as ethylene bisstearylamide and higher fatty acid esters, plasticizers, heat stabilizers, lubricants, ultraviolet inhibitors, colorants, flame retardants, and foaming agents.

[0105] Methods for producing the reinforced thermoplastic elastomer composition of the present invention include production in a molten state and production in a solution state. From the viewpoint of productivity, production in a molten state is preferred. For production in a molten state, melt kneading using an extruder, a Banbury mixer, a kneader, a mixing roll, or the like can be used. From the viewpoint of productivity, melt kneading using an extruder capable of continuous production is preferred. Examples of extruders include single-screw extruders, twin-screw extruders, multi-screw extruders such as four-screw extruders, and twin-screw single-screw composite extruders. A plurality of these extruders may be combined. From the viewpoint of improving kneading ability, reactivity, and productivity, multi-screw extruders such as twin-screw extruders and four-screw extruders are preferred, and twin-screw extruders are more preferred.

[0106] Examples of melt-kneading methods using a twin-screw extruder include premixing the thermoplastic resin (A), thermoplastic elastomer (B), and filler (C), as well as other components, if necessary, and feeding the mixture into a twin-screw extruder with a cylinder temperature set above the melting point of the thermoplastic resin (A). The order in which the raw materials are mixed is not particularly limited. Any of these methods may be used: melt-kneading all raw materials using the above method; melt-kneading some raw materials using the above method and then blending the remaining raw materials; or melt-kneading some raw materials while blending the remaining raw materials using a side feeder. A preferred method involves feeding the thermoplastic resin (A), thermoplastic elastomer (B), and optionally other components into the base of the extruder and melt-kneading them, and then adding the filler (C) midway through the extruder using a side feeder and melt-kneading the remaining raw materials. The base of the extruder refers to the upstream end of the screw, with the upstream side being the side where the raw materials are fed and the downstream side being the side where the molten resin is discharged. Another preferred method involves exposing the extruder to a vacuum midway through the extruder to remove any gases generated.

[0107] The reinforced thermoplastic elastomer composition of the present invention can be molded into molded articles by any method. Examples of molding methods include extrusion molding, injection molding, blow molding, calendar molding, compression molding, vacuum molding, foam molding, blow molding, and rotational molding. Examples of molded articles include injection-molded parts, extrusion-molded parts, blow-molded parts, films, sheets, fibers, and the like.

[0108] The reinforced thermoplastic elastomer composition of the present invention can be foam-molded. Foam molding methods include chemical foaming and physical foaming. Examples of chemical foaming include a method in which a foaming agent for the reinforced thermoplastic elastomer composition is added during melt-kneading of the reinforced thermoplastic elastomer composition, followed by melt-kneading and molding; and a method in which a foaming agent for the reinforced thermoplastic elastomer composition is dry-blended with the reinforced thermoplastic elastomer composition of the present invention before molding and then molding. Examples of physical foaming include a batch method in which a reinforced thermoplastic elastomer composition molded in an autoclave is impregnated with a supercritical gas to foam it, and a continuous method in which a supercritical gas is impregnated with the reinforced thermoplastic elastomer composition during melt-kneading and then foamed. Foam molding can produce, for example, foam injection molded products and foam sheets.

[0109] The resulting molded article has a high loss tangent and can therefore be suitably used as a vibration-damping material or a sound-absorbing material.

[0110] Vibration-damping components are materials, components, and devices used to suppress vibrations and shaking. They absorb vibration energy from external and internal sources such as earthquakes, wind, and machinery, thereby reducing vibrations and shaking.

[0111] Sound-absorbing materials are materials, components, and devices used to absorb sound and suppress reverberation. They absorb the energy of sound as it travels through the air, reducing reflected sound.

[0112] The molded article of the present invention can be used in a variety of applications, such as housings, internal members, and parts for electrical and electronic devices, automobiles, motorcycles, aircraft, drones, electric vertical take-off and landing unpiloted aircraft, industrial machinery, construction materials, office products, optical equipment, precision machinery, sporting goods, and artificial satellites. In particular, the molded article of the present invention can be preferably used in these applications as a vibration-damping member or sound-absorbing member. Specifically, in the following applications, members and parts can be replaced with the molded article of the present invention, or a sheet made of the molded article of the present invention can be attached to the following products.

[0113] Examples of electric and electronic devices include various elements and substrates such as parabolic antennas, mobile phones, digital still cameras, PDAs, liquid crystal displays, LED lamps, connectors, sockets, resistors, capacitors, optical pickups, oscillators, transformers, plugs, and printed wiring boards, as well as housings, internal members, and parts for electric and electronic devices such as tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, displays, chassis, HDDs, and motor brush holders.

[0114] For automobiles and motorcycles, floor panels, door panels, quarter panels, roof panels, roof headers, roof linings, wheel houses, pillars, tires, engine hoods, engine undercarriages, transmissions, motors, air conditioning hoses, wiper motors, dash inners, compressors, compressor covers, engine covers, door mirrors, motor mounts, engine mounts, transmission mounts, suspension mounts, door actuators, actuator brackets, floor pads, gears, hood liners, oil pans, engine head covers, engine capsules, floor undercovers, fender aprons, engine undercovers, transmission tunnels, piping, exhaust systems, intake ducts, battery cooling ducts, air conditioning ducts, air cleaners, gearboxes, gearbox covers, motor covers, inverter covers, inverter cases, PCU cases, cowl panels, dash outers, floor carpets, tunnels, instrument panels, center consoles, door trim, roofs, pillar garnishes, tibia pads, and transmissions. trim, room partitions, rear parcels, fender liners, tires, oil pans, cylinder head covers, front covers, timing belt covers, rocker covers, battery cases, motor cases, bearings, armrests, room mirrors, bumper parts, body panels, side shields, glass run channels, instrument panel skins, door skins, ceiling skins, weatherstrip materials, hoses, steering wheels, boots, wire harness covers, seat adjuster covers, seals, CVJ boots, suspension boots, rack and pinion boots, steering rod covers, AT cushions, AT slide covers, leaf spring bushes, ball joint retainers, timing belts, V-belts, engine compartment hoses, airbag covers, propeller shaft covers, airbag case lids, shift knobs, assist grips, side step mats, reclining covers, trunk seats, seat belt buckles, lever slide plates, door latch strikers, seat belt parts, dash silencers, hole plug switches,It can be suitably used for automobile and motorcycle components and parts such as air duct packing, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, opening seal / trunk seal members, window glass members, speaker members, bonnet cushions, fuel tank bands, cables, power ECUs, PCUs, ADASs, and battery ECUs.

[0115] For aircraft, drones, and electric vertical take-off and landing unpiloted aircraft, the material can be suitably used for components and parts of aircraft, drones, and electric vertical take-off and landing unpiloted aircraft, such as landing gear pods, winglets, spoilers, edges, rudders, failings, ribs, outer panels, engine covers, hydrogen tanks, frames, propellers, motors, flight controllers, ESCs, batteries, transmitters, receivers, FPV cameras, and VTXs.

[0116] Industrial machinery includes railway vehicle components and parts, boilers, steam engines, turbines, wind engines, water wheels, compressed air engines, pumps, air compressors, gas compressors, blowers, hydraulic and pneumatic equipment, power transmission devices, elevators, escalators, logistics and transportation equipment, freezers, temperature control devices, fire extinguishing equipment, fire extinguishing devices, valves and valve accessories, pipe processing and pipe accessories, ball bearings and roller bearings, piston rings, agricultural machinery, construction machinery, mining machinery, chemical fiber machinery, spinning machinery, weaving machinery, braiding machinery, textile machinery, sewing machinery, food machinery, food equipment, wood processing machinery, printing, bookbinding and paper processing machinery. The present invention can be suitably used for housings, internal members, and parts of industrial equipment such as machinery, packaging and packing machinery, casting equipment, chemical machinery, chemical equipment, plastic processing machinery, plastic processing accessory equipment, metal processing machinery, metal working machine, machine tools, semiconductor manufacturing equipment, flat panel display manufacturing equipment, vacuum equipment, vacuum equipment, robots, office machinery and instruments, service machinery and instruments, entertainment machinery, vending machines, measuring instruments, measuring machines, analytical equipment, testing equipment, surveying machinery and instruments, physical and chemical machinery and instruments, medical machinery and instruments, medical supplies, optical machinery and instruments, commercial washing machines, and other general-purpose machinery.

[0117] As building materials, the composition can be suitably used for wall materials, floor materials, roof materials, vibration damping devices, panels, sheets and other members and parts.

[0118] The composition can be suitably used for housings, internal members, and parts of household or office products such as telephones, facsimiles, VTRs, copy machines, personal computers, televisions, irons, hair dryers, rice cookers, microwave ovens, audio equipment, vacuum cleaners, compact discs, lighting, washing machines, refrigerators, air conditioners, typewriters, and word processors.

[0119] The film can be suitably used in optical instruments and precision instruments such as microscopes, binoculars, cameras, and clocks, as well as in housings, internal members, and parts of precision instruments.

[0120] Suitable sporting goods include golf-related goods such as golf clubs, shafts, grips, and golf balls; sports racket-related goods such as tennis rackets and badminton rackets and their strings; pickleball balls and paddles; sports body protection goods such as masks, helmets, breast pads, elbow pads, and knee pads for American football, baseball, softball, etc.; apparel-related goods such as sportswear; shoe-related goods such as soles for sports shoes; fishing tackle-related goods such as fishing rods and fishing lines; summer sports goods such as surfing; winter sports goods such as skiing and snowboarding; and other indoor and outdoor sports goods.

[0121] As for artificial satellites, the material can be suitably used as a member or part of an artificial satellite.

[0122] In particular, the reinforced thermoplastic elastomer composition of the present invention can be preferably used in electrical and electronic devices, automobiles, electric vehicles, fuel cell vehicles, aircraft, drones, electric vertical take-off and landing unpiloted aircraft, railway vehicle components, industrial machinery, construction components, office products, optical equipment, precision machinery, and artificial satellites, taking advantage of its excellent properties of vibration damping, heat resistance, and high-temperature rigidity.

[0123] The effects of the present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples. Evaluations in each example and comparative example were carried out by the following methods.

[0124] (1) Melting Point of Thermoplastic Resin The melting point of the thermoplastic resin used in each Example and Comparative Example was determined by DSC. First, a differential scanning calorimeter (PerkinElmer DSC-7) was used, and two-point calibration (indium, lead) and baseline correction were performed. 8 to 10 mg of the thermoplastic resin was weighed and heated from 30°C to 350°C at a heating rate of 20°C / min. The melting endothermic peak temperature observed during the heating process was taken as the melting point.

[0125] (2) Glass Transition Temperature of Copolymer (B1) and Copolymer (B2) The glass transition temperatures of copolymer (B1) and copolymer (B2) used in each Example and Comparative Example were determined by viscoelasticity measurement. First, a flat plate measuring 80 mm x 80 mm x 1 mmt was prepared using copolymer (B1) or copolymer (B2) kept in an absolute dry state in the same manner as in the Examples described below. A strip measuring 40 mm x 8 mm x 1 mmt was cut from the flat plate to serve as a measurement sample. The measurement sample kept in an absolute dry state was measured using a viscoelasticity measuring device (Seiko Instruments, DMS6100) under a nitrogen atmosphere, at a frequency of 100 Hz, and at a temperature rise rate of 2°C / min, in the temperature range of -90°C to 350°C, to determine the storage modulus and loss modulus. The loss tangent was determined by dividing the loss modulus by the storage modulus. The peak temperature of the determined loss tangent was taken as the glass transition temperature.

[0126] (3) Heat Resistance: Melting Point Heat resistance was evaluated by melting point. The melting points of the reinforced thermoplastic elastomer composition pellets obtained in each Example and Comparative Example were determined by DSC measurement. First, a differential scanning calorimeter (PerkinElmer DSC-7) was used, and two-point calibration (indium, lead) and baseline correction were performed. 8 to 10 mg of the reinforced thermoplastic elastomer composition was weighed and heated from 30°C to 350°C at a heating rate of 20°C / min. The melting endothermic peak temperature observed during the heating process was taken as the melting point. When the reinforced thermoplastic elastomer composition has a melting point of 200°C or higher, it imparts heat resistance to molded articles, allowing them to be used at high temperatures.

[0127] (4) Vibration Damping: Loss Tangent (tan δ) Measurement samples were obtained by cutting 40 mm x 8 mm x 1 mm strips from 80 mm x 80 mm x 1 mm thick plates molded from the reinforced thermoplastic elastomer compositions obtained in each Example and Comparative Example. The samples, kept bone dry, were measured using a viscoelasticity measuring device (Seiko Instruments, DMS6100) under a nitrogen atmosphere at a frequency of 100 Hz and a temperature rise rate of 2°C / min over a temperature range of -90°C to 350°C to determine the storage modulus and loss modulus. The loss modulus at 23°C was calculated by dividing the loss modulus by the storage modulus. A reinforced thermoplastic elastomer composition with a loss tangent of 0.10 or greater can impart vibration damping and sound absorption properties to molded articles.

[0128] (5) High-Temperature Stiffness: Storage Modulus Measurement samples were prepared by cutting 40 mm x 8 mm x 1 mm strips from 80 mm x 80 mm x 1 mm thick plates molded from the reinforced thermoplastic elastomer compositions obtained in each Example and Comparative Example. The samples, kept bone dry, were measured using a viscoelasticity measuring device (Seiko Instruments, DMS6100) under a nitrogen atmosphere at a frequency of 100 Hz and a heating rate of 2°C / min over a temperature range of -90°C to 350°C, to determine the storage modulus at 160°C. A reinforced thermoplastic elastomer composition with a storage modulus of 30 MPa or greater imparts high-temperature stiffness to molded articles, enabling them to maintain their shape even at high temperatures. Samples for which measurement was stopped before 160°C due to excessive displacement, are marked "unmeasurable" in the table.

[0129] The raw materials and their abbreviations used in each of the Examples and Comparative Examples are shown below.

[0130] [SEBS-3] To a nitrogen-purged reaction vessel, 700 parts by mass of cyclohexane, 7.5 parts by mass of styrene, and 0.07 parts by mass of sec-butyllithium were added, with the total amount of all monomers being 100 parts by mass. A first-stage polymerization was then carried out at a polymerization initiation temperature of 50°C. After completion of the reaction, the temperature was raised to 70°C, and 85 parts by mass of 1,3-butadiene was added to carry out adiabatic second-stage polymerization. After 30 minutes, 7.5 parts by mass of styrene was added to carry out third-stage polymerization. After the reaction, methanol was added to terminate the polymerization. Here, the total amount of all monomers refers to the combined amount of all monomers added at each stage of the polymerization process.

[0131] After the reaction, the reaction solution was returned to room temperature and pressure, removed from the reaction vessel, and poured into water with stirring. The solvent was then removed by steam distillation to obtain conjugated diene polymer 1. Cyclopentadienyl titanium dichloride was added to the obtained conjugated diene polymer 1 so that the amount of titanium atoms was 50 ppm relative to the mass of the polymer, and triethylaluminum was further added in an amount three times the molar amount relative to titanium. A hydrogenation reaction was carried out for one hour at a hydrogen pressure of 1 MPa and a temperature of 75°C to obtain SEBS-3. The glass transition temperature of the obtained SEBS-3 was measured and found to be -15°C (a copolymer corresponding to copolymer (B2) and copolymer (B2-1)).

[0132] [SEBS-g-MAH-2] 100 parts by mass of the obtained SEBS-3 were dry-blended with 1.4 parts by mass of maleic anhydride, 0.15 parts by mass of Perhexa 25B (manufactured by NOF Corporation, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane), and 0.1 parts by mass of "Irgafos" (registered trademark) P168 (manufactured by BASF, tris(2,4-di-tert-butylphenyl)phosphite), and the mixture was fed into a twin-screw extruder (manufactured by The Japan Steel Works, Ltd., "TEX" (registered trademark) 30XSSST) (L / D = 45.5 (here, L is the length from the raw material inlet to the discharge outlet, and D is the screw diameter)) with a cylinder temperature set to 230°C, and melt-kneaded to graft-add maleic anhydride to SEBS-3, thereby obtaining SEBS-g-MAH-2.

[0133] The resulting SEBS-g-MAH-2 was extracted and purified with acetone, dried, and the amount of maleic anhydride added was determined by titration with sodium methylate, revealing that 1.3% by mass of maleic anhydride had been added. The glass transition temperature of the resulting SEBS-g-MAH-2 was measured and found to be −15° C. (This copolymer corresponds to copolymer (B1) and copolymer (B1-1)).

[0134] PA6: Polyamide 6 resin "Amilan" (registered trademark) manufactured by Toray Industries, Inc. (melting point 224°C, relative viscosity 2.70 at 25°C in a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml) (thermoplastic resin corresponding to thermoplastic resin (A)) PA12: Polyamide 12 resin "DAIAMID" (registered trademark) manufactured by Daicel-Evonik Ltd. (melting point 178°C) (thermoplastic resin not corresponding to thermoplastic resin (A)) PBT: Polybutylene terephthalate resin "Toray Industries, Inc. (melting point 225°C, weight average molecular weight 18,000) (thermoplastic resin corresponding to thermoplastic resin (A)) PET: Polyethylene terephthalate resin "Toray Industries, Inc. (melting point 260°C, weight average molecular weight 19,000) (thermoplastic resin corresponding to thermoplastic resin (A)) PPS: polyphenylene sulfide resin "manufactured by Toray Industries, Inc." (melting point 279°C, MFR 200g / 10min (315.5°C, 5kg load) (thermoplastic resin corresponding to thermoplastic resin (A)) SEBS-g-MAH-1: maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer "Kraton" (registered trademark) FG1924 manufactured by Kraton Polymer Japan Co., Ltd. (styrene content 13.9%, acid-modified amount 1.0wt%, Tg = -55°C) (copolymer corresponding to copolymer (B1)) SEBS-g-MAH-2: maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer (styrene content 15%, acid-modified amount 1.3wt%, Tg = -15°C) produced in the above [SEBS-g-MAH-2] (copolymer corresponding to copolymer (B1) and copolymer (B1-1)) SEBS-1: styrene-ethylene butylene-styrene block copolymer "S.O.E" (registered trademark) S1605 manufactured by Asahi Kasei Corporation (Tg = 20°C) (copolymer corresponding to copolymer (B2) and copolymer (B2-1)). SEBS-2: styrene-ethylene butylene-styrene block copolymer "TUFTECH" (registered trademark) H1052 manufactured by Asahi Kasei Corporation (Tg = -44°C) (copolymer corresponding to copolymer (B2)). SEBS-3: styrene-ethylene butylene-styrene block copolymer (styrene content 15%, Tg = -15°C) produced in [SEBS-3] above (copolymer corresponding to copolymer (B2) and copolymer (B2-1)).SIS: styrene-isoprene-styrene block copolymer "Kraton" (registered trademark) D1161 manufactured by Kraton Polymer Japan, Ltd. (styrene content 15%, Tg = -50°C) (copolymer corresponding to copolymer (B2)). SBS: styrene-butadiene-styrene copolymer "Kraton" (registered trademark) D1102 manufactured by Kraton Polymer Japan, Ltd. (styrene content 29%, Tg = -90°C) (copolymer corresponding to copolymer (B2)). SEPS: styrene-ethylene propylene-styrene block copolymer "Kraton" (registered trademark) G1730 manufactured by Kraton Polymer Japan, Ltd. (styrene content 20%, Tg = -45°C) (copolymer corresponding to copolymer (B2)). Hydrogenated petroleum resin: C9 hydrogenated petroleum resin "Arcon" (registered trademark) P-140" (Arakawa Chemical Industries, Ltd.) (resin corresponding to hydrogenated petroleum resin (D)).

[0135] GF1: Glass fiber "T249H manufactured by Nippon Electric Glass Co., Ltd." (corresponding to filler (C)) GF2: Glass fiber "T251H manufactured by Nippon Electric Glass Co., Ltd." (corresponding to filler (C))

[0136] Examples 1 to 22, Comparative Examples 1 to 10 The raw materials listed in Tables 1 to 3 were fed into a twin-screw extruder (TEX® 30XSSST, manufactured by The Japan Steel Works, Ltd.) and melt-kneaded. The cylinder temperature of the extruder was set to 250°C, and the screw arrangement was equipped with two kneading zones. The screw rotation speed was 250 rpm, and L / D = 45.5 (where L is the length from the raw material inlet to the discharge outlet, and D is the screw diameter). The gut discharged from the die of the twin-screw extruder was quenched by passing it through a cooling bath filled with water adjusted to 10°C for 15 seconds to fix the structure, and then pelletized with a strand cutter to obtain pellets of reinforced thermoplastic elastomer composition. The obtained pellets were injection molded using an injection molding machine (SE-75DUZ-C250 manufactured by Sumitomo Heavy Industries, Ltd.) under molding conditions of a mold temperature of 80°C, an injection speed of 40 mm / sec, and a cooling time of 60 seconds to obtain a flat plate of 80 mm x 80 mm x 1 mmt. The temperature of the injection molding machine was set at 240°C, 245°C, 250°C, and 250°C from the bottom of the hopper to the tip. The obtained pellets or molded articles were evaluated by the above-mentioned methods, and the results are shown in Tables 1 to 3.

[0137] Examples 23 and 24: The raw materials listed in Table 2 were fed into a twin-screw extruder ("TEX" (registered trademark) 30XSSST, manufactured by The Japan Steel Works, Ltd.) and melt-kneaded. The extruder cylinder temperature was set to 295°C, and the screw arrangement was equipped with two kneading zones. The screw rotation speed was 250 rpm, and the L / D ratio was 45.5. The gut discharged from the die of the twin-screw extruder was quenched by passing it through a cooling bath filled with water adjusted to 10°C for 15 seconds to solidify the structure, and then pelletized with a strand cutter to obtain pellets of the reinforced thermoplastic elastomer composition. The resulting pellets were injection-molded using an injection molding machine (SE-75DUZ-C250, manufactured by Sumitomo Heavy Industries, Ltd.) under molding conditions of a mold temperature of 80°C, an injection speed of 40 mm / sec, and a cooling time of 60 seconds to obtain 80 mm x 80 mm x 1 mm thick flat plates. The temperature of the injection molding machine was set at 285°C - 290°C - 295°C - 295°C from the bottom of the hopper to the tip. The pellets or molded articles obtained were evaluated by the above-mentioned methods, and the results are shown in Table 2.

[0138] The reinforced thermoplastic elastomer compositions of Examples 1 to 24 had a loss tangent of 0.10 or more at a frequency of 100 Hz and a temperature of 23°C, a storage modulus of 30 MPa or more at a frequency of 100 Hz and a temperature of 160°C, and a melting point of 200°C or more as measured by differential scanning calorimetry (DSC), and were found to be excellent in vibration damping properties, high-temperature rigidity, heat resistance, and moldability.

[0139]

[0140]

[0141]

[0142] Molded articles made from the thermoplastic elastomer composition of the present invention have excellent vibration-damping properties, high-temperature rigidity, and heat resistance, and can be easily produced. Taking advantage of these properties, the thermoplastic elastomer composition of the present invention can be widely used in a variety of molded articles, such as sound-absorbing materials and vibration-damping materials, and is particularly suitable for use in automobiles, aircraft, electrical and electronic equipment, railway vehicles, building materials, and consumer applications.

Claims

1. A reinforced thermoplastic elastomer composition comprising a thermoplastic resin (A) having a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC), a thermoplastic elastomer (B), and a filler (C), wherein the reinforced thermoplastic elastomer composition has a loss tangent of 0.10 or higher at a frequency of 100 Hz and a temperature of 23°C, a storage modulus of 30 MPa or higher at a frequency of 100 Hz and a temperature of 160°C, and a melting point of 200°C or higher as measured by differential scanning calorimetry (DSC).

2. A reinforced thermoplastic elastomer composition according to claim 1, wherein the mass ratio of the thermoplastic resin (A) having a melting point of 200°C or higher as determined by differential scanning calorimetry (DSC) to the thermoplastic elastomer (B) contained in the reinforced thermoplastic elastomer composition is (A):(B) = 40:60 to 70:30, and the amount of filler (C) blended is 10 to 200 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A) and the thermoplastic elastomer (B).

3. The reinforced thermoplastic elastomer composition according to claim 1, wherein the thermoplastic resin (A) is at least one selected from the group consisting of polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, and polyphenylene sulfide resin.

4. A reinforced thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer (B) is at least one selected from the group consisting of a copolymer (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof, and having a reactive functional group, and a copolymer (B2) other than the component (B1) containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof.

5. A reinforced thermoplastic elastomer composition according to claim 4, wherein the polymer block mainly composed of a conjugated diene compound and / or its hydrogenated product is a polymer block derived from at least one member selected from the group consisting of isoprene, butadiene, ethylene-butylene, and ethylene-propylene.

6. The reinforced thermoplastic elastomer composition according to claim 4, wherein the mass ratios of the thermoplastic resin (A), copolymer (B1), and copolymer (B2) contained in the reinforced thermoplastic elastomer composition are (A):(B1) = 45:55 to 95:5, (B1):(B2) = 90:10 to 5:95, and (A):((B1) + (B2)) = 40:60 to 70:30, and the amount of filler (C) blended is 10 to 200 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A), copolymer (B1), and copolymer (B2).

7. The reinforced thermoplastic elastomer composition according to claim 4, wherein the copolymer (B1) containing a polymer block mainly made of an aromatic vinyl compound and a polymer block mainly made of a conjugated diene compound and / or a hydrogenated product thereof and having a reactive functional group is a copolymer (B1-1) having a glass transition temperature in the range of -20°C to 60°C.

8. A reinforced thermoplastic elastomer composition according to claim 4, wherein the copolymer (B2) other than the component (B1) containing the polymer block mainly composed of an aromatic vinyl compound and the polymer block mainly composed of a conjugated diene compound and / or a hydrogenated product thereof is a copolymer (B2-1) having a glass transition temperature in the range of -20°C to 60°C.

9. The reinforced thermoplastic elastomer composition according to claim 4, further comprising a hydrogenated petroleum resin (D), wherein the amount of the hydrogenated petroleum resin (D) is 0.01 to 20 parts by mass per 100 parts by mass of the total of the thermoplastic resin (A), copolymer (B1), and copolymer (B2).

10. A molded article made from the reinforced thermoplastic elastomer composition according to any one of claims 1 to 9.

11. The molded article according to claim 10, which is a sound absorbing member.

12. The molded article according to claim 10, which is a vibration-damping member.

13. Electrical and electronic devices, automobiles, electric vehicles, fuel cell vehicles, aircraft, drones, electric vertical take-off and landing unpiloted aircraft, railway vehicle components, industrial machinery, building materials, office products, optical equipment, precision machinery, or artificial satellites, in which the molded product according to claim 10 is used.

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