JPH0885740A - Thermoplastic elastomer resin composition and its production - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic elastomer resin compsn. excellent in mechanical characteristics and productivity by combining a thermoplastic resin with a cross-linked ethylene/α-olefin/arom.vinyl compd./nonconjugated diene copolymer. CONSTITUTION: An ethylene/α-olefin/arom.vinyl compd./nonconjugated diene copolymer having a molar ratio of ethylene units to a-olefin (e.g. propylene) units of (30070)-(90010), a content of arom.vinyl compd. (e.g. styrene) units of 0.01-30mol%, and a content of nonconjugated diene (e.g. 1,4-pentadiene) units of 0.1-30mol% is cross-linked by melt mixing it with a thermoplastic resin (e.g. polypropylene) in the presence of sulfur and/or an org. peroxide (e.g. dicumyl peroxide). Thus, a thermoplastic elastomer resin compsn. comprising a thermoplastic resin and an ethylene/α-olefin/arom.vinyl compd./nonconjugated diene copolymer is obtd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer resin composition having excellent mechanical properties and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a thermoplastic elastomer obtained by blending a thermoplastic resin and an uncrosslinked rubber and crosslinking the rubber while melt-kneading has physical properties at room temperature, but exhibits thermoplasticity. For this reason, demand is growing significantly, mainly as a substitute for vulcanized rubber. As such a thermoplastic elastomer material, a material made of ethylene / propylene rubber (EPR) is known. However, the above-mentioned thermoplastic elastomers are inferior in mechanical properties and their applications are limited at present. Further, from the viewpoint of improving productivity, further improvement in crosslinking rate has been desired.

At present, EPR is industrially produced using a vanadium catalyst or a titanium catalyst. And, for several years, a method for producing EPR using a metallocene catalyst has been shown. For example, Japanese Unexamined Patent Publication No. 62-121711
The publication discloses a method for producing an EPR which uses a catalyst composed of a metallocene compound and an aluminoxane, has a narrow molecular weight distribution and composition distribution, and is excellent in transparency, non-adhesiveness and mechanical properties. In addition, JP-A-2-64115
The publication describes a method for producing a high molecular weight EPR using a catalyst composed of a metallocene compound and an aluminoxane. However, the EP produced in this way
Even with R, the crosslinking rate is slow, and the same problems as described above cannot be avoided.

On the other hand, a copolymer of ethylene and an aromatic vinyl compound such as an ethylene / styrene copolymer has been known for a long time. For example, JP-A-48-8385,
Japanese Patent Laid-Open No. 58-11511 or Polymer
Bulletin, 20, 237 (1988) exemplifies a method for producing an ethylene / styrene copolymer using a Ziegler-Natta catalyst. Regarding the method for producing a propylene / styrene copolymer, JP-A-60-26011, JP-A-2-206602, and JP-A-4-31 are available.
No. 8006 is disclosed. With these methods, it was not possible to obtain a satisfactory polymerization activity.

An ethylene / α-olefin / aromatic vinyl compound copolymer with a new olefin polymerization catalyst has been proposed in the following series of prior art documents. That is,
Japanese Patent Application Laid-Open No. 3-250007 discloses a method for producing an alternating copolymer of ethylene and styrene having an isotactic structure by using a catalyst system composed of a specific transition metal compound and an aluminoxane. In addition, Japanese Patent Laid-Open No. 3-
Japanese Patent No. 163088 discloses a method for producing an ethylene / α-olefin / styrene copolymer with high activity using a catalyst composed of a constrained geometry complex and an aluminoxane. Similarly, Japanese Patent Laid-Open No. 5-194641 discloses that
The synthesis of ethylene / propylene / styrene copolymers is illustrated using a catalyst in which a constrained geometry complex is contacted with a Lewis acid. Further, JP-A-6-49132 discloses a method for producing an ethylene / styrene copolymer by using a catalyst composed of a specific transition metal compound and alumoxane.

As mentioned above, ethylene /
Although a method for producing an α-olefin / aromatic vinyl compound copolymer and its polymer structure have been reported, an ethylene / α-olefin / aromatic vinyl compound / nonconjugated diene copolymer using a non-conjugated diene has been reported. There is no report regarding the above and an example of applying it to a thermoplastic elastomer.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a thermoplastic elastomer having an improved crosslinking rate of the thermoplastic elastomer and excellent mechanical properties.

[0008]

The present inventors have completed the present invention as a result of intensive studies to achieve the above object. That is, the present invention relates to a thermoplastic elastomer resin composition comprising a thermoplastic resin and an ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer cross-linked product. The details will be described below.

The α-olefin used in the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer used in the present invention has 3 or more carbon atoms, for example, propylene, 1-butene, 1 -Pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1
-Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicodecene. And the like, and one or more of these are used. Above all, propylene, 1
-Butene, 1-heptene, 1-hexene, 1-octene and the like are preferable.

The aromatic vinyl compound used in the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer used in the present invention is styrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene, p-chlorostyrene, α-methylstyrene And the like, and one or more of these are used.

Further, ethylene / α-used in the present invention
The non-conjugated diene used in the olefin / aromatic vinyl compound / non-conjugated diene copolymer is 1,4-pentadiene, 1,4-hexadiene, 4-methyl-1,5-heptadiene, 5-methylene-2-norbornene. , 5-ethylidene-2-norbornene, 5-isopropenyl-2
-Norbornene, 2,5-norbonadiene, 1,6-cyclooctadiene, 2-ethylene-2,5-norbonadiene, 2-isopropenyl-2,5-norbonadiene,
Dicyclopentadiene, 1,6-octadiene, 1,7
-Octadiene, tricyclopentadiene and dihydrodicyclopentadienyloxyethylene and esters of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like, but are not limited to Not something. And 1 type or 2 or more types of these are used.

The ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer used in the present invention has the following composition and properties.

(1) The molar ratio of ethylene to α-olefin is preferably in the range of 30/70 to 90/10, and particularly in the range of 45/55 to 85/15 of the thermoplastic elastomer obtained. It is preferable from the viewpoint of rubber performance and improvement of cold resistance.

(2) The content of aromatic vinyl compound is 0.0
It is preferably in the range of 1 to 30 mol%, and particularly preferably 0.
It is preferable in the range of 1 to 15 mol% from the viewpoint of the low temperature characteristics of the thermoplastic elastomer obtained, the affinity with the crosslinking agent, the polymerization activity and the like.

(3) The content of non-conjugated diene is 0.1 to 30.
It is preferably in the range of mol%, particularly 0.1 to 10
It is preferable for the thermoplastic elastomer to be in the range of mol% from the viewpoints of low-temperature properties and crosslinking rate. The non-conjugated diene content can also be expressed by the iodine value. The iodine value can be measured by a known method (for example, “Rubber Test Method” p. 657, edited by Japan Rubber Association, (196
3)).

Ethylene / α-used in the present invention
The molecular weight of the olefin / aromatic vinyl compound / non-conjugated diene copolymer is not particularly limited, but the number average molecular weight measured by gel permeation chromatography (GPC) is 10,000 to 100 in terms of polyethylene.
It is preferably 1,000,000, and more preferably 10,000 to 600,000. Those within this range are particularly excellent in rubber performance, fluidity and processability.

The method for producing the above-mentioned ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer is not particularly limited, and various catalysts such as titanium-based catalysts, vanadium-based catalysts and metallocene-based catalysts can be used. It can be manufactured. Above all, it is preferable to produce using a metallocene catalyst having excellent copolymerizability. High activity by this method,
It is possible to obtain a copolymer having a narrow molecular weight distribution and a narrow composition distribution.

The thermoplastic resin used in the present invention is not particularly limited, but a crystalline resin is preferably used from the viewpoint of improving the physical properties and processability of the resulting thermoplastic elastomer. Examples of such a resin include: Polypropylene resin such as polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene-1 copolymer, syndiotactic polypropylene, high density polyethylene, low density polyethylene, polyethylene such as linear low density polyethylene Resins, polybutene, polyamide resins and the like can be mentioned, and among these, polypropylene resins are preferably used from the viewpoint of heat resistance, processability and the like.

The addition amount of ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer is based on 100 parts by weight of the thermoplastic resin in consideration of the balance between hardness and moldability of the thermoplastic elastomer obtained. 60 parts by weight or more and 1000 parts by weight or less, further 100 parts by weight or more 800
It is desirable that the amount is less than or equal to parts by weight.

In the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer used in the present invention, the crosslinking rate can be improved by appropriately selecting the crosslinking agent. Specifically, the dispersibility of the crosslinking agent is improved, and as a result, the physical properties of rubber represented by compression set characteristics are improved, and further the crosslinking time is shortened. This can be understood by the fact that the solubility parameters of the polymer and the cross-linking agent are close to each other. Generally, the compatibility between a polymer and a heterogeneous compound can be arranged by the difference in solubility parameter, and the smaller the compatibility, the better the compatibility. For example, sulfur is a typical cross-linking agent is the solubility parameter 14.55cal ^1/2 cc ^-3/2, the value of the general ethylene / propylene copolymer (7.95cal ^1/2 cc ^{-3 / 2} ) is very different.
However, ethylene / α-olefin / used in the present invention
The aromatic vinyl compound / non-conjugated diene copolymer has a large solubility parameter and has good compatibility with sulfur. As described above, the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer used in the present invention can shorten the crosslinking time when sulfur crosslinking is carried out, and the organic peroxide crosslinking is the same as above. Occurs, and the crosslinking time can be shortened.

Examples of the organic peroxide cross-linking agent used here include t-butyl peroxide, di (t-butyl) peroxide, t-butyl peroxy-isopropyl carbonate, t-butyl cumyl peroxide and t-butyl. Peroxybenzoate, dicumyl peroxide, cumene peroxide, benzoyl peroxide, cyclohexanone peroxide, diisopropylbenzene peroxide, 2,5-dimethylhexane-
2,5-diperoxide, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexyne-3,2,5-
Dimethyl-2,5-di (t-butyl) peroxyhexane, n-butyl-4,4-bis (t-butylperoxy) hexane, 3,3,5-trimethylhexanoyl peroxide, 2,4- Dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2'-bis (t-butylperoxy) -p-diisopropylbenzene, 1,3-bis (t-butylperoxy-isopropyl) ) Benzene and the like can be used, and these can be used alone or as a mixture.
It is also possible to use it in combination with sulfur.

The amount of the crosslinking agent added is preferably 0.1 to 10 parts by weight per 100 parts by weight of the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer used in the present invention. If it is less than 0.1 part by weight, crosslinking may not proceed sufficiently, and if it exceeds 10 parts by weight, odor may remain.

Further, in the present invention, when a crosslinking accelerator is used in combination, the crosslinking rate is improved, so that a crosslinking accelerator is preferably used in combination. Further, the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer used in the present invention has a good compatibility with the crosslinking accelerator, and therefore the effect is particularly remarkable.

As the crosslinking accelerator, N, N-diphenylguanidine, N, N-di (o-tolyl) guanidine, N,
Guanidine derivatives such as N-o-tolylguanidine; N, N-dibutylthiourea, N, N'-diethylthiourea, dilaurylthiourea, thiourea such as 2-mercaptoimidazoline, trimethylthiourea, tetramethylthiourea; Xanthates such as zinc dibutyl xanthate, sodium isopropyl xanthate, zinc isopropyl xanthate, etc .; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate. , Zinc dibenzyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, Dithiocarbamates such as copper dimethyldithiocarbamate, terium diethyldithiocarbamate, piperidinium pentamethylenedithiocarbamate, pipecoline piperidimethyldithiocarbamate, iron dimethyldithiocarbamate; hexamethylenetetramine, acetaldehydeaniline, butyraldehydeaniline, etc. Aldehyde ammonia-based compounds such as mercaptobenzothiazole, mercaptobenzothiazole sodium salt, dibenzothiazyl disulfide, 2- (4-morpholinodithio) benzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, etc. Thiazole compounds; tetramethylthiuram monosulfide, tetraethylthiuram monosulfide, tetramethylthiura Disulfide,
Thiuram sulfides such as tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide and the like; mercaptobenzothiazole, dibenzothiazyl disulfide, 2
Thiazole-based compounds such as mercaptobenzothiazole zinc; N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, Nt-butylbenzothiazole sulfenamide, etc. Examples thereof include, but are not limited to, such sulfenamide compounds. These crosslinking accelerators may be used alone or in combination of two or more.

When a cross-linking accelerator is used, its amount is 10 parts by weight or less, preferably 5 parts by weight or less, per 100 parts by weight of ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer. is there. If it exceeds 10 parts by weight, the physical properties of the thermoplastic elastomer obtained may deteriorate.

It is also possible to use a crosslinking accelerator and a dispersant typified by zinc white, active zinc white, surface-treated zinc white, zinc carbonate, litharge and magnesium oxide during the crosslinking.

Further, the use of a co-crosslinking agent in the present invention is effective because the crosslinking effect is improved.

Examples of the co-crosslinking agent include P.quinone dioxime, P.P dibenzoylquinone dioxime, N-methyl-N'-4-dinitrosoaniline, dinitrosobenzene, lauryl methacrylate and ethylene glycol dimetha. Acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, diaryl fumarate, diaryl phthalate, tetraaryloxyethane, triaryl cyanurate, aryl methacrylate, Maleimide, phenylmaleimide,
N, N'-m-phenylene bismaleimide, maleic anhydride, itaconic acid, divinylbenzene, diarylmelamine, diphenylguanidine, divinyl adipate, vinyltoluene, 1,2-polybutadiene, liquid styrene-butadiene copolymer rubber, dipenta Examples thereof include methylene thiuram pentasulfide, mercaptobenzothiazole, sulfur, and the like, and one or more of these are used as necessary.

Further, scorch inhibitors represented by phthalic anhydride, benzoic acid, salicylic acid, nitroso compounds, coumarone resins, terpene resins, petroleum hydrocarbon compounds, tackifiers represented by rosin derivatives, and paraffinic softeners. A naphthenic softening agent, an aromatic softening agent, a softening agent represented by asphalt, petrolatum, ozokerite and the like can be added as necessary.

Further, if necessary, calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, serisanite, zeolite, nepheline sinite,
Inorganic fillers and reinforcing agents such as attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, carbon black, gypsum, quartz Further, organic and inorganic pigments can be blended. Also, release agents, anti-blocking agents, slip agents, antistatic agents, lubricants, heat resistance stabilizers, light stabilizers, UV absorbers, weather resistance stabilizers, foaming agents, defoamers, rust preventives, anti-mold agents. If desired, an ion trap agent, a flame retardant, a flame retardant aid, a crystal nucleating agent, a clarifying agent and the like may be added.

Further, the thermoplastic elastomer of the present invention may be used as a mixture with another resin. In this case, the third
It is also possible to add a compatibilizer as a component. In particular, low-density polyethylene, linear low-density polyethylene, etc. are preferably used for the purpose of improving processability.

The method for producing the thermoplastic elastomer of the present invention is not particularly limited, but from the viewpoint of improving the mechanical properties, the thermoplastic resin and the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer are melted. A method of crosslinking the ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer with sulfur and / or organic peroxide while kneading and applying shear is preferable. The manufacturing machine used at this time is not particularly limited, but melt kneading and cross-linking of the rubber components are performed by a batch kneader such as a roll, a Banbury mixer, a kneader, a screw extruder, a continuous kneader such as a rotor type continuous kneader, or the like. . The temperature in the kneader is preferably 120 to 280 ° C., and the residence time is preferably 1 to 30 minutes. However, the temperature must be above the melting point of the thermoplastic resin used. The produced thermoplastic elastomer is taken out from the kneading machine, and if necessary, pelletized by a sheet pelletizing machine, an extruder, etc., and finally any molding such as extrusion, injection, calendering, compression, blowing, foaming and transfer molding. It can be molded by the method.

[0033]

EXAMPLES The present invention will be described below with reference to examples, but these are illustrative and not restrictive. Various measurements in the examples were carried out by the following methods.

(Ethylene / Propylene / Styrene / 5-
Measurement of propylene, styrene and 5-ethylidene-2-norbornene contents in ethylidene-2-norbornene copolymer) 1,1,2,2-tetrachloroethane was used as a solvent, 400 MHz, ¹ H-NMR spectrum (JEOL ( JNM GX400 manufactured by K.K.) and calculated.

(Measurement of molecular weight and molecular weight distribution) o-
Gel permeation chromatography (manufactured by Millipore Corporation) at 140 ° C using dichlorobenzene.
It was calculated in terms of polyethylene by using 150C type GPC).

Synthesis Example of Ethylene / Propylene / Styrene / 5-Ethylidene-2-norbornene Copolymer 2400 ml of toluene and 150 ml of styrene, 45 ml of 5-ethylidene-2-norbornene and 250 ml of propylene were added to a 5 l autoclave, and the mixture was stirred while stirring. The temperature was raised to 80 ° C. The internal pressure at this time is 4 kg
/ Cm ² , ethylene was introduced here, and the total pressure was 16
It was increased to kg / cm ² . Next, in another reaction container, 10 ml of toluene, 15 mmol of methylaluminoxane,
15 μmol of (dimethyl (t-butylamido) (tetramethyl-η5-cyclopentadienyl) silane) dichloride titanium synthesized by a known method was added, and the mixed solution was stirred for 20 minutes, and then introduced into an autoclave for polymerization. Started. In this polymerization, the total pressure was maintained at 16 kg / cm ² by continuously introducing ethylene at 80 ° C.
For 40 minutes.

After completion of the polymerization, the polymer was washed with a large amount of ethanol and dried under reduced pressure at 100 ° C. for 8 hours. As a result, the content of 5-ethylidene-2-norbornene was 0.6.
mol%, styrene content 1 mol%, propylene content 3
42 g of 1 mol% ethylene / propylene / styrene / 5-ethylidene-2-norbornene copolymer was obtained. This copolymer has a number average molecular weight of 50,000 and Mw / Mn =
2.2.

When the iodine value and Mooney viscosity were determined by known methods, the iodine value was 8.8 mg / g, M
It was L1 + 4 (100 ° C.) 59.

Example 1 Ethylene / propylene / styrene / 5 obtained in the synthesis example
-Ethylidene-2-norbornene copolymer 40 g, naphthene oil 40 g, zinc white 2 g, stearic acid 0.4 g
The internal volume is 100cc, the set temperature is 50 ° C, and the rotation speed is 70rp.
m. Internal mixer (Labo Plastomill, manufactured by Toyo Seiki Seisakusho) was kneaded for 5 minutes to obtain a compound. The compound was kneaded with an 8-inch roll kneader having a surface temperature set to 50 ° C., and a cross-linking agent (Perhexa 25B-4
0, manufactured by NOF CORPORATION 2g, divinylbenzene 0.6
g was added.

The compound to which the cross-linking agent was added was polypropylene (Tosoh Polypro J5100A, Tosoh Corp.).
(Made) with an internal volume of 15 cc, a set temperature of 50 ° C,
Rotation speed 70 rpm. I put it in the internal mixer of
Kneading was performed and the torque change was recorded.

Example 2 In Example 1, ultra low density polyethylene (LUMITA
Production was carried out by the same method except that 5 g of C12-1, manufactured by Tosoh Corporation was added together with polypropylene.

Comparative Example 1 Instead of the ethylene / propylene / styrene / 5-ethylidene-2-norbornene copolymer used in Example 1, an ethylene / propylene / 5-ethylidene-2-norbornene copolymer (JSREP93, manufactured by Nippon Synthetic Co., Ltd.) Made by Rubber Co., Ltd., iodine value 9.5 mg / g, ML1 + 4 (10
(0 ° C.) 54) was used and manufactured in the same manner.

Comparative Example 2 In Comparative Example 1, ultra low density polyethylene (LUMITA
Production was carried out by the same method except that 5 g of C12-1, manufactured by Tosoh Corporation was added together with polypropylene.

The manufacturing time was estimated based on the torque behavior during manufacturing as described above. The results are shown in Table 1.

(Estimation of Production Time) The torque behavior during kneading was evaluated as a measure of the time required to produce the dynamically crosslinked thermoplastic elastomer. The torque once decreases with the start of kneading, then rises again, reaches a peak, and then decreases again to reach an equilibrium value. At this time, the time required for the torque to reach the peak value was defined as Tm, and was used as a guide for the time required for manufacturing.

(Tensile test) According to JIS K6301,
A tensile test was conducted. The temperature was 23 ° C., the dumbbell was No. 3, and the tensile speed was 500 mm / min.

[0047]

[Table 1]

[0048]

As described above, the ethylene of the present invention /
A thermoplastic elastomer resin composition comprising a crosslinked α-olefin / aromatic vinyl compound / non-conjugated diene copolymer and a thermoplastic resin has excellent mechanical properties and is superior to conventional ethylene / α-olefin copolymers. The thermoplastic elastomer resin composition has excellent productivity and short crosslinking time.

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Claims (3)

[Claims] 1. A thermoplastic elastomer resin composition comprising a thermoplastic resin and an ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer cross-linked product. 2. The ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer having a molar ratio of ethylene to α-olefin of 30/70 to 90/10,
The thermoplastic elastomer resin composition according to claim 1, wherein the aromatic vinyl compound content is in the range of 0.01 to 30 mol% and the non-conjugated diene content is in the range of 0.1 to 30 mol%. 3. Ethylene / α-olefin / aromatic using sulfur and / or organic peroxide while melt-kneading a thermoplastic resin and ethylene / α-olefin / aromatic vinyl compound / non-conjugated diene copolymer. The method for producing a thermoplastic elastomer resin composition according to claim 1, wherein the group vinyl compound / non-conjugated diene copolymer is crosslinked.