JPH06287372A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To provide the title composition scarcely suffering from oil bleeding and being excellent in mechanical properties, appearance, etc. CONSTITUTION:The composition is prepared by mixing 100 pts.wt. partially crosslinked composition prepared by dynamically heat-treating a mixture comprising 40-95wt.% oil-extended olefin copolymer rubber containing 20-150 pts.wt. mineral oil softener per 100 pts.wt. olefin copolymer rubber having a Mooney viscosity (100 deg.C, ML1+4) of 120-350 and 5-60wt.% propylene polymer resin in the presence of an organic peroxide with 10-100 pts.wt. olefin polymer resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to thermoplastic elastomer compositions. More specifically, the present invention relates to an olefin-based thermoplastic elastomer composition which has excellent mechanical properties and can substitute for vulcanized rubber.

[0002]

2. Description of the Related Art Thermoplastic elastomer (hereinafter referred to as "TP
Say "E". ) Does not require a vulcanization process and can be processed with a normal thermoplastic resin molding machine, and its applications have been developed in a wide range of fields including automobile parts, home electric appliances parts and sundries. There is. Among them, the olefin-based TPE composition is known from JP-A-48-26838. However, this composition is inferior to the vulcanized rubber in terms of flexibility, tensile strength at break, elongation at break, compression set, etc. in the field of vulcanized rubber replacement, and thus has limited applications.
In order to improve these performances, the addition of a mineral oil-based softening agent or a peroxide non-crosslinking hydrocarbon-based rubber-like substance gives flexibility, and a crosslinking aid is also used to increase the degree of crosslinking and improve the compression set. Various attempts have been made. (For example, Japanese Patent Publication No. 56-15740).

However, in these compositions, even if the degree of cross-linking is increased to improve the compression set, the flexibility is lowered, the breaking strength and breaking elongation in the tensile test are lowered, or the composition surface is softened. It has been difficult to obtain an olefin-based TPE composition having an excellent balance of physical properties due to bleeding of the agent.

[0004]

Under these circumstances, the problems to be solved by the present invention are olefinic TPEs, particularly olefinic TPEs having a low hardness (Shore A hardness of 90 or less).
In PE, it is possible to substitute vulcanized rubber for its flexibility and mechanical properties (especially tensile rupture strength, elongation at break, compression set), and good olefinic TPE composition with blow moldability, extrusion moldability or injection moldability. To provide things.

[0005]

The inventors of the present invention have conducted extensive studies to overcome the drawbacks of the above-mentioned conventional methods, and as a result, an oil-extended olefin copolymer containing a specific mineral oil softener in advance. It was found that a composition obtained by partially cross-linking a mixture of an oil-extended olefin-based copolymer rubber containing a softening agent and a propylene-based polymer resin is excellent in flexibility and mechanical properties, Has been completed. That is, the present invention has a Mooney viscosity of 100 ° C. (ML _{1 + 4} 100 ° C.) of 12
40 to 95% by weight of an oil-extended olefinic copolymer rubber (A) containing 20 to 150 parts by weight of a mineral oil softening agent and 100 to 100 parts by weight of an olefinic copolymer rubber of 0 to 350, and a propylene polymer. Olefin-based polymer resin (C) 10 to 100 parts by weight of a partially crosslinked composition obtained by dynamically heat-treating a mixture of 5 to 60% by weight of resin (B) in the presence of an organic peroxide. The present invention relates to a thermoplastic elastomer composition containing 100 parts by weight. The present invention will be specifically described below.

In the present invention, the olefin copolymer rubber used in the oil-extended olefin copolymer rubber (A) is, for example, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene rubber, It is an amorphous random elastic copolymer containing an olefin as a main component, such as ethylene-butene-non-conjugated diene rubber and propylene-butadiene copolymer rubber. Among these, ethylene-propylene-non-conjugated diene rubber is particularly preferable.
Non-conjugated dienes include dicyclopentadiene, 1,4-
There are hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene and the like, but ethylidene norbornene is particularly preferable.

As a more preferred specific example, the propylene content is 10 to 55% by weight, preferably 20 to 40.
It is an ethylene-propylene-ethylidene norbornene copolymer rubber (hereinafter referred to as "EPDM") in which the content of non-conjugated diene such as ethylidene norbornene is 1 to 30% by weight, preferably 3 to 20% by weight. Part 1
00 ° C Mooney viscosity (ML _{1 + 4} 100 ° C) is 120 ~
It is 350, preferably 140-300. If the propylene content is less than 10% by weight, the flexibility is lost and 55
If it exceeds 5% by weight, mechanical properties tend to deteriorate. If the content of the non-conjugated diene typified by ethylidene norbornene is less than 1%, the mechanical properties tend to decrease, and if it exceeds 30% by weight, the injection moldability tends to decrease. If the Mooney viscosity at 100 ° C. (ML _{1 + 4} 100 ° C.) is lower than 120, mechanical properties are lost, and if it is higher than 350, the appearance of the molded product is deteriorated. However, when EPDM having a Mooney viscosity of 120 to 350 is used, the mechanical properties are large, the tensile rupture strength and the elongation at break are dramatically improved, and the crosslinking efficiency becomes high, so that the mechanical properties, especially the strength and compression set are improved. Provides improved distortion. EPDM manufactured by a known method can be used.

The mineral oil-based softening agent used in the present invention is a petroleum fraction having a high boiling point, which is blended for the purpose of improving processability and mechanical properties, such as paraffinic, naphthenic or aromatic compounds. Although there are group-based ones, paraffin-based ones are preferably used. When the amount of aromatic components is large, the staining property becomes strong, and there is a limit in the use intended for transparent products or light-colored products, which is not preferable.

The oil-extended olefinic copolymer rubber (A) is
Mineral oil-based per 100 parts by weight of olefin-based copolymer rubber
20 to 150 parts by weight of a softening agent, preferably 30 to 120
It is to contain by weight. If less than 20 parts by weight
The flowability of the reffin-based TPE composition is lowered, and especially, the extrusion process
Workability and injection moldability are impaired. On the other hand, 150 parts by weight
If the amount is too high, the plasticity increases remarkably and the processability deteriorates.
In addition, performance such as physical properties of the product will be deteriorated.
Not good. And oil-extended olefin-based copolymer rubber
(A) 100 ° C Mooney viscosity (ML _{1 + 4}100 ° C)
Is preferably 30 to 100, more preferably 40 to 9
It is 0. Below 30 the mechanical properties are lost and 100
If it is higher, the molding process tends to be difficult.

EPDM with Mooney viscosity of 120-350
When a large amount of a mineral oil-based softening agent is blended with, an olefin-based TPE composition capable of satisfying both flexibility and processability improvement by improving fluidity and mechanical properties at the same time is obtained. You can Generally, a mineral oil-based softening agent is used as a fluidity improver in an olefin-based TPE composition.
When PDM is not used, regardless of the viscosity of EPDM, 40 parts of mineral oil type softener is added per 100 parts by weight of EPDM.
If it is blended in an amount of more than 1 part by weight, bleeding of the softening agent will occur on the surface of the TPE composition, and contamination of the product, sticking and the like will be observed, which is not preferable. However, the 100 ° C Mooney viscosity is 120-350.
Of oil-extended EPDM containing 20 to 150 parts by weight of a mineral oil-based softening agent per 100 parts by weight of EPDM of
It is possible to obtain a TPE composition having no bleeding of a softening agent, no product contamination or tackiness being observed, and excellent physical properties such as breaking strength, breaking elongation, and compression set. Despite the large blending ratio of this mineral oil-based softening agent, no bleeding of the softening agent is observed because EPD has a high Mooney viscosity.
It is considered that when M is used, the upper limit of the allowable oil expansion amount of the mineral oil-based softening agent is increased, and the softening agent that is preferably added in advance is uniformly dispersed in EPDM.

A known method is used for the oil extension method of EPDM. For example, using a device such as a roll or a Banbury mixer, a method of oil-extending by a method of mechanically kneading EPDM and a mineral oil-based softening agent, or adding a predetermined amount of a mineral oil-based softening agent to an EPDM solution, and then , A method of removing the solvent by a method such as steam stripping, and the like.
Of these, the preferred oil extension method is a method using an EPDM solution, and the EPDM solution is an EPDM solution obtained by polymerization.
The operation is easier when using a solution.

The propylene polymer resin (B) used in the present invention is preferably polypropylene or a copolymer resin of propylene and an α-olefin having 2 or more carbon atoms. Specific examples of the α-olefin having 2 or more carbon atoms include ethylene, 1-butene, 1-pentene, and 3-methyl-.
1-butene, 1-hexene, 1-decene, 3-methyl-
1-Pentene, 4-methyl-1-pentene, 1-octene and the like. The melt flow rate of these polymer resins is
0.1 to 100 g / 10 minutes is preferable, more preferably
It is in the range of 0.5 to 50 g / 10 minutes. If the melt flow rate is smaller than 0.1 g / 10 minutes or larger than 100 g / 10 minutes, there is a problem in workability. Further, when the amount of the propylene-based polymer resin (B) in the olefin-based TPE composition according to the present invention is less than 5% by weight, the fluidity is deteriorated and the appearance of the molded article is deteriorated. There is no sex.

As an organic peroxide for partially crosslinking a mixture of an oil-extended olefin copolymer rubber (A) and a propylene polymer resin (B), 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, 2,5
-Dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t-butylperoxy) 3,5, 5-trimethylcyclohexane, 2,5-
Examples include dimethyl-2,5-di (peroxybenzoyl) hexyne-3 and dicumyl peroxide. Of these, 2,5-dimethyl-especially in terms of odor and scorch.
2,5-di (t-butylperoxy) hexane is preferred.

The amount of the organic peroxide added is 0.005 to 2.0 parts by weight, preferably 0.01 to 0.6, based on 100 parts by weight of the total of the oil-extended olefin copolymer rubber (A) and the propylene polymer resin (B). It can be selected within the range of parts by weight. 0.0
If it is less than 05 parts by weight, the effect of the crosslinking reaction is small, and if it exceeds 2.0 parts by weight, it is difficult to control the reaction and it is not economically advantageous.

In producing the composition of the present invention, N, N'-m- serves as a cross-linking aid at the time of partial cross-linking with an organic peroxide.
Multifunctionality such as phenylene bismaleimide, toluylene bismaleimide, P-quinone dioxime, nitrobenzene, diphenylguanidine, trimethylolpropane, divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate The compound of can be blended. By blending such a compound, a uniform and mild crosslinking reaction occurs,
It is possible to improve mechanical properties.

The amount of the crosslinking aid added is selected in the range of 0.01 to 4.0 parts by weight based on 100 parts by weight of the total of the oil-extended olefin copolymer rubber (A) and the propylene polymer resin (B). Can be done. It is preferably 0.05 to 2.0 parts by weight.
If it is less than 0.01 parts by weight, the effect is difficult to appear, and if it exceeds 4 parts by weight, it is not economically advantageous.

A specific cross-linking composition is obtained by dynamically heat treating a mixture of an oil-extended olefin copolymer rubber (A) and a propylene polymer resin (B) in the presence of an organic peroxide. The manufacturing method will be described below. The oil-extended olefin-based copolymer rubber (A), the propylene-based polymer resin (B), the organic peroxide, and, if necessary, further a crosslinking auxiliary agent are mixed in a specific ratio and dynamically heat-treated. That is, they are melted and kneaded. As the mixing and kneading device, a conventionally known non-open type Banbury mixer, a twin-screw extruder or the like is used.
The kneading temperature may be 150 ° C to 300 ° C for about 1 to 30 minutes. In the production of this composition, if necessary, auxiliary materials such as an inorganic filler, an antioxidant, a weather resistance agent, an antistatic agent and a coloring agent can be added.

A preferred method for mixing and kneading the oil-extended olefin-based copolymer rubber (A), the propylene-based polymer resin (B), the organic peracid, and the like is an oil-extended olefin-based copolymer rubber. A mixture of (A) and a propylene-based polymer resin (B), and if necessary, a crosslinking aid and the above-mentioned auxiliary materials are mixed in a predetermined ratio, and the mixture is mixed with a known non-release type kneading machine such as Banbury mixer for 150 to 150%. After sufficiently kneading and homogenizing in a temperature range of 250 ° C., this composition is thoroughly blended with an organic peroxide in a closed mixer such as a tumbler or a super mixer. Then, this blended product was heated at 200 ° C. to 3 by using a twin-screw continuous extruder capable of obtaining a strong kneading force.
It can be obtained by dynamically performing heat treatment at 00 ° C.

More specifically, the oil-extended olefin-based copolymer rubber (A) and the propylene-based polymer resin (B), if necessary, a crosslinking aid and the above-mentioned auxiliary materials are further compounded in a predetermined ratio, and the non-release type kneading is carried out. Using the Banbury mixer of the machine
After sufficiently kneading and homogenizing in a temperature range of 50 to 250 ° C., the obtained composition and an organic peroxide are sufficiently blended with a closed mixer such as a tumbler or a super mixer. Next, the partially crosslinked composition can be obtained by dynamically heat-treating this blend at 200 to 300 ° C. using a twin-screw continuous extruder or the like capable of obtaining strong mixing and strength.

Examples of the auxiliary material include the following as a specific example of the antistatic agent. That is,
(A) Cationic compounds such as primary amine salts, tertiary amines, quaternary ammonium compounds, and pyridine derivatives,
(B) Sulfated oil, soap, sulfated ester oil, sulfated amide oil, olefin sulfate ester salt, fatty alcohol sulfate ester salt, alkyl sulfate ester salt, fatty acid ethyl sulfonate, alkyl naphthalene sulfonate,
Anionic compounds such as alkylbenzene sulfonate, succinate sulfonate, and phosphate ester salt,
(C) Partial fatty acid ester of polyhydric alcohol, ethylene oxide addition product of fatty alcohol, ethylene oxide addition product of fatty acid, ethylene oxide addition product of fatty acid amino or fatty acid amide, ethylene oxide addition product of alkylphenol, ethylene oxide addition product of alkylnaphthol Adducts, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, nonionic ones such as polyethylene glycol, (d) carboxylic acid derivatives, amphoteric ones such as imidazoline derivatives are generally usable, Particularly, nonionic compounds, especially polyoxyethylene alkylamine, polyoxyethylene alkylamide or fatty acid ester thereof, fatty acid ester of glycerin, etc. are preferable.

The above-mentioned antistatic agent may be a single type or a mixture of two or more types. The amount thereof is preferably about 0.03 to 2 parts by weight, and more preferably about 100 parts by weight of the partially crosslinked composition according to the present invention.
It is 0.04 to 1 part by weight. If the blending ratio is higher than this,
It is not preferable because it exudes to the surface and deteriorates the physical properties of the thermoplastic elastomer composition. By adding this antistatic agent, it is possible to obtain a molded product having flexibility and having no stickiness. Further, the stickiness and the adhesion of dust and the like due to the elimination of the bleeding of the softening agent are reduced, and at the same time, the chargeability which is the original function of the antistatic agent is reduced, and the adhesion of dust due to the electrification is also reduced.

On the other hand, slipperiness may be desired as the property of the surface of the molded product, and higher fatty acid amide can be used for this. Specific examples of the higher fatty acid amide include lauric acid amide, valmitic acid amide,
Saturated fatty acid amides such as stearic acid amide and behenic acid amide, erucic acid amide, oleic acid amide, bridic acid amide, elaidic acid amide and other unsaturated fatty acid amides, methylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisstearin Acid amides, bis fatty acid amides such as ethylene bisoleic acid amide, and the like are used. Particularly preferred higher fatty acid amides are compounds having a melting point of about 70 ° C to 110 ° C. The amount of the above-mentioned higher fatty acid amide is preferably about 0.03 per 100 parts by weight of the partially crosslinked composition according to the present invention.
˜2 parts by weight, more preferably about 0.04 to 1 part by weight.
If the blending ratio is higher than this, leaching of the higher fatty acid amide to the surface and deterioration of the physical properties of the thermoplastic elastomer composition occur, which is not preferable.

The auxiliary materials can be added at the stage of producing the thermoplastic elastomer composition according to the present invention, which will be described later, and at the time of processing or use of the product after processing.

The olefin polymer resin (C) in the present invention includes ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, including the propylene polymer resin (B). Homopolymers or copolymers of α-olefins such as 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene, or a small amount of α-olefin such as 10 mol%
The following copolymers with other polymerizable monomers, for example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, etc. are referred to. Melt index of these olefin polymer resins (ASTM-D-1230-65T, 190 ° C.,
230 ° C for propylene-based polymer) is 5 to 100 g /
It is preferably 10 minutes, especially 10 to 50 g / 10 minutes. The olefin polymer resin (C) functions to improve the fluidity of the composition obtained by the method of the present invention without substantially impairing the rubber-like properties. That is, since it works almost the same as the component (B), it is preferable that the component (B) and the component (C) are mixed complementarily. On the other hand, such an effect of the component (C) is more remarkable when blended in the partially crosslinked composition, as shown in Examples described later.

In the present invention, when the (C) olefin polymer resin is 10 to 100 parts by weight, preferably 30 to 50 parts by weight, and more than 100 parts by weight, based on 100 parts by weight of partially crosslinked, the thermoplastic resin obtained is obtained. Flexibility of the elastomer composition,
It is not preferable because rubber properties such as impact resilience or heat resistance is impaired.

The thermoplastic elastomer composition according to the present invention contains an inorganic filler such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica as long as the fluidity and rubber properties are not impaired. powder,
Asbestos, alumina, barium sulphate, aluminum sulphate, calcium sulphate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fibers, glass spheres, shirasu balloons, carbon fibers etc. or colorants such as carbon black, titanium oxide, sub-pencil, Red iron oxide, ultramarine blue, navy blue, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment and the like can be added. In the present invention, known heat-resistant stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, antiaging agents, weathering stabilizers, antistatic agents, metal soaps, lubricants such as waxes, etc. Etc. can be blended to the extent of being used in an olefin-based plastic or an olefin-based copolymer rubber.

Next, in the present invention, the partially crosslinked composition and (C)
An olefin polymer resin is blended. As a preferred method for uniformly blending, the pellets of the partially crosslinked composition and the pellets of the olefin polymer resin are once mixed into a V-type blender, a tumbler blender, a ribbon blender,
After mixing with a Hensiel mixer or the like, a method of kneading with an extruder, a mixing roll, a kneader, a Banbury mixer or the like can be mentioned. The weather resistance agent, antioxidant, colorant and the like may be added at any stage of the above process.

The thermoplastic elastomer composition according to the present invention can be molded by an apparatus used for usual thermoplastics, and is suitable for extrusion molding, calender molding, and particularly injection molding.

Since the component (A) is partially crosslinked, the thermoplastic elastomer composition according to the present invention has excellent rubber properties such as heat resistance, weather resistance, tensile properties, flexibility and impact resilience. In addition, since it has good fluidity, when it is made into a large-sized thick product, a product with good appearance without flow marks or sink marks can be obtained.

The thermoplastic elastomer composition according to the present invention can be used for automobile parts such as body panels, bumper parts, side shields, steering wheels, footwear such as shoe soles and sandals, electric wire coatings, connectors, cap plugs and the like. Parts, golf club grips, baseball bat grips, swimming pools, swimming fins, leisure products such as underwater glasses, gaskets, waterproof cloths, garden hoses, belts and other products can be considered. The thermoplastic elastomer composition according to the present invention is particularly suitable for use in large-walled products such as bumper parts.

[0031]

EXAMPLES The contents of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The test methods used for the sheet forming process and the physical property measurement in these examples and comparative examples are as follows. (1) Mooney viscosity (ML _{1 + 4} 100 ° C): ASTM
According to D-927-57T. Number 1 for EPDM
Was calculated.

[0032]

## EQU1 ## log (ML ₁ / ML ₂ ) = 0.0066 (ΔPHR) ML ₁ : Mooney viscosity of EPDM ML ₂ : Mooney viscosity of oil-extended EPDM ΔPHR: Oil-extended amount per 100 parts by weight of EPDM

(2) Hardness: According to ASTM D-2240. (A type, instantaneous value) (3) Stress at break: Based on JIS K-6301.
(JIS-3 dumbbell, pulling speed 200 mm / mi
n) (4) Elongation at break: Same as above (5) Compression set: Based on JIS K-6301. (70 ° C, 22Hr, compression rate 25%)

(6) Injection moldability: Toshiba Machine IS10
Uses 0EN-3A type injection molding machine. Molding temperature 220 ° C, mold temperature 50 ° C, injection 10 seconds, cooling 30 seconds. Mold shape 150mm × 90mm × 2mm Pin gate is used. The presence or absence of flow marks and sink marks was observed. The judgment rank is as follows. Flow marks and sink marks ○: None. Δ: Only found in a very limited range. X: Seen over the entire surface.

(7) Extrudability: USV type 25 mmφ extruder manufactured by Union Plastics. Full flight type screw, screw speed 30
rpm. The T-die was used, and the judgment was performed on the extruded skin. The judgment ranks are as follows. ○: excellent △: good ×: bad

(8) Oil bleeding property: 7
Let stand for 1 hour in an oven at 0 ° C and visually observe the oil bleeding on the surface of the molded product. The judgment rank is as follows. ○: No bleeding. Δ: There is slight bleeding. ×: There is bleeding.

Examples 1 to 2 In a 5% by weight hexane solution of EPDM (ML _{1 + 4} 100 ° C. = 143, propylene content = 30% by weight, iodine value = 10), a mineral oil-based softener per 100 parts by weight of EPDM ( Idemitsu Kosan, Diana Process Oil PW-380) (40 parts by weight) was added, followed by steam stripping to remove the solvent. Oil-extended EPDM (ML _{1 + 4} 100 ° C. = 53) 77 parts by weight, Vistanex MML-100 (polyisobutylene). , Esso Chemical Co., Ltd.) 8 parts by weight, polypropylene (MF
R = 12g / 10min, Sumitomo Noblen FL8013) 1
After kneading 5 parts by weight and Sumilizer BM (N, N'-m-phenylene bismaleimide, 0.3 parts by weight manufactured by Sumitomo Chemical Co., Ltd.) with a Banbury mixer at 170 to 200 ° C. for 7 minutes, a pellet-shaped master was prepared using an extruder. A batch was made. Next, 0.1 part by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane per 100 parts by weight of the masterbatch (hereinafter referred to as "organic peroxide").
Using a Henschel mixer, perform a uniform blending operation
I went for a minute. This blend was subjected to a dynamic heat treatment at 220 ° C. ± 10 ° C. for 70 seconds using a twin-screw kneading extruder capable of obtaining a strong kneading force to obtain a partially crosslinked composition. To 100 parts by weight of the obtained partially crosslinked composition, 40 parts by weight of the polypropylene or polyethylene (Sumikasen G801) was blended, and molding and evaluation of physical properties were performed. Hardness, tensile test,
A 2 mm thick plate obtained by injection molding was used for measuring the physical properties of compression set. The evaluation results are shown in Table 1.

Comparative Examples 1-2 When the masterbatch in Example 1 was produced, oil-extended E
77 parts by weight of PDM are added to JSR EP-24 (ML _{1 + 4} 10
0 ° C. = 70, propylene content = 44% by weight, iodine value =
Example 12 was repeated except that 54 parts by weight of EPDM of No. 12, manufactured by Japan Synthetic Rubber Co., Ltd.) and 23 parts by weight of mineral oil-based softener PW-380 were used. The evaluation results are shown in Table 1.

[0039]

[Table 1]

[0040]

As described above, according to the present invention, it is possible to provide a thermoplastic elastomer composition having extremely little oil bleed and excellent mechanical properties, appearance and the like.

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Claims (6)

[Claims] 1. A Mooney viscosity at 100 ° C. (ML _{1 + 4} 100
Oil-extended olefin-based copolymer rubber (A) 40 containing 20 to 150 parts by weight of a mineral oil-based softening agent per 100 parts by weight of an olefin-based copolymer rubber having a temperature of 120 to 350.
~ 95 wt% and propylene polymer resin (B) 5-60
100 parts by weight of a partially cross-linked composition obtained by dynamically heat treating a mixture consisting of 1 wt% of the mixture in the presence of an organic peroxide,
A thermoplastic elastomer composition comprising 10 to 100 parts by weight of an olefin polymer resin (C). 2. An olefin copolymer rubber is ethylene-based rubber.
The composition according to claim 1, which is a propylene-non-conjugated diene rubber. 3. An ethylene-propylene-non-conjugated diene rubber is an ethylene-propylene-ethylidene norbornene copolymer rubber having a propylene content of 10 to 55% by weight and an ethylidene norbornene content of 1 to 30% by weight. Item 2. The composition according to Item 2. 4. An oil-extended olefinic copolymer rubber (A) 1
00 ℃ Mooney viscosity (ML _{1 + 4} 100 ℃) is 30-1
The composition of claim 1 which is 00. 5. The composition according to claim 1, wherein the propylene polymer resin (B) is polypropylene or a propylene-α-olefin copolymer resin. 6. The composition according to claim 1, wherein the mineral oil softener is a paraffin softener.