JP2003113278A - Thermoplastic elastomer composition, powder consisting of the composition, and formed body produced by subjecting powder consisting of the composition to powder molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition with which a molded product having excellent flexibility, having little whitening in the folded part even if it is folded, having little generation of glossing and bled material when stored at a temperature in the range higher than about 80 deg.C and not reaching the melting point of the polyolefin, and having excellent tensile strength and cold impact resistance, and further to provide a powder consisting of the composition and a formed body of powder produced by subjecting the powder consisting of the composition to powder molding. SOLUTION: The thermoplastic elastomer composition contains 100 pts.wt. of (I), 50-200 pts.wt. of (II) and 30-200 pts.wt. of (III). (I): A polyolefin resin. (II): A specific hydrogenated diene copolymer. (III): A specific ethylene-1-hexene copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition, a powder of the composition, and a powder compact formed by powder molding of the composition. More specifically, the present invention is a polyolefin resin,
Containing a hydrogenated diene-based copolymer having a specific structure and an ethylene-1-hexene copolymer having a specific structure as an essential component, it has excellent flexibility, and the whitening of the bent portion is small even when bent, A thermoplastic elastomer composition capable of obtaining a molded article excellent in tensile strength and cold impact resistance when it is stored at a temperature of from about 0 ° C to a temperature lower than the melting point of the polyolefin resin, and a thermoplastic elastomer composition from the composition. The present invention relates to a powder compact and a powder compact formed by powder molding the powder comprising the composition.

[0002]

2. Description of the Related Art Conventionally, substitution of vinyl chloride resin used for automobile interior / exterior parts, home electric appliances, stationery products, office automation equipment, etc. has been promoted. A thermoplastic elastomer composition containing a thermoplastic elastomer has been proposed.

For example, JP-A-3-72512 discloses a hydrogenated diene copolymer composition comprising polypropylene and a hydrogenated diene copolymer. The molded article made of the composition has excellent flexibility and has an advantage that even when the molded article made of the composition is bent, the bent portion does not whiten. However, a molded article made of the composition has a glossy surface when stored at a temperature of about 80 ° C. to a temperature lower than the melting point of polypropylene.
For example, when used as an automobile interior material, there is a problem in that a poor appearance occurs (when a vehicle is stored outdoors in the summer, the temperature inside the vehicle may be about 80 to 120 ° C).

In Japanese Patent Laid-Open No. 2001-49052, the flexibility is excellent, and the bent portion does not whiten when bent,
Polypropylene and a hydrogenated diene-based copolymer having a specific structure are used as the thermoplastic elastomer for powder molding, which makes it possible to obtain a molded body that does not generate gloss when stored at a temperature of about 80 ° C. to a temperature lower than the melting point of polypropylene. Disclosed is a thermoplastic elastomer composition for powder molding containing, and a composition comprising the composition and an ethylene-propylene copolymer rubber.

However, the cold shock resistance of the molded article made of the above composition is not sufficiently satisfactory, and for example, an airbag mechanism of an instrument panel incorporating an airbag deploying apparatus using the above composition as the outermost layer is used. , When operated at low temperature, fragments of the instrument panel may be scattered.

[0006]

Under these circumstances, the problems to be solved by the present invention include polyolefin resin,
Containing a hydrogenated diene-based copolymer having a specific structure and an ethylene-1-hexene copolymer having a specific structure as an essential component, it has excellent flexibility, and even when bent, the whitening of the bent portion is small, and 80 ° C. Provided is a thermoplastic elastomer composition capable of obtaining a molded article excellent in tensile strength and cold shock resistance, with less occurrence of gloss and bleeding when stored at a temperature lower than the melting point of the polyolefin-based resin,
Further, it is to provide a powder comprising the composition and a powder compact formed by powder molding the powder comprising the composition.

[0007]

That is, the first invention of the present invention is that the following component (I) is 100 parts by weight, the following component (II) is 50 to 200 parts by weight and the following component (III) is 30 to 30 parts by weight.
The present invention relates to a thermoplastic elastomer composition containing 200 parts by weight. (I): Polyolefin resin (II): Hydrogenated diene copolymer satisfying all of the following conditions: Hydrogenated raw material diene copolymer containing the structural units (A) and (B) below. (A): vinyl aromatic compound polymer block (B): at least one block (B1) selected from the following (B1) and (B2): copolymer of vinyl aromatic compound and conjugated diene Block (B2): Conjugated diene polymer block: Content of vinyl aromatic compound unit (T: wt%) in the hydrogenated diene copolymer is 10 to 18 wt%: hydrogenated diene copolymer The content (V:% by weight) of the hydrogenated conjugated diene unit having 2 or more carbon atoms in the side chain is 60 with respect to the content of the hydrogenated conjugated diene unit in the combined product of 100% by weight.
Must exceed weight%. : (A) Content of vinyl aromatic compound unit in vinyl aromatic compound polymer block (S: wt%, where content of vinyl aromatic compound unit in hydrogenated diene copolymer is 100 wt% The condition (T) and the condition (V) satisfy the following formula (1): V ≦ 0.375 × S + 1.25 × T + 40 (1) (III): Sufficient ethylene-1-
Hexene copolymer: Density at 23 ° C. is 850 to 890 kg / m ³ : Melt flow rate at 190 ° C. is 5 to 100
g / 10 minutes

The second invention of the present invention relates to a powder comprising the thermoplastic elastomer composition of the first invention.

Further, the third invention of the present invention relates to a powder compact formed by powder molding the powder of the second invention.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Component (I) used in the present invention
Is a polymer containing a repeating unit derived from an olefin and having a crystallinity of 50% or more as determined by X-ray diffractometry. Examples of the olefin include ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like. Examples of the component (A) include olefin homopolymers such as ethylene homopolymer, propylene homopolymer and 1-butene homopolymer; copolymers composed of propylene and olefins other than propylene. The copolymer may be a random copolymer or a block copolymer. These may be used alone or in combination of two or more. Moreover, these can be manufactured by a well-known method.

From the viewpoint of the heat resistance of the powder compact, the component (I) is preferably a polyolefin resin having a content of repeating units (propylene units) derived from propylene of more than 70% by weight, and further propylene. Propylene-ethylene copolymer having a unit content of more than 90% by weight and / or propylene unit content of 80% by weight
A propylene-1-butene copolymer of more than 1 is preferred.
When it is desired to further improve the cold shock resistance of the powder compact, the propylene-ethylene copolymer having a propylene unit content of more than 98% by weight, and the propylene unit content of 98% by weight.
It is preferable to use a propylene-1-butene copolymer or a propylene homopolymer having a viscosity of more than 1.

According to JIS K-7210 of component (I), the melt flow rate (MFR) measured at 230 ° C. and a load of 21.18 N is preferably 10 to 500 g / from the viewpoint of further increasing the tensile strength of the powder compact. It is 10 minutes, more preferably 20 to 300 g / 10 minutes.

The component (II) used in the present invention is a hydrogenated diene copolymer which satisfies all the above conditions (1) to (3).

The component (II) is a polymer obtained by hydrogenating a raw material diene-based copolymer containing the structural units (A) and (B) below (conditions). (A): Vinyl aromatic compound polymer block (B): At least one kind of block (B1) selected from the following (B1) and (B2): Copolymer block (B2) of vinyl aromatic compound and conjugated diene : Conjugated diene polymer block

As the conjugated diene used for the production of the component (II), for example, a conjugated diene having 4 to 8 carbon atoms is used, and 1,3-butadiene, isoprene, pentadiene, 2-3-dimethylbutadiene and the like are used. These may be used, and these may be used alone or in combination of two or more. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of further increasing the tensile strength of the obtained molded product. As the vinyl aromatic compound, for example, a vinyl aromatic compound having 8 to 12 carbon atoms is used, and the 1-position or 2-position of the vinyl group may be substituted with an alkyl group such as a methyl group. Specifically, styrene, p-
Methyl styrene, α-methyl styrene and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, styrene is preferable from the viewpoint of further increasing the tensile strength of the obtained molded product.

Component (II) is usually represented by the general formula [(A)-
(B)] n, [(A)-(B)] n- (A), [(B)
-(A)] n- (B) (where n is an integer of 1 or more,
When (A) and (B) are plural, plural (A) and (B) may be the same or different. ), For example, [(A)-(B
1)] n- (A) or [(A)-(B2)] n- (A)
(However, n is an integer of 1 or more and is a repeating unit (A),
(B1) and (B2) may be the same or different. ) And hydrogenated diene-based copolymers.

The component (II) is a hydrogenated diene represented by (A)-(B1)-(A) or (A)-(B2)-(A) from the viewpoint of the tensile strength of the resulting molded article. -Based copolymers are preferable, for example, styrene homopolymer block-butadiene-styrene copolymer block (random copolymer block or tapered block in which styrene gradually increases) -hydrogenation of a polymer composed of styrene homopolymer block , A styrene homopolymer block-a butadiene homopolymer block-a hydrogenated product of a polymer composed of a styrene homopolymer block, a styrene homopolymer block-isoprene-styrene copolymer block (random copolymer block or styrene Taper block) -a hydrogenated product of a polymer composed of a styrene homopolymer block, Ren homopolymer block - isoprene homopolymer block - hydrogenated products such as styrene homopolymer consists block a polymer and the like. Among these, a hydrogenated diene-based copolymer represented by (A)-(B2)-(A) is preferable from the viewpoint of further increasing the tensile strength and cold shock resistance of the obtained molded product, and styrene-
A hydrogenated product of a butadiene-styrene copolymer is particularly preferable.

The content (T) of the vinyl aromatic compound unit of the component (II) is 10 to 18% by weight (condition), preferably 12 to 17% by weight. However, component (II)
The total amount of the monomer units contained in is 100% by weight. If the content of the vinyl aromatic compound unit is too large, the flexibility of the obtained molded article may be poor, and when the molded article is bent, whitening of the bent portion may be large. Also,
When the content of the vinyl aromatic compound unit is too small, when the obtained molded product is stored at a temperature of 80 ° C. to a temperature lower than the melting point of component (I), gloss and bleeding on the surface of the molded product occur. There are many cases. The content of the vinyl aromatic compound unit can be determined by ¹ H-NMR measurement using a solution of component (II) such as carbon tetrachloride.

By hydrogenating the raw material diene-based copolymer, the unsaturated bond of the conjugated diene unit is saturated. When the saturated monomer unit is a hydrogenated conjugated diene unit, the component ( The content of hydrogenated conjugated diene units in II) is 100
In the component (II), the content (V: wt%) of hydrogenated conjugated diene units having 2 or more carbon atoms in the side chain is more than 60 wt% with respect to wt% (conditions), It is preferably 65 to 85%, and particularly preferably 70 to 8%.
It is 0%. If the ratio is too small, the flexibility of the obtained molded article may be poor, and there is a problem that when the molded article is bent, whitening of the bent portion is large. Also,
If the ratio is too large, when the obtained molded product is stored at a temperature of 80 ° C. to a temperature lower than the melting point of component (I), gloss and bleeding may often occur on the surface of the molded product.
The content can be determined by the Morello method using infrared analysis.

(A) Content of vinyl aromatic compound unit in vinyl aromatic compound polymer block (S:% by weight However, the content of vinyl aromatic compound unit in the hydrogenated diene copolymer is 100% by weight. %), The condition (T), and the condition (V) must satisfy the following expression (1) (condition) V ≦ 0.375 × S + 1.25 × T + 40 (1) ) In the equation (1), when the value on the left side exceeds the value on the right side,
When the obtained molded product is stored at a temperature of 80 ° C. to a temperature lower than the melting point of component (I), gloss and bleeding may often occur on the surface of the molded product. Also, the cold shock resistance of the obtained molded article may be insufficient.

When the molded product is stored at a temperature from 80 ° C. to a temperature lower than the melting point of component (I), the hydrogenated diene-based co-polymer is used from the viewpoint of further reducing gloss and bleeding on the surface of the molded product. Content of vinyl aromatic compound unit in coalescence 100
Content of vinyl aromatic compound unit in the (A) vinyl aromatic compound polymer block as weight% (S:% by weight)
Is preferably 3 to 100% by weight, more preferably 30 to 100% by weight, and further preferably 50 to 1%.
It is 00% by weight. (conditions)

From the viewpoints of further increasing the flexibility of the obtained molded product, further reducing the whitening of the bent portion when the molded product is folded, and enhancing the light resistance of the molded product, the diene-based raw material By hydrogenating the polymer,
The unsaturated bond of the conjugated diene unit is saturated, but when the saturated monomer unit is a hydrogenated conjugated diene unit,
The content of the conjugated diene unit in the raw material diene-based copolymer is 100% by weight, the content of the hydrogenated conjugated diene unit in the hydrogenated diene-based copolymer is preferably 80% by weight or more, and It is preferably 90% by weight or more, and more preferably 96% by weight or more. (Hereinafter, the content is referred to as hydrogenation rate.) (Conditions) The content can be determined by ¹ H-NMR measurement using a carbon tetrachloride solution of the component (II).

From the viewpoint of enhancing the heat resistance retention and the light resistance of the obtained molded product, when the molded product is stored at a temperature of from 80 ° C. to a temperature lower than the melting point of component (I), the gloss and bleed on the surface of the molded product. From the viewpoint of further reducing the generation of the component (II), the number average molecular weight of the component (II) is preferably 50,000 or more, more preferably 100,000 or more. Further, from the viewpoint of further increasing the flexibility of the obtained molded product, from the viewpoint of enhancing the appearance of the molded product obtained by powder molding the powder comprising the thermoplastic elastomer composition of the present invention (reducing flesh and pinholes), The number average molecular weight of the component (II) is preferably 400,000 or less, more preferably 300,000 or less. (Condition) The number average molecular weight is measured by a gel permeation chromatography (GPC) method.

The melt flow rate (MFR) measured according to JIS K-7210 of component (II) at 230 ° C. and a load of 21.18 N is, from the viewpoint of further increasing the tensile strength of the molded product, the cold impact strength of the molded product. From the viewpoint of increasing the appearance and the appearance of the molded body, 0.1 to 20 is preferable.
0 g / 10 minutes, more preferably 1 to 100 g / 1
It is 0 minutes, more preferably 3 to 80 g / 10 minutes.

The component (II) of the present invention may be modified with a functional group, and the functional group is at least selected from an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an isocyanate group and an epoxy group. One type of functional group can be used. When a hydrogenated diene-based copolymer modified with these functional groups is used, for example, when the resulting molded article is bonded to a polyurethane foam layer to produce a two-layer molded article or a multilayer molded article, It is possible to get the advantage of improved adhesion.

The component (II) of the present invention is disclosed, for example, in JP-A-3-
-72512, JP-A-5-271325,
Japanese Patent Application Laid-Open Nos. 5-271327 and 6-28736.
It can be produced by the method described in Japanese Patent Publication No. 5 or the like.

The component (III) used in the present invention is an ethylene-1-hexene copolymer satisfying the above conditions and.

The specific gravity of component (III) at 23 ° C. is 8
It is 50 to 890 kg / m ³ (condition), preferably 860 to 885 kg / m ³ . If the specific gravity is too small, gloss and bleeding may often occur on the surface of the molded product when the resulting molded product is stored at a temperature of 80 ° C. to a temperature lower than the melting point of component (I). If the specific gravity is too large, the flexibility and the cold shock resistance of the obtained molded article deteriorate,
When the obtained molded product is stored at a temperature of 80 ° C. to a temperature lower than the melting point of component (I), gloss and bleeding may often occur on the surface of the molded product. Here, the specific gravity is JI
It is measured under the condition without annealing according to the method described in SK6922-1.

The melt flow rate (MFR) of component (III) measured at 190 ° C. and a load of 21.18 N according to JIS K-7210 is 5 to 100 g / 10 minutes (conditions), preferably 6 to 50 g / 10 minutes. If the melt flow rate is too small, the tensile strength of the obtained molded article may be lowered, and when a molded article produced by powder-molding a powder comprising the thermoplastic elastomer composition of the present invention is produced, The appearance of the body may be deteriorated (for example, defects such as flesh thickness and pinholes may occur). If the melt flow rate is too high, the tensile strength and cold impact resistance of the resulting molded article may decrease. Furthermore, the obtained molded article is stored at a temperature of 80 ° C. to a temperature lower than the melting point of component (I). Occasionally, there are many cases where gloss and bleeding are generated on the surface of the molded body.

The content of 1-hexene unit of the component (III) is usually 10 to 35% by weight. In addition, the component (II
I) may contain 5% by weight or less of a monomer unit other than the monomer unit consisting of ethylene and 1-hexene based on 100% by weight of all the monomer units of the component (III). As the monomer constituting the other monomer unit,
Examples include non-conjugated dienes having 5 to 15 carbon atoms such as dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-cyclooctadiene, and 5-methylene-2-norbornene. You can The component (III) may have a long chain branch in the molecule.

The component (III) can be produced by a known polymerization method using a known olefin polymerization catalyst. Examples of the polymerization catalyst include Ziegler-Natta type catalysts, JP-A-6-306121, and JP-A-9-
Complex-based catalysts such as metallocene complexes and non-metallocene complexes disclosed in JP-A-179216 are used. Among these, the catalyst using a metallocene complex or a nonmetallocene complex is ethylene-1 having a narrow molecular weight distribution and composition distribution.
-A hexene copolymer can be produced, and the use of the ethylene-1-hexene copolymer is preferable because it is possible to obtain a molded article which is more flexible and is less likely to cause gloss and bleeding on the surface. .

The known polymerization method of the component (III) is as follows:
Examples thereof include a slurry polymerization method, a solution polymerization method using an inert medium, a bulk polymerization method in which an inert medium is substantially absent, and a gas phase polymerization method. As the polymerization conditions, the temperature is -1.
The polymerization is carried out at a temperature of 0 to 300 ° C. and a polymerization pressure of 3500 kg / cm ² or less.

As the component (III), for example, commercially available products such as "EXACT" manufactured by ExxonMobil Chemical Co., Ltd. and "Excellen FX" manufactured by Sumitomo Chemical Co., Ltd. can be used.

The component (III) may be subjected to a crosslinking treatment such as the dynamic crosslinking described below.

The thermoplastic elastomer composition of the present invention comprises
In addition to the essential components (I) to (III), a hydrogenated diene-based copolymer other than the component (II) may be contained within a range that does not impair the effects of the present invention. As the hydrogenated diene-based copolymer other than the component (II), for example, a hydrogenated diene-based copolymer containing the same structural units (A) and (B) as those described in the component (II) (provided that (II) For example, the condition ~
A hydrogenated diene-based copolymer which does not satisfy at least one of the conditions), a hydrogenated product of a vinyl aromatic compound-conjugated diene random copolymer, and the like.

For example, in the case where a hydrogenated diene-based copolymer satisfying the conditions (1) and (2) is satisfied together (V> 0.
In the case where the relational expression of 375 × S + 1.25 × T + 40 is satisfied), a molded product having excellent scratch resistance can be obtained.

Further, a hydrogenated diene-based copolymer which does not satisfy the conditions (when the hydrogenated conjugated diene unit content in the hydrogenated diene-based copolymer is 100% by weight, the number of carbon atoms in the side chain is 2 or more) When a content of a certain hydrogenated conjugated diene unit (V: weight%) is 60 weight% or less in combination, a molded product having more excellent strength can be obtained.

The thermoplastic elastomer composition of the present invention comprises
Ethylene-α-other than ethylene-1-octene copolymer
Olefin copolymers, hydrogenated products of conjugated diene polymers, natural rubber, butyl rubber, chloroprene rubber, epichlorohydrin rubber, rubber polymers such as acrylic rubber, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer Polymers and saponified products thereof, ethylene-methyl methacrylate copolymer, ethylene-glycidyl acrylate-vinyl acetate copolymer, other polymer components such as ethylene-glycidyl methacrylate-vinyl acetate copolymer, Usually, 50 parts by weight or less may be contained per 100 parts by weight of (I) as long as the effects of the invention are not impaired.

The thermoplastic elastomer composition of the present invention comprises
Further, by adding the following component (IV), the tensile strength of the molded article can be improved. (IV): Hydrogenated conjugated diene polymer As the hydrogenated conjugated diene polymer, for example, one conjugated diene having 4 to 8 carbon atoms such as 1,3-butadiene, isoprene, pentadiene, and 2-3-dimethylbutadiene. Alternatively, a material obtained by hydrogenating a raw material conjugated diene polymer that is a polymer of two or more kinds can be used, and a hydrogenated product of polybutadiene, a hydrogenated product of polyisoprene, and the like can be used. By hydrogenating the raw material conjugated diene polymer, the unsaturated bond of the conjugated diene unit is saturated. When the saturated monomer unit is the unit Z, the hydrogenated conjugated diene polymer is: From the viewpoint of the flexibility of the obtained molded product, the content of the unit Z having 2 or more carbon atoms in the side chain is 50% by weight.
Is preferable. However, the content of the unit Z in the hydrogenated conjugated diene polymer is 100% by weight. The hydrogenated conjugated diene polymer may be composed of two or more blocks having different ratios. As such a hydrogenated conjugated diene polymer, a polymer described in JP-A-3-74409, "Dyalon CEBC620" manufactured by JSR Corporation is used.
Commercially available products such as "0" are listed.

The content of the component (IV) is preferably 1 to 50 parts by weight, more preferably 3 to 20 parts by weight based on 100 parts by weight of the component (I) from the viewpoint of tensile strength and flexibility of the molded product. Parts by weight, more preferably 4 to 15 parts by weight.

The thermoplastic elastomer composition of the present invention comprises
For example, mineral oil-based softeners, phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine- and amide-based heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, pigments, metallic soaps, paraffin-based, Wax such as microcrystalline type, hydrogenated terpene resin, fungicide,
It may contain various additives such as an antibacterial agent, a filler and a foaming agent.

When the thermoplastic elastomer composition of the present invention contains a pigment, a molded product having a desired color can be obtained. Examples of the pigments include organic pigments such as azo-based, phthalocyanine-based, slene-based, dyeing lake, oxide-based such as titanium oxide, molybdic acid chromoate-based, selenium sulfide compounds, ferrocyanine compounds, and inorganic pigments such as carbon black. Used.

When the thermoplastic elastomer composition of the present invention contains a foaming agent, a foam molded article can be produced by foam molding the thermoplastic elastomer composition of the present invention. In this case, it is preferable that the foaming agent is contained in the thermoplastic elastomer composition in advance. A thermal decomposition type foaming agent is usually used as the foaming agent. Examples of such a pyrolytic foaming agent include azodicarbonamide, 2,
Azo compounds such as 2′-azobisisobutyronitrile and diazodiaminobenzene, benzenesulfonyl hydrazides, benzene-1,3-sulfonyl hydrazides, sulfonyl hydrazide compounds such as p-toluenesulfonyl hydrazide, N, N′-dinitrosopenta Examples include nitroso compounds such as methylenetetramine, N, N'-dinitroso-N, N'-dimethylterephthalamide, azide compounds such as terephthalazide, and carbonates such as sodium bicarbonate, ammonium bicarbonate and ammonium carbonate. Among them, azodicarbonamide is preferably used. The foaming agent is usually compounded at a temperature equal to or lower than the decomposition temperature of the foaming agent. Moreover, you may contain a foaming auxiliary agent and a cell regulator together with a foaming agent.

The thermoplastic elastomer composition of the present invention comprises
It contains the components (I) to (III) as essential components and optionally other components. The content of the component (II) relative to 100 parts by weight of the component (I) is 50 to 200 parts by weight, preferably 60 to 180 parts by weight. If the content of component (II) is too low, the flexibility of the resulting molded article may be reduced, and if the content of component (II) is too high, the resulting molded article is heated from 80 ° C. to component (I). When stored at a temperature lower than the melting point of the molded product, gloss and bleeding may often occur on the surface of the molded product, and heat resistance retention and light resistance of the molded product may be insufficient. .

Component (I) Component (II) based on 100 parts by weight
The content of I) is 30 to 200 parts by weight, preferably 50 to 180 parts by weight. If the content of the component (III) is too low, the cold shock resistance of the resulting molded article may be lowered, and if the content of the component (III) is too high, the resulting molded article is heated at 80 ° C. to the component (I). When stored at a temperature lower than the melting point of (1), gloss and bleeding may often occur on the surface of the molded product, and the heat resistance retention of the molded product may be insufficient.

In order to obtain the thermoplastic elastomer composition of the present invention, the components (I) to (III) and, if necessary, other polymer components and / or additives may be melt-kneaded. . Further, it can also be produced by selecting all or some of the above components, kneading or dynamically crosslinking, and then melt-kneading the components not selected.
Here, for the melt kneading, known kneading equipment such as a single-screw extruder, a twin-screw extruder, a kneader, and a roll can be used. The other polymer components and additives described above can be blended by using the component (I), component (II) or component (III) in which these are blended in advance, or by kneading the above components or It can also be blended during dynamic crosslinking.

Dynamic crosslinking can be carried out by kneading the components to be dynamically crosslinked and the crosslinking agent under heating. The cross-linking agent is usually 2,5-dimethyl-2,
Organic peroxides such as 5-di (tert-butylperoxyno) hexane and dicumyl peroxide are used. The cross-linking agent is usually 1 part by weight or less, preferably 0.1 to 100 parts by weight per 100 parts by weight of the components to be dynamically crosslinked.
It is used in an amount of 0.8 parts by weight, more preferably 0.2 to 0.6 parts by weight.

When an organic peroxide is used as the cross-linking agent, a molded article having excellent heat resistance can be obtained by dynamic cross-linking with a cross-linking aid such as a bismaleimide compound. The amount of the crosslinking aid used is usually not more than 1.5 parts by weight, preferably 0.2 to 1 part by weight, more preferably 0.1 part by weight per 100 parts by weight of the components to be dynamically crosslinked.
It is in the range of 4 to 0.8 parts by weight. The cross-linking aid is preferably added before the addition of the cross-linking agent, and is usually added at the time of pre-kneading the components to be cross-linked. The dynamic cross-linking can be performed by kneading under heating with a single-screw extruder or a twin-screw extruder, for example, in a temperature range of 150 to 250 ° C. It is also possible to carry out the crosslinking by a method such as sulfur crosslinking.

For example, the component (I), the component (II) and the component (III) are contained, and the component (I) and / or the component (III) are intramolecularly and / or intermolecularly crosslinked. The thermoplastic elastomer composition can be produced by dynamically cross-linking the component (I) and the component (III), then adding the component (II) and kneading. Here, for kneading, a single-screw extruder, a twin-screw extruder, a kneader, a roll or the like can be used. The above-mentioned various additives and various other polymers are the components (I) and (II) in which these are pre-blended.
Alternatively, it can be blended by using the component (III), or can be blended during kneading or dynamic crosslinking of the above components.

In the thermoplastic elastomer composition of the present invention,
By applying a molding method such as a powder molding method, an injection molding method, an extrusion molding method, a vacuum molding method, or a compression molding method, a molded body having a desired shape can be manufactured. Among these molding methods, the thermoplastic elastomer composition of the present invention is suitable for the powder molding method. The molding temperature in these moldings is not a problem as long as it is a temperature equal to or higher than the melting point of the polyolefin resin, but is usually 160 to 320 ° C., preferably 180 to 300.
Within the range of ° C.

When the thermoplastic elastomer composition of the present invention is applied to the powder molding method, the complex dynamic viscosity η ^* (1) at 250 ° C. of the composition is 1 from the viewpoint of further enhancing the appearance of the powder molded body. The range of x10 ² to 8 x 10 ⁴ poise is preferable, further 3 x 10 ^{2 to} 5 x 10 ⁴ poise, and especially 3
It is preferably in the range of × 10 ² to 1 × 10 ⁴ poise. Here, the complex dynamic viscosity η ^* (1) means a temperature of 250
Storage modulus G'at ℃, vibration frequency 1 rad / sec
It is a value calculated by the following calculation formula (2) using (1) and loss elastic modulus G ″ (1). η ^* (1) = {[G ′ (1)] ² + [G ″ (1)] ² } ^1/2 / ω (2)

The powder comprising the thermoplastic elastomer composition used when powder-molding the thermoplastic elastomer composition of the present invention can be obtained by a method of mechanically pulverizing the thermoplastic elastomer composition of the present invention, a strand cut method,
It can be manufactured by a method such as a die face cutting method or a solvent treatment method.

Examples of the method for mechanically pulverizing the thermoplastic elastomer composition of the present invention include a freeze pulverization method and a room temperature pulverization method. In the freeze-pulverization method, the thermoplastic elastomer composition is treated at a temperature not higher than its glass transition temperature, preferably -70.
This is a method of cooling to below ℃, more preferably below -90 ℃, and pulverizing while maintaining the cooled state. From the viewpoint of making the particle diameter of the powder made of the thermoplastic elastomer more uniform and enhancing the powder moldability, the freeze pulverization method is preferable.

As a method of crushing the thermoplastic elastomer composition while keeping it in a cooled state, a method of crushing by a method having good crushing efficiency and less heat generation is preferable. For example, a machine using an impact crusher such as a ball mill. The crushing method is used. The powder of the thermoplastic elastomer composition obtained by this method has a size which normally passes through a Tyler standard sieve 24 mesh (opening 700 μm × 700 μm), preferably 28 mesh (opening 5
90 μm × 590 μm), more preferably 32 mesh (opening 500 μm × 500 μm)
m), particularly preferably 42 mesh (opening 355 μm
X 355 μm).

The powder comprising the thermoplastic elastomer composition can be further improved in powder fluidity by coating the surface thereof with a fine powder. As the fine powder, a fine powder having a primary particle size of 10 μm or less is used. As fine powder, alumina,
Inorganic oxides such as silica, alumina silica, calcium carbonate (the surface may be coated with dimethyl silicone oil or the like, or may be surface-treated with trimethylsilyl group, etc.), vinyl chloride resin for paste,
Fatty acid metal salt, calcium carbonate, powder pigment (However, when the pigment is contained in the thermoplastic elastomer composition, it is preferable that it has the same color as the pigment. Azo-based, phthalocyanine-based, slene-based, dye lake, etc. Examples thereof include pigments, oxides such as titanium oxide, chromolybdenum molybdates, selenium sulfide compounds, ferrocyanines, and inorganic pigments such as carbon black). The primary particle size of the fine powder needs to be 10 μm or less, preferably 5 μm or less, and further 5 nm to 5 μm.
Is preferred. Here, the primary particle size is obtained by taking a photograph of fine powder with a transmission electron microscope (TEM), arbitrarily selecting about 1000 particles, and measuring the diameter of the particles. It is a value divided by the number of particles.

These fine powders may be used alone or in combination of two or more. For example, the inorganic oxide may be used alone, or the powder pigment and the inorganic oxide may be used in combination. Further, as the fine powder, two or more fine powders having different primary particle sizes may be used in combination, and for example, fine powder having a primary particle size of 300 nm or less and fine powder having a particle size of 300 nm to 10 μm. When used in combination, it is possible to obtain a thermoplastic elastomer composition powder which is more excellent in packing property and aggregation resistance as compared with the case where each is used alone.

The amount of the fine powder added is usually 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, based on 100 parts by weight of the powder made of the thermoplastic elastomer composition. If the added amount is too small, the effect of improving the powder fluidity may be reduced, and if the added amount is too large, heat fusion between the powders of the thermoplastic elastomer composition is reduced, and thus it is obtained. The tensile strength of the powder compact may decrease.

The method of blending the fine powder with the powder of the thermoplastic elastomer composition is not particularly limited as long as the fine powder is uniformly deposited on the powder of the thermoplastic elastomer composition. Absent. For example, a blending method using a blender with a jacket or a high-speed rotary mixer can be used. Among them, the method of blending using a Henschel mixer or a super mixer is preferable because it is a method of preventing mutual adhesion of powders by applying shearing force and uniformly dispersing the powders. Further, the compounding is usually performed at room temperature.

The powder comprising the thermoplastic elastomer composition can also be produced by the following solvent treatment method, strand cutting method and die face cutting method. In this case, a powder excellent in powder fluidity can be obtained without blending the above-mentioned fine powder, but the blending of the fine powder can further improve the powder fluidity.

Solvent treatment method: The thermoplastic elastomer composition is cooled to its glass transition temperature or lower (usually -70 ° C or lower, preferably -90 ° C or lower) and ground. Then, a powder comprising the thermoplastic elastomer composition produced by the freeze-pulverization method is added to a thermoplastic elastomer composition in a solvent that is a poor solvent for the thermoplastic elastomer composition in the presence of a dispersant and an emulsifier. Stirring is performed at a melting temperature or higher, preferably 30 to 50 ° C. higher than the melting temperature. A method for producing a powder comprising a thermoplastic elastomer composition by cooling the solvent after stirring.

In the solvent treatment method, as the solvent, for example, ethylene glycol, polyethylene glycol,
Polypropylene glycol or the like is used, and the amount of the solvent used is usually 300 to 1000 parts by weight, preferably 400 to 800 parts by weight, per 100 parts by weight of the thermoplastic elastomer composition. As the dispersant, for example, ethylene-acrylic acid copolymer, silicic acid anhydride, titanium oxide or the like is used, and the amount of the dispersant used is usually 5 to 20 per 100 parts by weight of the thermoplastic elastomer composition.
Parts by weight, preferably 10 to 15 parts by weight. As the emulsifier, for example, polyoxyethylene sorbitan monolaurate, polyethylene glycol monolaurate, sorbitan tristearate and the like are used, and the amount of the emulsifier used is usually 3 to 15 per 100 parts by weight of the thermoplastic elastomer composition. Parts by weight, preferably 5 to 10 parts by weight. As the solvent treatment method, for example, the method described in JP-A-62-280226 can be exemplified.

Strand cutting method: A method of producing a powder of a thermoplastic elastomer composition by extruding a molten thermoplastic elastomer composition into the air from a die to form a strand, cooling the strand and cutting the strand.

In the strand cut method, the discharge port diameter of the die is usually 0.1 to 3 mm, preferably 0.2 to 2 mm. The discharge rate of the thermoplastic elastomer composition per discharge port of the die is usually 0.1.
-5 kg / hour, preferably 0.5-3 kg / hour. Strand take-up speed is usually 1-100 m /
Min, preferably 5 to 50 m / min. The cooled strand is usually cut to 1.4 mm or less, preferably 0.3 to 1.2 mm. As the strand cutting method, for example, JP-A-50-149747 is used.
The method described in the publication can be exemplified.

Die face cutting method: A method for producing a powder of a thermoplastic elastomer composition by cutting a molten thermoplastic elastomer composition while extruding it from a die into water.

In the die face cutting method, the diameter of the discharge port of the die is usually 0.1 to 3 mm, preferably 0.2 to 2 mm. The discharge rate of the thermoplastic elastomer composition per discharge port of the die is usually 0.
It is 1 to 5 kg / hour, preferably 0.5 to 3 kg / hour. The temperature of water is usually 30 to 70 ° C, preferably 40 to 60 ° C.

The powder comprising the thermoplastic elastomer composition of the present invention is prepared by powder slush molding, fluidized dipping,
It can be applied to various powder molding methods such as an electrostatic coating method, a powder spraying method and a powder rotational molding method, and is particularly suitable for the powder slush molding method.

The molded product of the thermoplastic elastomer composition of the present invention may be used as a single-layer molded product, and one layer and / or both surfaces of the layer of the thermoplastic elastomer composition of the present invention may be provided with another layer. You may use it as a laminated multilayer molded body. Examples of the other layer include a synthetic resin layer and a metal layer, and examples of the synthetic resin forming the synthetic resin layer include polypropylene resins such as polypropylene and polyethylene, polyolefin resins, thermoplastic elastomers, polyamide resins, and ethylene-vinyl. Examples thereof include alcohol copolymers, polyester resins, ABS (acrylonitrile-butadiene-styrene copolymers), and adhesive resins.
These layers may be foamed.

The molded product of the present invention can be optimally used for automobile interior parts such as instrument panels, door trims, console boxes and pillars.

[0069]

EXAMPLES The present invention will be described in detail below with reference to examples. First, the method for measuring physical properties in the present invention will be described. [1] Physical Properties of Material (1) Content of Vinyl Aromatic Compound Unit in Hydrogenated Diene Copolymer (T: wt%) Using a carbon tetrachloride solution of the hydrogenated diene copolymer, ¹ H
-It was determined by the NMR measurement method (frequency 90 MHz). (2) Content of vinyl aromatic compound unit in (A) vinyl aromatic compound polymer block (S:% by weight) Using a carbon tetrachloride solution of a hydrogenated diene copolymer, ¹ H
-It was determined by the NMR measurement method (frequency 90 MHz). (3) Content of hydrogenated conjugated diene unit having 2 or more carbon atoms in side chain (V: wt%) It was determined by the Morello method using infrared analysis. (4) Hydrogenation rate of hydrogenated diene-based copolymer Using a raw material diene-based copolymer carbon tetrachloride solution and a hydrogenated diene-based copolymer carbon tetrachloride solution, ¹ H-NMR measurement method (frequency 90 MHz). (5) Number average molecular weight of hydrogenated diene-based copolymer It was determined as a polystyrene conversion value by gel permeation chromatography (GPC) method at 38 ° C. using a tetrahydrofuran solution of the hydrogenated diene-based copolymer.

(6) Density According to JIS K6922-1, the density was measured without annealing. (7) Melt flow rate (MFR) According to JIS K-7210, the measurement was performed with a load of 21.18N. The measurement temperature of the (I) polyolefin resin and (II) hydrogenated diene copolymer is 230.
C., and the measurement temperature of the (III) ethylene-1-hexene copolymer was 190.degree.

(8) Complex dynamic viscosity η ^{* at} 250 ° C.
(1) Rheometrics dynamic analyzer (RD
S-7700 type), the storage elastic modulus G '(1) and the loss elastic modulus G''(1) at a temperature of 250 ° C and a vibration frequency of 1 radian / sec are measured, and the above-mentioned calculation formula (2) is used. It was calculated. In addition, the measurement is a parallel plate mode, and the applied strain is 5
It went in%.

[2] Flexible molded product 2 m obtained by press molding of the thermoplastic elastomer composition
The flexural modulus of the m-thick sheet was measured at 23 ° C.

[3] Luminance when the molded body was heated, bleeding A 1 mm thick powder molded body obtained by the powder slush molding method described later was cut into 15 cm × 15 cm, and the inside of the tank was controlled at 120 ° C. 1 in a gear oven (Tabai Corporation, perfect oven, model number PH-200)
I put it in for 00 hours. (1) Situation of occurrence of bleeding material Visually determined according to the following criteria. 1: The appearance was inferior because the granular bleeding material was generated. 2: No granular bleeding material was generated and the appearance was excellent. (2) Difference in gloss (gloss value) before and after heating The gloss value before and after heating is measured by a digital variable angle photometer (manufactured by Suga Test Instruments Co., Ltd., model number UGV-5DI, reflection angle 60).
°) and determined based on the difference in gloss value before and after heating. 1: The difference in gloss value was larger than 0.6. 2: The difference in gloss value was in the range of more than 0.3 and 0.6 or less. 3: The difference in gloss value was 0.3 or less.

[4] Tensile physical properties of molded article A dumbbell-shaped No. 1 test piece described in JIS K6251 was punched out from a 1 mm-thick powder molded article obtained by the powder slush molding method described below and stretched at 23 ° C. Speed 2
A tensile test was performed at 00 mm / min to measure strength and elongation at break.

[5] Bending whitening property of molded body A 1 mm thick powder molded body obtained by the powder slush molding method described below was cut into 1 cm × 5 cm, and at 23 ° C.
After bending with a bending load of 1 kg, the load was removed 1 minute later, and the evaluation was performed according to the following criteria based on the width of the whitened portion by bending. 1: A whitened part was recognized. 2: No whitening part was observed.

[6] Cold Impact Resistance of Molded Article High Speed Impact Tester HRIT-800 manufactured by Rheometrics Co.
0 was used for measurement in an atmosphere of −15 ° C. A 1 mm thick powder compact obtained by the powder slush molding method described later was cut into 9 cm × 9 cm. After fixing the molded sheet to a folder in a constant temperature bath, the temperature inside the constant temperature bath was −
At 15 ° C., the formed sheet was impacted with a stainless steel dirt (made of 5/8 inch φ) at a speed of 5 m / sec to give an impact to the formed sheet. The cold shock resistance was evaluated according to the following criteria. 1: Brittle fracture of the molded sheet 2: Ductile fracture of the molded sheet

Example 1 [Production of Thermoplastic Elastomer Composition Powder] Propylene-ethylene copolymer resin (P manufactured by Sumitomo Chemical Co., Ltd.
PD200, content of ethylene unit 5% by weight, MFR
(230 ° C. = 220 g / 10 minutes) 100 parts by weight, hydrogenated product of styrene-butadiene-styrene copolymer ((A))
Corresponding to the-(B2)-(A) structure, the content of the styrene unit is 15% by weight, and the content of the styrene unit in the (A) part relative to the content of the styrene unit in the hydrogenated product of the styrene-butadiene-styrene copolymer is included. 100% by weight, MFR (230
C.) = 30 g / 10 min, content of hydrogenated conjugated diene unit having side chain carbon number of 2 or more 80% by weight, hydrogenation rate 98% by weight, number average molecular weight 130,000) 100 parts by weight, ethylene-1
-Hexene copolymer (Excellen CX50 manufactured by Sumitomo Chemical Co., Ltd.
05, density (23 ° C.) = 870 kg / m ³ , MFR (1
90 ° C.) = 17 g / 10 minutes) 117 parts by weight, wax (Yasuhara Chemical Co., M115) 17 parts by weight, and black pigment carbon black 1 part by weight are mixed with a twin-screw kneader (Tanabe Plastic Machinery Co., Ltd., VS40 mm extruder). Was kneaded at a temperature of 170 ° C. to obtain a composition, which was cut using a cutting machine to obtain pellets. The pellets were cooled to −120 ° C. using liquid nitrogen, and then pulverized while maintaining the cooled state (passed through Tyler standard sieve 42 mesh (opening 355 μm × 355 μm)). To 100 parts by weight of the obtained pulverized product, 1 part by weight of silica (OX50 manufactured by Nippon Aerosil Co., Ltd.) and 2 parts by weight of alumina silica (JC-30 manufactured by Mizusawa Chemical Co., Ltd.) as an anti-mutation agent were mixed by a mixer (manufactured by Kawata Manufacturing Co., Ltd., 5 liter super mixer) was used for blending to obtain a powder composed of the thermoplastic elastomer composition.

[Production of Molded Body by Powder Slush Molding Method] Powder obtained from the thermoplastic elastomer composition obtained was heated to 280 ° C. to give a mold (30
(cm square), and then allowed to stand for 15 seconds, excess powder was blown off and stored in an oven at 280 ° C. for 1 minute. Then, a mold on which powder made of the thermoplastic elastomer composition melted into a sheet was placed was cooled with water, and the sheet was removed from the mold to obtain a powder compact. Table 1 shows the evaluation results of the obtained molded body.

Example 2 As an ethylene-1-hexene copolymer, Excellen CX5010 manufactured by Sumitomo Chemical Co., Ltd., density (23 ° C.) = 880 kg
/ M ³ , MFR (190 ° C.) = 12 g / 10 minutes), and the same procedure as in Example 1 was performed. The results are shown in Table 1.

Example 3 As an ethylene-1-hexene copolymer, Excellen CX5007 manufactured by Sumitomo Chemical Co., Ltd., density (23 ° C.) = 877 kg
/ M ³ , MFR (190 ° C.) = 19 g / 10 minutes), except that the same procedure as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 1 As an ethylene-1-hexene copolymer, Excellen CX5012 manufactured by Sumitomo Chemical Co., Ltd., density (23 ° C.) = 905 kg
/ M ³ , MFR (190 ° C.) = 40 g / 10 minutes), and the same procedure as in Example 1 was performed. The results are shown in Table 2.

Comparative Example 2 Instead of the ethylene-1-hexene copolymer, an ethylene-propylene copolymer (Spren V0115 manufactured by Sumitomo Chemical Co., Ltd., density (23 ° C.) = 870 kg / m ³ ,
MFR (190 ° C.) = 5 g / 10 min)
The same procedure as in Example 1 was performed. The results are shown in Table 2.

Comparative Example 3 Instead of the hydrogenated product of styrene-butadiene-styrene copolymer in Example 1, a hydrogenated product of styrene-butadiene / styrene-styrene copolymer ((A)-(B1)) was used.
-Corresponding to the structure (A), the content of styrene unit is 9% by weight,
The content of the styrene unit in the part (A) is 48% by weight with respect to the content of the styrene unit in the hydrogenated product of the styrene-butadiene / styrene-styrene copolymer, MFR (230 ° C.) =
10 g / 10 minutes, 80 weight% of hydrogenated conjugated diene units having 2 or more carbon atoms in the side chain, 98 weight% of hydrogenation rate, 100 weight parts of number average molecular weight of 200,000) were used, and ethylene-1
The same procedure as in Example 1 was carried out except that the amount of the hexene copolymer blended was 50% by weight. The results are shown in Table 3.

Comparative Example 4 In Comparative Example 3, an ethylene-propylene copolymer (Sprene V0115 manufactured by Sumitomo Chemical Co., Ltd., density (23 ° C.)) was used instead of the ethylene-1-hexene copolymer.
870 kg / m ³ , MFR (190 ° C) = 5 g / 10
Min) The same operation as in Comparative Example 3 was carried out except that 50 parts by weight was used. The results are shown in Table 3.

Example 4 As a raw material of the thermoplastic elastomer composition powder, a propylene-ethylene copolymer resin (PPD200 manufactured by Sumitomo Chemical Co., Ltd., content of ethylene unit 5% by weight, M
FR (230 ° C.) = 220 g / 10 minutes) 100 parts by weight,
Hydrogenated product of styrene-butadiene-styrene copolymer (corresponding to the structure of ((A)-(B2)-(A), content of styrene unit: 15% by weight), hydrogenated product of styrene-butadiene-styrene copolymer Content of styrene unit in part (A) relative to the content of styrene unit in 100% by weight, MFR
(230 ° C.) = 30 g / 10 min, content of hydrogenated conjugated diene unit having side chain carbon number of 2 or more 80% by weight, hydrogenation rate 98% by weight, number average molecular weight 130,000) 112 parts by weight, ethylene -1-Hexene copolymer (Sumitomo Chemical Co., Ltd. Excellen CX4002, density (23 ° C.) = 879 kg / m ³ , M
Example 1 was repeated except that 76 parts by weight of FR (190 ° C.) = 9 g / 10 minutes) and 15 parts by weight of wax (M115, manufactured by Yasuhara Chemical Co., Ltd.) were used. The results are shown in Table 4.

Example 5 In Example 4, the blending amount of the ethylene-1-hexene copolymer was set to 66 parts by weight, and the hydrogenated conjugated diene polymer (JSR) was added to 100 parts by weight of the propylene-ethylene copolymer resin. CEBC6200 manufactured by K.K., density (23
℃) = 880 kg / m ³ , MFR (230 ℃) = 2.5
(g / 10 minutes) The same procedure as in Example 4 was carried out except that 8 parts by weight were blended. The results are shown in Table 4.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

According to the present invention, a polyolefin resin,
Containing a hydrogenated diene-based copolymer having a specific structure and an ethylene-1-hexene copolymer having a specific structure as an essential component, it has excellent flexibility, and even when bent, the whitening of the bent portion is small, and 80 ° C. A thermoplastic resin composition capable of obtaining a molded article excellent in tensile strength and cold shock resistance when it is stored at a temperature of less than the melting point of the polyolefin resin to a degree, and further, the composition. It was possible to provide a powder compact formed by powder-molding a powder made of a material and a powder made of the composition. The powder composed of the thermoplastic resin composition of the present invention is also excellent in powder moldability, and the powder molded product obtained by powder molding the powder composed of the thermoplastic resin composition of the present invention has heat resistance, light resistance, and Since the molded article can be excellent in appearance, it is preferably used for automobile interior parts such as instrument panels, door trims, console boxes and pillars.

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Claims (5)

[Claims] 1. The following component (I) 100 parts by weight, the following component (II) 50 to 200 parts by weight and the following component (III) 30 to
A thermoplastic elastomer composition containing 200 parts by weight. (I): Polyolefin resin (II): Hydrogenated diene copolymer satisfying all of the following conditions: Hydrogenated raw material diene copolymer containing the structural units (A) and (B) below. (A): vinyl aromatic compound polymer block (B): at least one block (B1) selected from the following (B1) and (B2): copolymer of vinyl aromatic compound and conjugated diene Block (B2): Conjugated diene polymer block: Content of vinyl aromatic compound unit (T: wt%) in the hydrogenated diene copolymer is 10 to 18 wt%: hydrogenated diene copolymer The content (V:% by weight) of the hydrogenated conjugated diene unit having 2 or more carbon atoms in the side chain is 60 with respect to the content of the hydrogenated conjugated diene unit in the combined product of 100% by weight.
Must exceed weight%. : (A) Content of vinyl aromatic compound unit in vinyl aromatic compound polymer block (S:% by weight, where content of vinyl aromatic compound unit in hydrogenated diene copolymer is 100% by weight The condition (T) and the condition (V) satisfy the following expression (1): V ≦ 0.375 × S + 1.25 × T + 40 (1) (III): Sufficient ethylene-1-
Hexene copolymer: Density at 23 ° C. is 850 to 890 kg / m ³ : Melt flow rate at 190 ° C. is 5 to 100.
g / 10 minutes 2. The thermoplastic elastomer composition according to claim 1, wherein the component (II) satisfies all the following conditions. : The condition (S) is 3% by weight or more: The hydrogenated conjugated diene unit in the hydrogenated diene-based copolymer is 100% by weight of the content of the conjugated diene unit in the starting diene-based copolymer. Content of 80% by weight or more. : Number average molecular weight of hydrogenated diene copolymer is 50,000 to 40
Be ten thousand 3. The thermoplastic elastomer composition according to claim 1, which contains 1 to 50 parts by weight of the following component (IV) with respect to 100 parts by weight of the component (I). (IV): Hydrogenated conjugated diene polymer 4. A powder comprising the thermoplastic elastomer composition according to claim 1. 5. A powder molded product obtained by powder molding a powder comprising the thermoplastic elastomer composition according to claim 4.