JPH1030036A - Thermoplastic elastomer composition and molded article thereof - Google Patents

Abstract

(57) [Abstract] [Problem] It is not easily whitened even when bent.
Provided is a thermoplastic elastomer composition capable of providing a molded article having excellent flexibility. SOLUTION: An ethylene / α-olefin-based copolymer rubber, a polyolefin-based resin, and the ethylene / α-
0.1 to 150 parts by weight of a hydrogenated diene polymer represented by the following (A) per 100 parts by weight of the total amount of the olefin copolymer rubber and the polyolefin resin,
A thermoplastic elastomer composition having a complex dynamic viscosity η ^* (1) of 1.5 × 10 ⁵ poise or less and a Newton viscosity index n of 0.67 or less. (A) A conjugated diene-vinyl aromatic compound random copolymer having a conjugated diene polymer or vinyl aromatic compound unit content of 25% by weight or less is hydrogenated, and the degree of hydrogenation is 70% or more. Hydrogenated diene polymer

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic elastomer composition and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, a molded article having a complicated pattern such as grain and stitch on its surface has been used as a skin material for interior parts for automobiles. As such a skin material, vinyl chloride resin or vinyl chloride resin is used. BACKGROUND ART A vinyl chloride resin molded article composed of a composition containing a main component is widely known. However, there is a problem that a special incineration facility is required because such a vinyl chloride resin molded body generates hydrogen chloride gas when incinerated after use.

In order to solve such a problem, a thermoplastic elastomer molded article comprising an ethylene / α-olefin-based copolymer rubber and a polyolefin-based resin has been proposed (Japanese Patent Laid-Open Nos. 5-1183 and 5-505).
No. 0). However, since such a thermoplastic elastomer molded article has a property of being easily whitened when bent as compared with a vinyl chloride-based resin molded article, the thermoplastic elastomer molded article may be produced when the molded article is released from a mold or when the molded article is removed. When the body is shaped into a desired shape in advance, there is a problem that the bent portion tends to whiten to cause poor appearance, and the feel is inferior due to poor flexibility.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present inventors
As a result of intensive studies to develop a thermoplastic elastomer composition capable of giving a molded article having excellent flexibility that does not easily whiten even when bent, ethylene-α-olefin copolymer rubber, polyolefin resin It has been found that a thermoplastic elastomer composition containing a specific hydrogenated diene polymer and having specific physical properties does not easily whiten even when bent, and can give a molded article having excellent flexibility. Thus, the present invention has been completed.

[0005]

That is, the present invention provides an ethylene / α-olefin copolymer rubber, a polyolefin resin, and a total amount of 100% of the ethylene / α-olefin copolymer rubber and the polyolefin resin. It contains 0.1 to 150 parts by weight per part by weight of a hydrogenated diene polymer represented by the following (A), and has a complex dynamic viscosity η.
^* It is intended to provide a thermoplastic elastomer composition characterized in that (1) is 1.5 × 10 ⁵ poise or less and Newton viscosity index n is 0.67 or less. (A) A conjugated diene-vinyl aromatic compound random copolymer having a conjugated diene polymer or vinyl aromatic compound unit content of 25% by weight or less is hydrogenated, and the degree of hydrogenation is 70% or more. Hydrogenated diene polymer

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylene / α-olefin copolymer rubber in the thermoplastic elastomer composition of the present invention is a copolymer of ethylene and α-olefin, or a copolymer of ethylene, α-olefin and non-conjugated diene. It is a non-crystalline material such as a polymer. Here, as the α-olefin, propylene, 1-butene, 3-methyl-1
An α-olefin having 3 to 10 carbon atoms such as butene, and a non-conjugated diene having 5 carbon atoms such as dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, cyclooctadiene and methylene norbornene.
To 15 non-conjugated dienes and the like. As such ethylene / α-olefin copolymer rubber,
For example, ethylene / propylene copolymer rubber, ethylene / propylene
Propylene-ethylidene norbornene copolymer rubber (hereinafter referred to as EPDM) and the like can be mentioned. Among them, EPDM is preferable in that a thermoplastic elastomer composition capable of providing a molded article having excellent heat resistance, tensile properties and the like can be obtained.
Such an ethylene / α-olefin copolymer rubber may be crosslinked. Crosslinking of the ethylene / α-olefin copolymer rubber can be performed by a conventionally known method.

The polyolefin resin is a polymer or copolymer having crystallinity obtained by polymerizing or copolymerizing one or more olefins. Here, the olefin includes two carbon atoms such as ethylene, propylene, and butene.
Examples of the polymer or copolymer include polyethylene, polypropylene, a copolymer of propylene and ethylene, and an α-olefin other than propylene and propylene, such as a copolymer of butene and the like. Is done. Among them, a copolymer of propylene and ethylene is preferable in that a thermoplastic elastomer composition capable of giving a molded article having excellent heat resistance can be obtained. Such a polyolefin-based resin may be crosslinked. Crosslinking of the polyolefin resin can be performed by a conventionally known method. When a molded article is produced by using the powder of the thermoplastic elastomer composition of the present invention by a powder molding method described below, the melt flow rate of these polyolefin-based resins (JIS K A value measured at a temperature of 230 ° C. and a load of 2.16 kg in accordance with −7210,
Hereinafter, it is called MFR. ) Is preferably 20 g / 10 min or more, more preferably 50 g / 10 min or more.

The hydrogenated diene polymer represented by the above (A) is obtained by hydrogenating a conjugated diene polymer or a conjugated diene-vinyl aromatic compound random copolymer.
Here, the conjugated diene polymer is a polymer obtained by polymerizing or copolymerizing one or more conjugated dienes. Examples of such conjugated dienes include conjugated dienes having 4 to 8 carbon atoms, such as butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene. Examples of such a conjugated diene polymer include polybutadiene, polyisoprene, and polypentadiene.

The conjugated diene-vinyl aromatic compound random copolymer is a random copolymer of a conjugated diene and one or more vinyl aromatic compounds as described above. Here, in the vinyl aromatic compound, the 1- or 2-position of the vinyl group may be substituted with an alkyl group such as a methyl group. Such vinyl aromatic compounds include styrene, p-
Examples thereof include vinyl aromatic compounds having 8 to 12 carbon atoms such as methylstyrene and α-methylstyrene. Such conjugated diene-vinyl aromatic compound random copolymers include, for example, butadiene-styrene random copolymer, isoprene-styrene random copolymer, butadiene-p
-Methylstyrene random copolymer and the like. When the content of the vinyl aromatic compound unit in the conjugated diene-vinyl aromatic compound random copolymer exceeds 25% by weight, the molded product obtained by molding the thermoplastic elastomer composition becomes white when bent. Since it tends to be easy, the content needs to be 25% by weight or less, and preferably 20% by weight or less.

The conjugated diene unit of the conjugated diene polymer or the conjugated diene-vinyl aromatic compound random copolymer includes a conjugated diene unit having an olefinically unsaturated bond in a side chain according to a polymerization site of the conjugated diene. There are conjugated diene units having an olefinically unsaturated bond in the main chain, and the ratio of the number of conjugated diene units having an olefinically unsaturated bond to the total number of conjugated diene units is usually 5%.
９５95%, preferably 30-95%, more preferably 40-90%.

Such a conjugated diene polymer or a conjugated diene-vinyl aromatic compound random copolymer can be easily produced by a known method. For example, as described in JP-A-2-36244, To produce a conjugated diene polymer, a conjugated diene may be subjected to living anion polymerization in a hydrocarbon solvent, and to produce a conjugated diene-vinyl aromatic random copolymer, a conjugated diene and a vinyl aromatic compound can be similarly produced. May be subjected to living anionic polymerization.

In the living anionic polymerization, an initiator such as an organolithium compound is usually used. Such organic lithium compounds include, for example, n-butyl lithium,
Alkyl lithium such as sec-butyl lithium and t-butyl lithium. Examples of the hydrocarbon solvent include hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene, xylene,
2-methylbutene-1, 2-methylbutene-2 and the like. The method of living anionic polymerization may be a batch type or a continuous type, and the polymerization temperature is usually 0 to 1
It is in the range of 20 ° C.

In the above living anionic polymerization, for example, alkoxides, phenoxides, etc. of alkali metals such as ethers, tertiary amines, sodium and potassium are used.
A conjugate having an olefinically unsaturated bond in a side chain in the obtained conjugated diene polymer or conjugated diene-vinyl aromatic compound copolymer by appropriately using a sulfonate or the like and appropriately selecting the type and the amount to be used. The ratio of the number of diene units to the number of all conjugated diene units can be easily controlled.

Further, the molecular weight of the polymer can be increased by adding a polyfunctional coupling agent or a crosslinking agent immediately before the end of the polymerization to effect a coupling reaction or crosslinking. Such coupling agents include tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis (trichlorosilyl) ethane, and the like, and crosslinking agents such as divinylbenzene, adipic diester, and epoxidized liquid butadiene. Epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate, diphenylmethane diisocyanate, 1,2,4-benzene triisocyanate, and the like.

To hydrogenate such a conjugated diene polymer or a conjugated diene-vinyl aromatic compound random copolymer, for example, as described in JP-A-2-36244, a conjugated diene polymer or a conjugated diene- A vinyl aromatic compound random copolymer is prepared in a hydrocarbon solvent in the presence of a hydrogenation catalyst under a hydrogen pressure of 1 to 100 kg / cm ² and a temperature of 20.
What is necessary is just to make it react at ~ 150 degreeC.

Examples of the hydrogenation catalyst include a catalyst in which a noble metal such as palladium, ruthenium, rhodium and platinum is supported on a carrier such as silica, carbon and diatomaceous earth, a complex of a noble metal such as rhodium, ruthenium and platinum, cobalt,
A catalyst comprising an organic carboxylate such as nickel and an organic aluminum or organic lithium, dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl titanium ditolyl,
Examples include a catalyst comprising a titanium compound such as dicyclopentadienyldibenzyl and an organic metal compound such as lithium and aluminum magnesium.

By such hydrogenation, the olefinically unsaturated bond in the side chain or main chain contained in the conjugated diene unit of the conjugated diene polymer or the conjugated diene-vinyl aromatic compound random copolymer is hydrogenated. A hydrogenated diene-based polymer represented by A) is obtained, and the hydrogenation rate in such a hydrogenated diene-based polymer needs to be 70% or more.
Here, the hydrogenation rate means the number of olefinically unsaturated bonds in the hydrogenated side chain or main chain with respect to the number of olefinically unsaturated bonds in the side chain or main chain of the conjugated diene unit before hydrogenation. Is a value indicating the ratio of, preferably 90% or more,
It is more preferably at least 95%. Such a hydrogenated diene polymer may be crosslinked. Crosslinking of the hydrogenated diene polymer can be performed by a conventionally known method.

The thermoplastic elastomer composition of the present invention comprises:
(A) per 100 parts by weight of the total amount of the ethylene / α-olefin copolymer rubber and the polyolefin resin
It is necessary to contain 0.1 to 150 parts by weight of a hydrogenated diene polymer represented by the formula: 3 to 100 parts by weight when ethylene / α-olefin copolymer rubber is not crosslinked -When the α-olefin copolymer rubber is crosslinked, it is preferably contained in an amount of 3 to 50 parts by weight. If the hydrogenated diene-based polymer is less than 0.1 part by weight, it is inferior in flexibility and tends to give a molded body which is easily whitened when bent, and if it exceeds 150 parts by weight, a sticky molded body is used. Tend to give. In addition, ethylene
The weight ratio of the olefin copolymer rubber to the polyolefin resin is usually in the range of 5:95 to 80:20.

In order to produce the thermoplastic elastomer composition of the present invention, for example, an ethylene / α-olefin copolymer rubber, a polyolefin resin and a hydrogenated diene polymer may be kneaded. Further, a hydrogenated diene-based polymer may be added to a composition obtained by previously kneading an ethylene / α-olefin-based copolymer rubber and a polyolefin-based resin and kneaded.

When the ethylene / α-olefin copolymer rubber is crosslinked, for example, an uncrosslinked ethylene / α-olefin copolymer rubber and a polyolefin resin are kneaded. Later, a crosslinking agent may be added for dynamic crosslinking, and then a hydrogenated diene-based polymer may be added and kneaded, or an uncrosslinked ethylene / α-olefin-based copolymer rubber, polyolefin-based resin and hydrogenated diene may be added. After kneading the system polymer, dynamic crosslinking may be performed by adding a crosslinking agent.

Examples of the crosslinking agent include organic peroxides such as dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxyno) hexane. -The amount is usually 1 part by weight or less, preferably 0.8 part by weight or less based on 100 parts by weight of the total amount of the olefin-based copolymer rubber and the polyolefin-based resin.

By dynamically crosslinking with a crosslinking agent in the presence of a crosslinking aid, the ethylene / α-olefin-based copolymer rubber is appropriately crosslinked and has excellent heat resistance and excellent melt fluidity. A plastic elastomer composition can be obtained. As such a crosslinking aid, for example, a bismaleimide compound and the like can be mentioned.
-It is usually 1.5 parts by weight or less, preferably 0.8 parts by weight or less based on 100 parts by weight of the total amount of the olefin-based copolymer rubber and the polyolefin-based resin. When such a crosslinking aid is used, the amount of the crosslinking agent used is usually 0.8 parts by weight or less, preferably 0.6 part by weight, based on 100 parts by weight of the total amount of the ethylene / α-olefin-based copolymer rubber and the polyolefin-based resin. Not more than parts by weight.

In the case of dynamic crosslinking, for example, a uniaxial kneader,
Kneading may be carried out using a continuous kneader such as a twin-screw kneader under heating, for example, in a temperature range of 150 to 250 ° C. The ethylene / α-olefin copolymer rubber is preferentially crosslinked by such dynamic crosslinking. Also, the polyolefin resin may be cross-linked, ethylene-α-olefin copolymer rubber, when dynamically cross-linked after kneading the polyolefin resin and hydrogenated diene polymer,
The hydrogenated diene polymer may be crosslinked.

The thermoplastic elastomer composition of the present invention comprises:
For example, mineral oil-based softeners, phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based, amide-based heat stabilizers, antioxidants, weathering stabilizers,
It may contain additives such as antistatic agents, lubricants such as metal soaps and waxes, internally added release agents such as methylpolysiloxane compounds, and coloring pigments. These additives may be used by being previously contained in an ethylene / α-olefin-based copolymer rubber, a polyolefin-based resin or a hydrogenated diene-based polymer, or during or after the kneading or dynamic crosslinking. It may be blended by kneading or the like.

Among them, a mineral oil-based softener is preferably used because a thermoplastic elastomer composition containing the same is excellent in melt fluidity and can give a molded article having excellent flexibility. When the mineral oil-based softener uses an oil-extended olefin-based copolymer rubber previously contained in the ethylene / α-olefin-based copolymer rubber, the above-described kneading and dynamic crosslinking can be easily performed.

The thermoplastic elastomer composition of the present invention comprises:
The complex dynamic viscosity η ^* (1) measured at a temperature of 250 ° C. and an oscillation frequency ω = 1 radian / second needs to be 1.5 × 10 ⁵ poise or less, and 1 × 10 ⁵ poise or less, Is preferably 1 × 10 ⁴ poise or less. Here, the complex dynamic viscosity η ^* (ω) is calculated using the storage viscoelastic modulus G ′ (ω) and the loss viscoelastic modulus G ″ (ω) at a temperature of 250 ° C. and a vibration frequency ω. ^* (Ω) = {[G ′ (ω)] ² + [G ″ (ω)] ² ｝ ^1/2 (1) η ^* (1) is 1.5 × 1
Exceeds 0 ⁵ poise, poor melt flowability of the thermoplastic elastomer composition, the shear rate at the time of molding such as powder molding method for producing a molded article by a molding method generally 1 sec ^-1 as low It becomes difficult.

The thermoplastic elastomer composition of the present invention must have a Newtonian viscosity index n of 0.67 or less, and preferably 0.6 or less. Here, the Newtonian viscosity index n is the complex dynamic viscosity η ^* (1)
Temperature 250 ° C., vibration frequency omega = 100 radian / second complex dynamic viscosity measured at eta ^* (100) and the calculation equation using the ^{(2) n = {logη *} (1) -logη * (100)} / 2 (2). If the Newtonian viscosity index n exceeds 0.67, the mechanical strength of the obtained molded body tends to decrease, which is not preferable.

In order to produce the thermoplastic elastomer composition of the present invention which satisfies the physical properties indicated by the above-mentioned complex dynamic viscosity and Newton's viscosity index, the above-mentioned degree of kneading and dynamic crosslinking, the thermoplastic elastomer The type and amount of each component constituting the composition, the type and amount of the cross-linking agent and cross-linking aid in dynamic cross-linking, the type and amount of additive, and the like are appropriately selected. Above all, the shear rate in kneading and dynamic crosslinking greatly affects the above physical properties, and it is preferable to perform kneading and dynamic crosslinking at a shear rate of 1 × 10 ³ sec ⁻¹ or more.

By molding the thermoplastic elastomer composition of the present invention, a molded article can be easily produced. Examples of the molding method include a method of molding a powder of the thermoplastic elastomer composition into powder.

The powder of the thermoplastic elastomer composition may be prepared, for example, by mixing the thermoplastic elastomer composition with a glass transition temperature or lower, preferably -70 ° C or lower, more preferably-
It can be easily manufactured by a freezing / pulverization method of cooling to 90 ° C. or lower and pulverizing while keeping the cooling state. When the thermoplastic elastomer composition is pulverized at a temperature higher than its glass transition temperature, the resulting powder has an irregular particle size, which tends to make powder molding difficult. In addition, in order to pulverize the thermoplastic elastomer composition while maintaining the cooling state, it is preferable that the pulverization is performed by a method with good pulverization efficiency and low heat generation, such as a mechanical pulverization method using an impact pulverizer such as a ball mill. Is used.

The powder of such a thermoplastic elastomer composition is usually prepared using a 24 mesh Tyler standard sieve (700 μm mesh).
m × 700 μm), and preferably through 28 meshes (mesh size 590 μm × 590 μm).

The powder of the thermoplastic elastomer composition thus obtained can be easily melted by the heat supplied from the mold even at a low shear rate and a low molding pressure, so that it is suitably used for a powder molding method. . Examples of such a powder molding method include a fluid immersion method, an electrostatic coating method, a powder spraying method, a powder rotation method, and a powder slush molding method.

In order to powder-mold the thermoplastic elastomer composition powder, for example, a mold which may have a complicated pattern on its molding surface is heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition. The powder of the thermoplastic elastomer composition is supplied onto the molding surface of the mold, and the powders are thermally fused to each other to obtain a sheet-like melt on the molding surface, and then the excess powder that has not been thermally fused is removed. It may be removed. After removing the powder, the mold may be further heated. Then, it cools and demolds, and can obtain the target molded object.

Examples of the method for heating the mold include a gas heating furnace method, a heating medium oil circulation method, a dipping method in heating medium oil or hot fluidized sand, and a high-frequency induction heating method. The mold temperature when the powder is heat-sealed to the mold is usually in the range of 150 to 300C, preferably 190 to 270C. The time from the supply of the powder onto the molding surface to the removal thereof is not particularly limited, and is appropriately selected depending on the size and thickness of the target compact.

The molded article thus obtained hardly whitens even when it is bent during demolding, and is excellent in flexibility.

[0036]

The thermoplastic elastomer composition of the present invention does not easily whiten even when bent, and can provide a molded article having excellent flexibility.

[0037]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,
The following methods were used to evaluate the thermoplastic elastomer composition and the molded article.

[1] Complex dynamic viscosity η ^* (1), Newtonian viscosity index n Dynamic analyzer (RD) manufactured by Rheometrics
S-7700), the storage viscoelastic modulus G ′ (ω) and the loss viscoelastic modulus G ″ (ω) were measured at a vibration frequency ω = 1 radian / sec or 100 radian / sec, and the above-described calculation formula was used. The complex dynamic viscosity η ^* (1) and η ^* (10
0) was calculated. The measurement was performed in a parallel plate mode, an applied strain of 5%, and a sample temperature of 250 ° C. Also, η ^*
Using (1) and η ^* (100), the Newtonian viscosity index n was determined by the above-mentioned equation (2).

[2] Flexibility of the molded article Ten pieces of the molded article cut into 1 cm × 5 cm were overlaid, and the Shore A hardness was determined in accordance with JIS K-6301.

[3] Bending whitening The molded body was cut into 1 cm × 5 cm, and the bending load was 500
1 minute after bending at g or 1 kg, remove the load,
Evaluation was made according to the following criteria based on the width of the whitened portion by bending. 1: The width of the whitened portion is 2 mm or more 2: The width of the whitened portion is 1 mm or more and less than 2 mm 3: The width of the whitened portion is less than 1 mm 4: The whitened portion is not recognized

Reference Example 1 Oil containing 100 parts by weight of a mineral oil-based softener (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.) per 100 parts by weight of EPDM (propylene unit content = 28% by weight, iodine value = 12) 50 parts by weight of expanded EPDM, 50 parts by weight of a propylene / ethylene random copolymer resin (ethylene unit content = 5% by weight, MFR = 90 g / 10 min) and a crosslinking assistant (Sumitomo Chemical Co., Ltd., Sumifine BM, bismaleimide compound) ) 0.4 parts by weight were kneaded for 10 minutes using a Banbury mixer, and then processed into pellets using an extruder to obtain a master batch. This masterbatch 100
0.1 part by weight of an organic peroxide [Sanperox APO, 2,5-dimethyl-2,5-di (t-butylperoxyno) hexane] manufactured by Sanken Kako Co., Ltd. 220 using a kneader (manufactured by Nippon Steel Works, TEX-44)
The composition subjected to dynamic crosslinking at ℃ ^{[η * (1) = 5.2 ×} 1
0 ³ poise, n = 0.31] and cut with a cutting machine to obtain pellets.

Example 1 100 parts by weight of pellets of the composition obtained in Reference Example 1 and a hydrogenated diene-based polymer [hydrogenated butadiene-styrene random copolymer, manufactured by Nippon Synthetic Rubber Co., Dynalon 1320P;
Styrene unit content 10% by weight, hydrogenation rate 99%, η
^* (1) = 2.1 × 10 ⁴ poise, n = 0.23] 5 parts by weight were melt-kneaded at 180 ° C. using a ⁴⁰ mm φ extruder to obtain a thermoplastic elastomer composition, which was then cut using a cutter. And cut to obtain pellets. After cooling the pellets to -120 ° C using liquid nitrogen, the pellets were pulverized while keeping the cooling state, and the powder of the thermoplastic elastomer composition [Tyler standard sieve 32 mesh (opening 500 µm x 500 µm)
Passed]. 1000 g of the thermoplastic elastomer composition powder obtained above was applied to a nickel electroformed grain plate (30 cm × 30 cm, thickness 3 m) heated to a surface temperature of 250 ° C.
m), and after 14 seconds, excess powder not heat-sealed was removed. Then, in a heating furnace at 250 ° C., 6
The sheet was heated for 0 second, then cooled, and then released from the mold to obtain a sheet-like molded body (thickness: 1 mm). Table 1 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

Examples 2 to 5 and Comparative Examples 1 to 2 The procedure of Example 1 was repeated, except that the amount of the hydrogenated diene polymer was changed as shown in Table 1, to prepare a thermoplastic elastomer composition. Thus, a molded product was obtained. Table 1 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

Example 6 An organic solvent was added to 100 parts by weight of the master batch obtained in Reference Example 1.
Oxide [Sanperox APO, 2,5, manufactured by Sanken Kako Co., Ltd.
-Dimethyl-2,5-di (t-butylperoxyno)
Xan] 0.1 part by weight and a hydrogenated diene polymer (die
5 parts by weight of Nalon 1320P) and a twin-screw kneader (Japanese
Dynamic mounting at 220 ° C using TEX-44)
A bridge-forming thermoplastic elastomer composition [η^*(1) =
4 × 10 ^ThreePoise, n = 0.31], which is
To obtain pellets. This pellet is liquid
After cooling to -120 ° C using nitrogen, the cooling state was maintained.
Pulverized to obtain a thermoplastic elastomer composition powder [Tyler
-Passed through a 32 mesh standard sieve]. Then, the embodiment
Obtained in place of the thermoplastic elastomer powder obtained in
Except that powdered thermoplastic elastomer composition was used.
By operating in the same manner as in Example 1, a molded body was obtained. Thermoplastic gill
Table 1 shows the evaluation results of the stoma composition and the molded article.

Comparative Examples 3 and 4 In place of the hydrogenated diene polymer, an ethylene-propylene random copolymer [SPO V0141, manufactured by Sumitomo Chemical Co., Ltd.]
Propylene unit content 27% by weight, η ^* (1) = 5.2
× 10 ⁴ poise, n = 0.2], styrene-butadiene random copolymer [SBR 1502, manufactured by Sumitomo Chemical Co., Ltd.]
Styrene unit content = 23% by weight, η ^* (1) = 3.1
× 10 ⁵ poise, n = 0.62] was used in the same manner as in Example 1 except that 20 parts by weight of each was obtained to obtain a thermoplastic elastomer composition and a molded article. Table 1 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

[0046]

Table 1 Thermoplastic Elastomer Hydrogenated Diene Composition Molded Example Polymer η ^* (1 ) n Flexible Whitening (parts by weight) Poise 500 g 1 kg Example 1 5 4.4 × 10 ³ 0.23 89 4 3 Example 2 10 3.7 x10 ³ 0.20 88 4 4 example ³ 20 2.5x10 3 0.10 86 4 4 example 4 40 4.5x10 ³ 0.14 82 4 4 example 5 80 6.5x10 ³ 0.15 80 4 4 example 6 5 4.0x10 ³ 0.25 89 ^{3 3} Comparative Example 1 0 5.2x10 ³ 0.31 92 2 2 Comparative Example 2 0.05 5.1x10 ³ 0.31 92 2 2 Comparative Example 3 (SPO V0141) 2.6x10 ⁴ 0.38 88 1 1 Comparative Example 4 (SBR 1052) 1.5x10 ⁴ 0.42 88 1 1

Comparative Examples 5-9 Hydrogenated butadiene-styrene random copolymer [Dynalon 1910P, manufactured by Nippon Synthetic Rubber Co., Ltd., styrene unit content 30% by weight, water Attachment ratio 99%, η ^* (1) = 8.4 ×
10 ³ poise, n = 0.12], hydrogenated styrene - butadiene - styrene block copolymer [manufactured by Shell Chemical, Kraton G1657X, styrene unit content of 13 wt%, hydrogenation ratio 99%, η ^* (1) = 7 × 10 ³ poise, n
= 0.1], hydrogenated styrene-isoprene-styrene block copolymer (Septon 2043, manufactured by Kuraray Co., Ltd., styrene unit content 20% by weight, hydrogenation rate 99%, η ^* (1)
= 1.3 × 10 ⁵ poise, n = 0.63], styrene-
Butadiene-crystalline polyethylene block copolymer [Dynalon E4600P, manufactured by Nippon Synthetic Rubber Co., Ltd., styrene unit content 20% by weight, hydrogenation rate 99%, η ^* (1) = 7.
2 × 10 ³ poise, n = 0.21], crystalline polyethylene-butadiene-crystalline polyethylene block copolymer [Dynalon E6100P, manufactured by Nippon Synthetic Rubber Co., hydrogenation rate 99%, η ^* (1) = 7. 2 × 10 ³ poise, n = 0.
21] was used in the same manner as in Example 1 except that 20 parts by weight of each was used to obtain a thermoplastic elastomer composition and a molded article. Table 2 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

[0048]

Table 2 Example of molded article of thermoplastic elastomer composition Polymer η ^* (1 ) n flexible whitening (poise) 500 g 1 kg Comparative Example 5 Tainarone 1910P 1.1 × 10 ⁴ 0.34 88 1 1 Comparative Example 6 Clayton G1657X 1.0 × 10 ⁴ 0.34 88 1 1 Comparative Example 7 Hypler HVS-3 1.2x10 ⁴ 0.44 88 1 1 Comparative Example 8 Thainaron E4600P 1.7x10 ⁴ 0.34 88 1 1 Comparative Example 9 Thainaron E6100P 3.9x10 ⁴ 0.42 89 1 1

Reference Example 2 66.7 parts by weight of an ethylene-propylene copolymer resin [ethylene unit content: 4.5% by weight, MFR = 90 g / 10 minutes] and ethylene-propylene copolymer rubber [Sumitomo Chemical Co., Ltd. SPO V0141, propylene unit content 2
7% by weight, MFR = 0.7 g / 10 min] and kneading 33.3 parts by weight using a twin-screw kneader at a shear rate of 1.2 × 10 ³ sec ^-1 and a temperature of 200 ° C. to obtain a composition [η ^* (1) = 2.7 × 1
0 ³ obtained poise, n = 0.08 to], to obtain pellets by cutting using a cutting machine it.

Example 7 In place of the pellet of the composition obtained in Reference Example 1, 100 parts by weight of the pellet of the composition obtained in Reference Example 2 was used, and the amount of the hydrogenated diene polymer (Dynalon 1320P) was changed to 66. Except for using 0.7 parts by weight, the same operation as in Example 1 was carried out to obtain a thermoplastic elastomer composition and a molded article. Table 3 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

Comparative Example 10 A thermoplastic elastomer composition was obtained in the same manner as in Example 7 except that no hydrogenated diene polymer was used, to obtain a molded article. Table 3 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

Comparative Example 11 A hydrogenated styrene-butadiene-styrene block copolymer [Clayton G1657X, manufactured by Shell Chemical Co., having a styrene unit content of 13% by weight instead of the hydrogenated diene polymer,
Hydrogenation rate 99%, η ^* (1) = 7 × 10 ³ poise, n =
0.1] was used in the same manner as in Example 7 except that 66.7 parts by weight was used, to obtain a thermoplastic elastomer composition and a molded article. Table 3 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

Comparative Example 12 A hydrogenated styrene-isoprene-styrene block copolymer [Hybler HVS-3, manufactured by Kuraray Co., Ltd., a styrene unit content of 20% by weight, a hydrogenation rate of 99%, instead of the hydrogenated diene polymer, η ^* (1) = 1.3 × 10 ⁵ poise, n = 0.
[63] was used in the same manner as in Example 7 except that 25 parts by weight of [63] was used to obtain a thermoplastic elastomer composition and a molded article. Table 3 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

Comparative Example 13 An ethylene-propylene random copolymer [SPO V0141, manufactured by Sumitomo Chemical Co., Ltd., propylene unit content 27% by weight, η ^* (1) = 5.2 ×
10 ⁴ poise, n = 0.2] was used in the same manner as in Example 7 except that 66.7 parts by weight was used to obtain a thermoplastic elastomer composition and a molded article. Table 3 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

Example 8 The procedure of Reference Example 2 was repeated, except that the amount of the ethylene-propylene copolymer resin was changed to 69 parts by weight and the amount of the ethylene-propylene copolymer rubber was changed to 31 parts by weight. Composition [η ^* (1) = 2.3 × 10 ³ poise, n = 0.0
8] to give pellets. In place of the pellet obtained in Reference Example 1, 100 parts by weight of the pellet obtained above was used, and the amount of the hydrogenated diene polymer (Dynalon 1320P) was changed to 54.
Except for using parts by weight, the same operation as in Example 1 was carried out to obtain a thermoplastic elastomer composition and a molded article. Table 3 shows the evaluation results of the thermoplastic elastomer composition and the molded article.

[0056]

Table 3 Example of molded article of thermoplastic elastomer composition Polymer η ^* (1 ) n flexible whitening (poise) 500 g 1 kg Example 7 Thainaron 1320P 5.0 × 10 ³ 0.17 86 4 4 Comparative Example 10-2.7 × 10 ³ 0.08 922 1 Comparative example 11 Kraton G1657X 4.2x10 ³ 0.10 87 1 1 Comparative example 12 Hythe Bu Ra ^{HVS-3 5.4x10 3 0.13 87 1} 1 Comparative example ^{13 SPO V0141 6.7x10 3 0.09 87 1} 1 example 8 data Bu Inaron 1320P 7.3x10 ³ 0.12 88 4 4

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shinichiro Nagai 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Yuji Goto 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Inside the corporation

Claims (5)

[Claims] 1. An ethylene / α-olefin copolymer rubber, a polyolefin resin, and the ethylene / α-olefin copolymer
0.1 to 150 parts by weight of a hydrogenated diene polymer represented by the following (A) per 100 parts by weight of the total amount of the olefin copolymer rubber and the polyolefin resin,
A thermoplastic elastomer composition having a complex dynamic viscosity η ^* (1) of 1.5 × 10 ⁵ poise or less and a Newton viscosity index n of 0.67 or less. (A) A conjugated diene-vinyl aromatic compound random copolymer having a conjugated diene polymer or vinyl aromatic compound unit content of 25% by weight or less is hydrogenated, and the degree of hydrogenation is 70% or more. Hydrogenated diene polymer 2. The weight ratio of the ethylene / α-olefin copolymer rubber to the polyolefin resin is from 5:95 to 20: 2.
The thermoplastic elastomer composition according to claim 1, wherein the composition is 80. 3. A molded article comprising the thermoplastic elastomer composition according to claim 1. 4. A molded article obtained by molding a powder of the thermoplastic elastomer composition according to claim 1. 5. A method for producing a molded product, comprising powder-forming the powder of the thermoplastic elastomer composition according to claim 1.