JP2003213051A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition having excellent flexibility, heat distortion and oil resistances and molding processability. <P>SOLUTION: This thermoplastic elastomer composition is obtained by melt kneading a composition comprising (a) 100 pts.wt. of an olefinic copolymer rubber, (b) 25-400 pts.wt. of a block copolymer composed of at least two polymer blocks A consisting essentially of an aromatic vinyl compound and at least one polymer block B consisting essentially of a conjugated diene compound, (c) 1-50 pts.wt. of a terminal hydroxy group-containing liquid polybutadinene and (d) 0.01-3 pts.wt. of an organic peroxide. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition, and more particularly to a thermoplastic elastomer composition having excellent flexibility, heat distortion resistance, oil resistance, extrusion moldability and injection moldability.

[0002]

2. Description of the Related Art In recent years, a thermoplastic elastomer, which is a soft material having rubber elasticity and which does not require a vulcanization step and has the same moldability and recyclability as a thermoplastic resin, has been used in automobile parts, home electric appliance parts, It is widely used in the fields of wire coating, medical parts, footwear, and sundries.

Among thermoplastic elastomers, olefin-based thermoplastic elastomers and styrene-based thermoplastic elastomers are highly flexible and have good rubber elasticity at room temperature, and thermoplastic elastomer compositions obtained from them are processed. It has excellent properties and is widely used as a substitute for vulcanized rubber.

However, the olefin-based thermoplastic elastomer or the styrene-based thermoplastic elastomer does not improve the cross-linking efficiency even if it is cross-linked, and the ethylene-propylene-conjugated diene co-weight of the blended ethylene-based copolymer rubber is increased. Polymer rubber (EPDM), ethylene / propylene copolymer rubber (EPR), ethylene / butene copolymer rubber (EBR), styrene-block copolymer styrene-butadiene block copolymer (SBS), styrene-ethylene / Butene-styrene block copolymer (SE
BS), styrene-ethylene / propylene-styrene block copolymer (SEPS), styrene-ethylene / ethylene / propylene-styrene block copolymer (SE
The oil resistance of EPS itself was poor, and there were problems in heat distortion resistance and oil resistance. Although a thermoplastic elastomer resin composition that solves these problems has been proposed (see, for example, Patent Document 1 and Patent Document 2), fuel oil (Fuel-
Oil resistance to C and Fuel-D) is not yet sufficient,
There has been a problem that only vulcanized rubber can be used in parts where oil resistance is required, such as engine engine peripheral members and fuel system peripheral members.

[0005]

[Patent Document 1] JP-A-8-225713

[Patent Document 2] Japanese Patent Application Laid-Open No. 9-151295

[0006]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a thermoplastic elastomer composition which is excellent in flexibility, heat distortion resistance, oil resistance, molding processability and the like.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have blended an olefin copolymer rubber with a styrene block copolymer and liquid polybutadiene, It was found that a thermoplastic elastomer composition excellent in flexibility, heat distortion resistance, oil resistance, molding processability and the like can be obtained by carrying out an organic peroxide crosslinking treatment, and completed the present invention.

That is, the first aspect of the present invention is (a)
A block composed of 100 parts by weight of an olefin-based copolymer rubber, (b) at least two polymer blocks A mainly containing an aromatic vinyl compound, and at least one polymer block B mainly containing a conjugated diene compound. Copolymer 25
To 400 parts by weight, (c) 1 to 50 parts by weight of liquid polybutadiene having a hydroxyl group at the terminal, and (d) thermoplastic obtained by melt-kneading a composition containing 0.01 to 3 parts by weight of organic peroxide. It is an elastomer composition.

The second invention of the present invention further comprises (e) 0.1 to 20 parts by weight of an ester crosslinking aid, the thermoplastic elastomer composition according to the first invention. Is.

The third invention of the present invention further comprises (f) an unsaturated glycidyl compound or its derivative in an amount of 0.1 to 5 parts by weight. It is a plastic elastomer composition.

Further, the fourth invention of the present invention is any one of the first to third inventions characterized in that it further comprises (g) 0.1 to 5 parts by weight of an unsaturated carboxylic acid or a derivative thereof. The thermoplastic elastomer composition according to the invention.

The fifth invention of the present invention is that (a) the olefin copolymer rubber has a polyolefin crystallinity of 20 wt% or less as measured by DSC and a Mooney viscosity (ML).
_{1 + 4} , test temperature 100 degreeC) is 7-90, It is the thermoplastic elastomer composition as described in any one of the invention of the 1st-4th invention characterized by the above-mentioned.

A sixth aspect of the present invention is that the aromatic vinyl compound of the block copolymer (b) is styrene,
The styrene content is 20 to 45 wt%, (b)
The viscosity of a 5 wt% toluene solution (ASTM D-2196) of the block copolymer at 25 ° C. is 5 to 500 cps.
The thermoplastic elastomer composition according to any one of the first to fifth inventions, characterized in that

Further, the seventh invention of the present invention is characterized in that (h) the hydrogenated block copolymer is further contained in an amount of 1 to 30 parts by weight. It is a plastic elastomer composition.

The eighth invention of the present invention is the thermoplastic elastomer composition according to any one of the first to seventh inventions, further comprising (i) 1 to 80 parts by weight of a softening agent for rubber. .

Further, the ninth invention of the present invention further comprises (j) 3 to 150 parts by weight of an olefin resin, wherein the thermoplastic resin according to any one of the inventions of 1 to 8 is characterized. It is an elastomer composition.

The tenth invention of the present invention further comprises (k) 1 to 150 parts by weight of an inorganic filler, wherein the thermoplastic resin according to any one of the first to ninth inventions is characterized. It is an elastomer composition.

The eleventh invention of the present invention is the first to the first invention.
No. 0 invention, an automobile interior / exterior member, a building member, or a home appliance member, which is obtained by molding and processing the thermoplastic elastomer composition.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic elastomer composition, the production method and the use of the present invention will be described in detail below.

1. Component (1) Olefin Copolymer Rubber (a) of Thermoplastic Elastomer Composition The olefin copolymer rubber component (a) used in the thermoplastic elastomer composition of the present invention includes ethylene, propylene, 1-butene, Examples thereof include an elastomer obtained by copolymerizing an α-olefin such as 1-pentene, or an olefin copolymer rubber obtained by copolymerizing these with a non-conjugated diene. Of these, an olefin-based copolymer rubber obtained by copolymerizing a non-conjugated diene is preferable.

The non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene,
Examples thereof include methylene norbornene and 5-ethylidene-2-norbornene.

Specific examples of such olefinic copolymer rubbers include ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene-1-butene copolymer rubber, Ethylene-1
Examples include butene-non-conjugated diene copolymer rubber and ethylene-propylene-1-butene copolymer rubber.

The polyolefin crystallinity of the olefin copolymer rubber component (a) measured by DSC is preferably 20 wt% or less, more preferably 15 w.
t% or less, and more preferably 1 wt% or less. If the crystallinity exceeds 20 wt%, the flexibility of the thermoplastic elastomer composition obtained will decrease, the hardness of the thermoplastic elastomer composition will become too high and the flexibility will be lost, and a product having a rubber-like feel cannot be obtained. . In addition, the compatibility between the thermoplastic elastomer composition and the resin having a polar group is deteriorated, and peeling or deformation of the resulting thermoplastic resin composition and flow marks are likely to occur in the molded product.

Here, the crystallinity of the polyolefin by DSC (differential scanning calorimetry) is measured by the following method. (I) The sample is placed in an aluminum pan of known weight, and dried under a pressure of about 10 Pa for 24 hours before encapsulation. (Ii) After drying, immediately measure the weight of the entire sample container, and seal under pressure. (Iii) The sample container is set in the DSC sample holder, and the temperature is raised to 230 ° C. at a temperature rising rate of 10 ° C./min. (Iv) Hold at 230 ° C. for 60 minutes to completely melt or relax the sample. (V) Cool to 30 ° C. at the same rate (10 ° C./min) as the temperature rising rate. (Vi) The crystallinity is evaluated from the heat of crystallization (ΔHc), assuming that the crystal perfection generated in the isothermal crystallization process is constant regardless of the crystal formation time. (Vii) Crystallinity is 10 times the heat of crystallization (ΔHc) of HDPE (HJ560: Nippon Polychem, specific gravity 0.964).
The heat of crystallization (ΔHc) of the olefin copolymer rubber (a) is designated as 0 in%.

Furthermore, the Mooney viscosity (ML _{1 + 4} , test temperature 100) of the olefinic copolymer rubber component (a).
C) is preferably 7 to 90, more preferably 15 to 75. When the Mooney viscosity (ML _{1 + 4} , test temperature 100 ° C.) is less than 7, the oil resistance and heat resistance are poor,
Further, when it exceeds 90, the moldability is deteriorated.

Specific components (a) include, for example, N
ordel IP 4520 (EPDM, Dupont
Dow Elastomers).

(2) Block Copolymer (b) The block copolymer component (b) used in the thermoplastic elastomer composition of the present invention comprises at least two polymer blocks A containing an aromatic vinyl compound as a main component. , A block copolymer composed of at least one polymer block B containing a conjugated diene compound as a main component. For example, AB-
Examples thereof include vinyl aromatic compound-conjugated diene compound block copolymers having a structure of A, B-A-B-A, A-B-A-B-A and the like.

The above block copolymer contains an aromatic vinyl compound in an amount of 5 to 60% by weight, preferably 20 to 50% by weight.
Including. The polymer block A containing an aromatic vinyl compound as a main component preferably comprises only an aromatic vinyl compound,
Alternatively, it is a copolymer block of 50% by weight or more, preferably 70% by weight or more of an aromatic vinyl compound and an optional component such as a conjugated diene compound.

The polymer block B containing a conjugated diene compound as a main component preferably consists of the conjugated diene compound alone, or 50% by weight or more, preferably 70% by weight or more of the conjugated diene compound and an optional component such as an aromatic vinyl compound. Is a copolymer block with.

As the aromatic vinyl compound constituting the block copolymer, for example, one kind or two or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. But styrene is preferred. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3
-Dimethyl-1,3-butadiene or the like is selected from one kind or two or more kinds, and among them, butadiene, isoprene and a combination thereof are preferable.

When the aromatic vinyl compound is styrene, the content of styrene is preferably 20 to 45 wt%, more preferably 28 to 35 wt%. If the styrene content is less than 20 wt%, the oil resistance and compression set are poor, and if it exceeds 45 wt%, the rubber elasticity becomes poor.

Also, the viscosity of a 5 wt% toluene solution of the block copolymer at 25 ° C. (ASTM D-2196)
Is preferably 5 to 500 cps, more preferably 20 to 300 cps. 25 at 25 ° C
When the viscosity of the wt% toluene solution is less than 5 cps, the heat resistance decreases, and when it exceeds 500 cps, the processability deteriorates.

In the polymer block A mainly composed of the aromatic vinyl compound and the polymer block B mainly composed of the conjugated diene compound, the distribution of the units derived from the conjugated diene compound or the aromatic vinyl compound in the molecular chain. May be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks A mainly containing an aromatic vinyl compound or polymer blocks B mainly containing a conjugated diene compound, each polymer block may have the same structure or different structures. It may be.

A number of methods have been proposed as a method for producing these block copolymers. As a typical method, for example, a method described in Japanese Patent Publication No. 40-23798, a lithium catalyst or a Ziegler catalyst is used. It can be obtained by block polymerization in an inert medium using a type catalyst.

Specific examples of the block copolymer include:
Styrene-butadiene-styrene copolymer (SBS),
Styrene-isoprene-styrene copolymer (SIS),
Etc. can be mentioned.

The blending amount of the component (b) is 100 parts of the component (a).
25 to 400 parts by weight is preferable, and 75 to 150 parts by weight is more preferable. If the blending amount is less than 25 parts by weight, the oil resistance is lowered, and if it exceeds 400 parts by weight, the mechanical properties and molding processability of the thermoplastic elastomer composition obtained are deteriorated.

(3) Liquid polybutadiene (c) having a hydroxyl group at the terminal The liquid polybutadiene component (c) having a hydroxyl group at the terminal used in the thermoplastic elastomer composition of the present invention is used when melt-processing the thermoplastic elastomer composition. , (A) and / or (b) are graft-polymerized in the presence of an organic peroxide to improve the compatibility. The component (c) is a liquid polymer which is transparent at room temperature and has a main chain fine structure of vinyl 1,2-bond type, trans 1,4-bond type, and cis 1,4-bond type. Here, the vinyl 1,2-bond is preferably 30% by weight or less, and the vinyl 1,2-bond is
When the bond content exceeds 30% by weight, the low temperature properties of the obtained thermoplastic elastomer composition are deteriorated, which is not preferable.

The terminal hydroxyl group content of component (c) (J
IS K 1557) is 0.05 to 3.0 mol / k.
g is preferable, and more preferably 0.1-1.5 mol
/ Kg range. Further, the number average molecular weight of the liquid polybutadiene is preferably 1,000 to 5,000, more preferably 2,000 to 4,000. When the number average molecular weight is less than 1,000, the heat distortion resistance of the obtained thermoplastic elastomer composition is lowered, and when it exceeds 5,000, the compatibility of the obtained thermoplastic elastomer composition is lowered.

Specific examples of the component (c) include commercially available products of R-45HT (trademark) manufactured by Idemitsu Petrochemical Co., Ltd.

The blending amount of the component (c) is 100 parts of the component (a).
1 to 50 parts by weight, preferably 3
~ 20 parts by weight. When the blending amount is less than 1 part by weight, the compatibility of the component (b) with the component (a) and other components deteriorates,
Moldability deteriorates due to peeling of molded articles and generation of flow marks, and when it exceeds 50 parts by weight, the softening agent easily bleeds out from the resulting thermoplastic elastomer composition, resulting in peeling, deformation and flow marks on molded articles. It tends to occur.

(4) Organic peroxide (d) The organic peroxide component (d) used in the thermoplastic elastomer composition of the present invention generates radicals and causes the radicals to react in a chain reaction to form the component ( It serves to crosslink a) and / or component (b). Further, at the same time, the component (c) and the components (e) to (h) to be blended as necessary.
Is graft-polymerized with the component (a) and / or the component (b) to improve the compatibility between the component (a) and the component (b). Furthermore, the component (j) to be blended if necessary
Is decomposed or crosslinked to control the fluidity of the thermoplastic elastomer composition at the time of melt-kneading so that the rubber component is well dispersed.

Examples of the component (d) include dicumyl peroxide, di-tert-butyl peroxide, 2,
5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t
ert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ter
t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, ter
Examples thereof include t-butyl cumyl peroxide. Of these, 2,5-dimethyl-2,5-di- (ter) is preferable from the viewpoint of odor, coloring, and scorch safety.
t-butylperoxy) hexane, 2,5-dimethyl-
2,5-di- (tert-butylperoxy) hexyne-3 is particularly preferred.

The blending amount of the component (d) is 100 parts of the component (a).
0.01 to 3 parts by weight, preferably 0.
1 to 1.5 parts by weight. If the blending amount is less than 0.01 part by weight, grafting and crosslinking cannot be sufficiently achieved, the oil resistance of the obtained thermoplastic elastomer composition is deteriorated, and the mechanical properties and moldability are deteriorated. On the other hand, when it exceeds 3 parts by weight, the moldability of the obtained thermoplastic elastomer composition is deteriorated and mechanical properties such as tensile elongation are deteriorated.

(5) Ester-based cross-linking aid component (e) In the thermoplastic elastomer composition of the present invention, an ester-based cross-linking aid component (e) can be used, if necessary. The component (e) can be added during the crosslinking treatment of the thermoplastic elastomer composition of the present invention with the (d) organic peroxide, whereby a uniform and efficient crosslinking reaction can be carried out. In addition, by blending a large amount, a non-aromatic softening agent for rubber, particularly a low molecular weight paraffin oil, etc. can be appropriately cross-linked and bleed-out from the thermoplastic elastomer composition can be suppressed.

Specific examples of the component (e) include, for example, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and ethylene glycol having a repeating number of 9 to 14. Polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate, polyfunctional methacrylate compounds such as 1,9-nonanediol dimethacrylate, polyethylene glycol diacrylate, 1,6
Mention may be made of polyfunctional acrylate compounds such as hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polyfunctional vinyl compounds such as vinyl butyrate or vinyl stearate. These may be used alone or in combination of two or more. Of these crosslinking aids, trimethylolpropane trimethacrylate is particularly preferred.

The blending amount of the component (e), when blended, is
It is preferably 0.1 to 100 parts by weight of the component (a).
20 parts by weight is preferable, and more preferably 0.5 to 10 parts by weight. If it exceeds 20 parts by weight, the degree of crosslinking is lowered due to self-polymerization, and the effect cannot be obtained.

(6) Unsaturated glycidyl compound or derivative thereof (f) In the thermoplastic elastomer composition of the present invention, an unsaturated glycidyl compound or derivative component (f) thereof may be added, if necessary.
Can be blended. The component (f) is used as a modifier, preferably a glycidyl compound having an unsaturated group capable of copolymerizing with an olefin and a glycidyl group in the molecule is used, and particularly preferably glycidyl methacrylate (GMA). Is used. The modifying agent modifies the component (a), and further the olefin resin (j) and the component (h), etc., which are blended as necessary, to improve the compatibility with the component (b) and to improve the elongation at break. Is further improved. By adding the component (f), the range of molding conditions is broadened, and even in low-speed injection molding, defects such as peeling and flow marks are less likely to occur in the molded product.

The blending amount of the component (f) is as follows.
The amount is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 2 parts by weight, based on 100 parts by weight of the component (a). When the blending amount exceeds 5 parts by weight, not only the thermoplastic elastomer composition undergoes severe yellowing, but also the heat distortion resistance and mechanical properties are deteriorated, and when other resins are blended,
The effect of improving the compatibility with the components cannot be recognized.

(7) Unsaturated carboxylic acid or its derivative (g) In the thermoplastic elastomer composition of the present invention, if necessary, unsaturated carboxylic acid or its derivative component (g)
Can be blended. Component (g) is used as a modifier and is preferably acrylic acid, methacrylic acid, maleic acid, dicarboxylic acid or a derivative thereof, such as an acid, a halide, an amide, an imide, an anhydride or an ester derivative. Can be mentioned. Particularly preferably, maleic anhydride (MAH) is used. The modifier modifies the component (a) and optionally the olefin resin of the component (h) and the component (j), preferably polypropylene, etc., to improve the compatibility with the component (b). The breaking elongation is further improved. By adding the component (g), the range of molding conditions is widened, and it becomes difficult for defects such as peeling and flow marks to occur in molded products even in low-speed injection molding.

When compounding the component (g),
The amount is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 2 parts by weight, based on 100 parts by weight of the component (a). If the blending amount exceeds 5 parts by weight, not only the thermoplastic elastomer composition undergoes severe yellowing, but also the heat distortion resistance and the mechanical properties are deteriorated, and the compatibility with the component (b) is improved. Will not be recognized.

By adding the components (f) and / or (g), the bending fatigue characteristics are improved.

(8) Hydrogenated block copolymer (h) If necessary, a hydrogenated block copolymer component (h) is added to the thermoplastic elastomer composition of the present invention to adjust flexibility. can do. The hydrogenated block copolymer component (h) includes at least two polymer blocks A (h-1) mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound. And a hydrogenated product of a block copolymer consisting of, for example, ABA, BABAA, ABABA
Hydrogenated block copolymer of aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as (h-
2) A hydrogenated product of a conjugated diene polymer, which may be a block copolymer composed of an amorphous olefin block and a crystalline olefin block. Among them, the component (h
-1) is preferable.

The above component (h-1) is preferably a hydrogenated product of a block copolymer containing 5 to 60% by weight, preferably 20 to 50% by weight of an aromatic vinyl compound. It is a hydride of the block copolymer used in the component (b).

In the polymer block B mainly composed of the conjugated diene compound in the component (h-1), its microstructure is arbitrary. For example, when the block B is composed of butadiene alone, Preferably has a 1,2-microstructure of 20 to 50
%, Particularly preferably 25 to 45% by weight. The hydrogenation rate is arbitrary, but is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more.
Alternatively, the 1,2-bond may be selectively hydrogenated. When block B is composed of a mixture of isoprene and butadiene, the 1,2-microstructure is preferably less than 50%, more preferably less than 25%, even more preferably less than 15%. When block B is composed of isoprene alone. In the polyisoprene block, preferably 70 to 100% by weight of isoprene is 1,4-
Those having a microstructure and preferably at least 90% of the aliphatic double bonds derived from isoprene are hydrogenated.

The number average molecular weight of the component (h-1) is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000, further preferably 9
The range is from 10,000 to 400,000, and the molecular weight distribution is 10 or less. The molecular structure of the component (h-1) may be linear, branched, radial, or any combination thereof.

Specific examples of the component (h-1) include styrene-ethylene / butene-styrene copolymer (SEB
S), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-butadiene-butylene-styrene copolymer (partially hydrogenated styrene-butadiene) -Styrene copolymer, SBB
S) etc. can be mentioned.

Examples of the component (h-2) include a hydrogenated product of a conjugated diene polymer and a block copolymer comprising an amorphous polyolefin block and a crystalline polyolefin block. Examples of such hydrogenated diene polymers include the polymers described in JP-A-3-74409 and CEBC6100 and 6200 manufactured by JSR Corporation.

The blending amount of the component (h) is as follows.
The amount is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the component (a). When it exceeds 30 parts by weight, the crosslinking efficiency of the obtained thermoplastic elastomer composition deteriorates, and the heat distortion resistance and oil resistance decrease.

(9) Softener component for rubber (i) In the thermoplastic elastomer composition of the present invention, a softener component for rubber (i) can be added, if necessary. The rubber softener component (i) used in the present invention may be either a non-aromatic component or an aromatic component, and an ester plasticizer may be used. In particular, a non-aromatic mineral oil or ester is used. System plasticizers are preferred. As a non-aromatic mineral oil softener, the paraffin chain carbon number is 50 or less.
A paraffin-based softening agent occupying at least 100% is included.

Among the ester plasticizers, examples of the cyclic plasticizer include phthalic anhydride ester and trimellitic acid ester, N-cyclohexyl-p-toluenesulfonamide, dibenzyl sebacate, diethylene glycol dibenzoate, and the like. Di-t-octyl phenyl ether, dipropanediol dibenzoate, N-
Ethyl-p-toluenesulfonamide, isopropylidene diphenoxypropanol, alkylated naphthalene,
Examples thereof include polyethylene glycol dibenzoate, o, p-toluenesulfonamide, trimethylpentanediol dibenzoate and trimethylpentanediol monoisobutyrate monobenzoate. Among these, phthalic anhydride ester and trimellitic acid ester are preferable.

Typical examples of the phthalic anhydride ester are, for example, butyl octyl phthalate and butyl 2-.
Ethylhexyl phthalate, butyl n-octyl phthalate, dibutyl phthalate, diethyl phthalate, diisodecyl phthalate, dimethyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate,
Diisooctyl phthalate, diisononyl phthalate (DINP), di-tridecyl phthalate, n-hexyl n-decyl phthalate, n-octyl n-decyl phthalate, alkyl benzyl phthalate, bis (4
-Methyl-1,2-pentyl) phthalate, butyl benzyl phthalate, butyl cyclohexyl phthalate, di (2-butoxyethyl) phthalate, cyclohexyl isodecyl phthalate, dicyclohexyl phthalate, diethyl isophthalate, di-n-heptyl phthalate, Dihexyl phthalate, di (2-methoxyethyl) phthalate, dimethylisophthalate, dinonylphthalate, dioctylphthalate, dicaprylphthalate, di (2-ethylhexyl) isophthalate, mixed dioctylphthalate, diphenylphthalate, 2- (ethylhexyl) isobutylphthalate, Butyl phthalyl butyl glycolate, ethyl (and methyl) phthalyl ethyl glycolate, polypropylene glycol bis (amyl) phthale DOO, hexyl isodecyl phthalate, isodecyl-tridecyl phthalate include isooctyl-isodecyl phthalate.

Typical examples of trimellitic acid ester include, for example, triisooctyl trimellitate, tri-n-octyl.n-decyl trimellitate, trioctyl trimellitate, tri (2-ethylhexyl) trimellitate. (TOTM), tri-n-hexyl.n-decyl trimellitate, tri-n-hexyl trimellitate, triisodecyl trimellitate and triisononyl trimellitate.

As the acyclic plasticizer, phosphoric acid ester, adipic acid ester, azelaic acid ester, citric acid ester, acetyl citric acid ester, myristic acid ester, ricinoleic acid ester, acetylricinoleic acid ester, sebacic acid ester, Stearic acid ester, epoxidized ester, and 1,4-
Butanediol dicaprylate, butoxyethyl pelargonate di [(butoxyethoxy) ethoxy] methane, dibutyl tartrate, diethylene glycol dipelargonate, diisooctyl diglycolate, isodecyl nonanoate, tetraethylene glycol di (2
-Ethyl-butyrate), triethylene glycol di (2-ethyl-hexanoate), triethylene glycol dipelargonate and 2,2,4-trimethyl-1,3 which is an ester compound of a branched aliphatic dihydric alcohol.
-Pentanediol monoisobutyrate, 2,2,4-
Trimethyl-1,3-pentanediol diisobutyrate (TXIB), an acrylic polymer, etc. may be mentioned.

Representative examples of the phosphoric acid ester include, for example, cresyl diphenyl phosphate, tricresyl phosphate, dibutyl phenyl phosphate, diphenyl octyl phosphate, methyl diphenyl phosphate, tributyl phosphate, triphenyl phosphate, tri (2-butoxy). Mention may be made of ethyl) phosphate, tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate and trioctylphosphate.

As typical examples of the adipic acid ester, for example, di [2- (2-butoxyethoxy) ethyl] adipate, di (2-ethylhexyl) adipate, diisononyl adipate (DINA), diisodecyl adipate, dioctyl adipate ( Diisooctyl adipate), n-hexyl n-decyl adipate, n-octyl n-decyl adipate and di-
Examples include n-heptyl adipate.

Representative examples of the sebacic acid ester include dibutyl sebacate, di (2-ethylhexyl) sebacate, dibutoxyethyl sebacate, diisooctyl sebacate and diisopropyl sebacate.

Representative examples of azelaic acid esters include, for example, di (2-ethylhexyl) azelaate,
Included are dicyclohexyl azelaate, diisobutyl azelaate and diisooctyl azelaate.

Examples of the acrylic polymer plasticizer include (i)
Examples of the polymer include a reaction product obtained by reacting a mixture of a radically polymerizable monomer and a (ii) modifying compound in the presence or absence of a polymerization initiator. This polymer is preferably a polymer in which the binding mode of the modifying compound to the polymer is (ii) an ester bond, (i) using (meth) acrylic acid as a radically polymerizable monomer, and (ii) ) It may be a polymer using an aliphatic or alicyclic alcohol as the modifying compound.

In the acrylic polymer plasticizer, the radical polymerizable monomer (i) is (meth) acrylic acid;
Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. Hydroxyl group-containing (meth) acrylate; maleic anhydride, maleic acid,
Mono and dialkyl esters of maleic acid; styrene,
Aromatic vinyl monomers such as α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; (meth) acrylonitrile, (meth) acrylamide, chloride Examples thereof include vinyl, vinylidene chloride, allyl chloride and allyl alcohol.

As the modifying compound (ii), cycloalkanol such as cyclohexyl alcohol; alkanol such as isopropyl alcohol; halogen group-containing alcohol such as fluoroalkyl alcohol; alkylene diol such as ethylene glycol and butane diol;
Cycloalkylene diols such as cyclohexane diol and cyclohexyl dimethanol; modifiers containing hydroxyl groups such as polyethers having terminal hydroxyl groups, polymers such as polyesters, cyclohexyl carboxylic acid, cyclohexyl dicarboxylic acid, adipic acid, sebacic acid, fluoroalkyl dicarboxylic acid , Carboxyl group-containing compounds such as maleic anhydride and fumaric acid; ethyl acetate, butyl acetate,
Examples thereof include ester group-containing modifiers such as cellosolve acetate, methyl propylene glycol acetate, carbitol acetate and ethyl carbitol acetate, and alkenes such as cyclohexene, cyclopentene and isobutene.

Examples of the acrylic polymer in the combination of (i) and (ii) include (i) (meth) acrylic acid, maleic anhydride, maleic acid or a monoalkyl ester of maleic acid. A polymer having a modifying compound introduced into the polymer is obtained by an esterification reaction using the compound having a hydroxyl group of ii). Also,
When the ester group-containing monomer such as methyl (meth) acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate of (i) and the compound having a hydroxyl group of (ii) are used, a transesterification reaction causes A polymer is obtained. further,
By forming an ester bond by reacting the hydroxyl group-containing monomer of (i) 2-hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate with the carboxyl group- or ester group-containing compound of (ii), a functional group is formed. A polymer in which is introduced is obtained. Furthermore, by using a carboxyl group-containing monomer (i) such as (meth) acrylic acid and an alkene (ii), the carboxyl group is subjected to an addition reaction with an ethylenically unsaturated bond to form an ester bond. A polymer having the quality compound introduced therein is obtained.

In the acrylic polymer plasticizer that can be used in the present invention, as the above (i), butyl acrylate, ethyl acrylate, hexyl acrylate, mesooxyethyl acrylate and glycidyl acrylate are preferable, and ethyl acrylate is the main. Optimal is a component.

The weight average molecular weight (Mw) of the acrylic polymer plasticizer is preferably 500 to 10,000,
The viscosity is more preferably 1000 to 6000, further preferably 1000 to 3000, and the viscosity is 100 to 9000.
mPa · s is preferable, and more preferably 1000 to 60
00 mPa · s, and more preferably 3000 to 5000
mPa · s and Acetone-Water To
SP value calculated from the tolerance is 10.5 to 16.
5 is preferable, 13 to 16 is more preferable, and 14 to 16 is still more preferable.

Among these ester type plasticizers, DINP, DINA and TOTM are particularly preferable.

The blending amount of the component (i) is as follows.
The amount is preferably 1 to 80 parts by weight, more preferably 3 to 30 parts by weight, relative to 100 parts by weight of the component (a). When the amount is less than 1 part by weight, the flexibility and moldability of the thermoplastic elastomer composition obtained are not improved. If it exceeds 80 parts by weight, the softening agent is likely to bleed out from the resulting thermoplastic elastomer composition, and peeling or deformation and flow marks are likely to occur in the molded product. Furthermore, the gas generated during processing becomes remarkable.

(10) Olefin Resin (j) In the thermoplastic elastomer composition of the present invention, an olefin resin component (j) may be added, if necessary. The component (j) improves the rubber dispersion of the obtained thermoplastic elastomer composition, improves the appearance of the molded product, and has the effect of adjusting the hardness and the shrinkage ratio. The component is preferably a peroxide-decomposable olefin-based polymer or copolymer that is thermally decomposed by heat treatment in the presence of peroxide to reduce the molecular weight and increases fluidity at the time of melting. For example, isotactic Polypropylene or propylene and other α-olefins,
Examples thereof include copolymers with ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

D of the homo portion of the above olefin-based copolymer
The melting point measured by SC is preferably Tm of 150 to 1
70 ° C., ΔHm is in the range of 25 to 90 mJ / mg. The crystallinity can be estimated from Tm and ΔHm measured by DSC. When Tm and ΔHm are out of the above ranges, the obtained thermoplastic elastomer composition has oil resistance and 100 ° C.
The rubber elasticity in the above is not improved.

Further, the melt flow rate of component (j) (MFR, ASTM D-1238, L condition, 230
C) is preferably 0.1 to 200 g / 10 minutes, more preferably 0.5 to 100 g / 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the moldability of the obtained thermoplastic elastomer composition will deteriorate, and if it exceeds 200 g / 10 minutes, the rubber elasticity of the obtained thermoplastic elastomer composition will deteriorate.

The blending amount of the component (j) is as follows.
The amount is preferably 3 to 150 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the component (a). When it is 3 parts by weight or less, the moldability of the obtained thermoplastic elastomer composition is deteriorated, and when it exceeds 150 parts by weight, the hardness of the obtained thermoplastic elastomer composition becomes too high and the flexibility is lost, resulting in a rubber-like product. Can't get

(11) Inorganic Filler Component (k) In the thermoplastic elastomer composition of the present invention, an inorganic filler component (k) may be added, if necessary. The component (k) has an effect of improving some physical properties such as compression set of a molded article obtained from the thermoplastic elastomer composition, and has an economic advantage by increasing the amount. Examples of the component (k) include chlorite, calcium carbonate, talc, silica, diatomaceous earth, barium sulfate, magnesium carbonate, magnesium hydroxide, mica, clay, titanium oxide, carbon black, glass fiber, hollow glass balloon, carbon fiber. , Calcium titanate fiber, natural silicic acid,
Examples thereof include synthetic silicic acid (white carbon). Of these, chlorite, calcium carbonate and talc are particularly preferred.

The blending amount of the component (k) is as follows.
The amount is preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the component (a). 1
If it exceeds 50 parts by weight, the mechanical strength of the obtained elastomer composition is remarkably lowered, and the hardness is increased to lose the flexibility, so that a product having a rubber-like feel cannot be obtained.

(12) Other components In addition to the above components, the thermoplastic elastomer composition of the present invention may further contain various antiblocking agents, sealability improving agents, heat stabilizers, and oxidants, if necessary. It is also possible to contain an inhibitor, a light stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a coloring agent and the like. Here, as the antioxidant,
For example, 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol,
2,4-dimethyl-6-tert-butylphenol,
Examples thereof include phenolic antioxidants such as 4,4-dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants, and thioether antioxidants. Of these, phenol-based antioxidants and phosphite-based antioxidants are particularly preferable. The antioxidant is the above component (a).
To (d) and (e) to (j), a total of 100 parts by weight is preferable, and 0 to 3.0 parts by weight is particularly preferable.
1 to 1.0 parts by weight.

2. Production of Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention comprises the above components (a) to (d) or, if necessary, components (e) to (j).
, And each component is added simultaneously or in any order and melt-kneaded.

The melt-kneading method is not particularly limited, and a commonly known method can be used. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. For example, a moderate L / D twin-screw extruder,
The above operation can be continuously performed by using a Banbury mixer, a pressure kneader or the like. Here, the temperature of the melt-kneading is preferably 160 to 220 ° C.

The thermoplastic elastomer composition of the present invention comprises
Since it has excellent heat distortion resistance, oil resistance, extrusion moldability, injection moldability, etc., it can be used as a material for automobile interior / exterior members, building materials, household appliances, etc., and is particularly excellent in oil resistance to fuel oil. Therefore, it can be used as a material for a portion where oil resistance is required, such as an engine peripheral member and a fuel system peripheral member of an automobile.

Specifically, examples of the electric wire / electrical part include a connector, a switch cover, a plug, a gasket, a grommet, a cable jacket curl cord, an electric wire insulation coating, and the like. Examples include hoses, diaphragms, gaskets, packings, casters, grommets, roller coupling grips, hoses, and medical device / food related parts such as syringe tips, drug stoppers, grommets, blood collection tube caps, cap seals, etc. Examples of automobile parts include CVJ boots, rack and opinion boots, shock absorber dust boots, vacuum connectors, air ducts, tubes,
Examples include run channels, grommets, handle covers, airbag outer cover steering, mudguards, and the like, and examples of building materials include window frame seals, expansion joints, sponge seals, handrail coatings, stair-slip stoppers, and the like. As other uses, for example, grip materials such as pen grips, bicycle grips, toothbrush grips, toy parts, mats,
Examples include goggles, dust / gas masks, and shoe soles.

[0087]

EXAMPLES The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The measuring methods of physical properties and samples used in the present invention are shown below.

1. Test method (1) Specific gravity: According to JIS K 7112, a test piece was measured using a 1 mm thick press sheet. (2) Hardness: According to JIS K 6253, the hardness was measured with a durometer hardness and type A. The test piece is 6.3 mm
A thick press sheet was used. (3) Tensile strength: In accordance with JIS K 6251, a 1 mm thick press sheet was used as a test piece by punching out a No. 3 dumbbell type test piece. The pulling speed was 500 mm / min. (4) 100% elongation stress: According to JIS K 6251, a 1 mm thick press sheet was punched out from a No. 3 dumbbell type test piece to be used. Pulling speed is 500mm /
Minutes (5) Elongation at break: According to JIS K 6251, a 1 mm thick press sheet was used as a test piece by punching out a No. 3 dumbbell type test piece. The pulling speed was 500 mm / min. (6) Compression set (CS%): JIS K 6262
In accordance with, the test piece uses a 6.3 mm thick press sheet,
It was measured under the conditions of 120 ° C. × 72 hours and 25% deformation. (7) Heat aging resistance: In accordance with JIS K 6251, a test piece of 1 mm thick press sheet was punched out into a No. 3 dumbbell-shaped test piece, and the residual tensile strength (TS) and breaking elongation after 150 ° C. and 168 hrs. The residual rate (EL) was measured. The pulling speed was 500 mm / min. (8) Volume swelling rate (%): In accordance with JIS K 6258, the test piece uses a 1 mm thick press sheet, 120 ° C ×
72 hours, after immersion in IRM # 903 and at 23 ° C. for 72 hours,
The swelling ratio of the fuel oil C was measured. (9) Extrudability: A 50 mm × 1 mm sheet was extruded, and the drawdown property, surface appearance and shape were observed and evaluated according to the following criteria. ○: Good ×: Poor (10) Injection moldability: Using an injection molding machine with a mold clamping pressure of 120 tons, molding temperature 220 ° C, mold temperature 40 ° C, injection speed 55 mm / sec, injection pressure 600 kg / cm ² , retention A pressure of 400 kg / cm ² , an injection time of 6 seconds, and a cooling time of 45 seconds were used to form a 13.5 × 13.5 × 2 mm sheet. The presence or absence of flow marks that delaminate, peel off the surface layer, deform, and significantly deteriorate the appearance was visually evaluated, and evaluated according to the following criteria. ◯: Good ×: Poor (11) Flexural fatigue characteristics: Measured according to (JIS K 6260).

2. Sample (1) Olefin-based copolymer rubber (a) used in Examples and Comparative Examples: Nordel
IP 4520 (EPDM, polyolefin crystallinity 1 wt% or less, Mooney viscosity (ML _{1 + 4} test temperature 1
00 ° C): 35, specific gravity: 0.86; Dupont Do
w Elastomers) (2) SBS block copolymer component (b): VECTO
R2518 (trademark; manufactured by DEXCO POLYMERS) Styrene amount: 30%, 5 wt% toluene solution viscosity at 25 ° C .: 75 cps, specific gravity: 0.95 (3) Terminal hydroxyl group-containing liquid polybutadiene component (c):
R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.), containing a hydroxyl group (0.83 mol / kg) and a copolymerization-reactive unsaturated double bond (1,4 bond: 80%) as a functional group, and a number average molecular weight of 2800 ( 4) Organic peroxide component (d): Perhexa 25B
(2,5-dimethyl 2,5-di- (tert-butylperoxy) hexane) (trademark; manufactured by NOF CORPORATION),
Active oxygen amount: 9.92%, molecular weight: 290.45, decomposition temperature for obtaining a one-minute half-life: 179.8 ° C. (5) Ester-based crosslinking aid component (d): TMPT (Tr
Imetyl Propane Trimeth
Acrylate; manufactured by Shin Nakamura Chemical Co., Ltd.) Molecular weight: 3
38 (6) Unsaturated glycidyl compound component (f): Glycidyl methacrylate (GMA) (manufactured by Kanto Chemical Co., Inc.) (7) Unsaturated carboxylic acid component (g): Maleic anhydride (MAH) (manufactured by Kanto Chemical Co., Ltd.) (8) Hydrogenated block copolymer component (h); Septon 4
077 (SEPS; manufactured by Kuraray Co., Ltd.), styrene content: 30% by weight, number average molecular weight: 260,000, weight average molecular weight: 320,000, molecular weight distribution: 1.23,
Hydrogenation rate: 90% or more (9) Softener component (i): Diana Process Oil P
W-90 (mineral oil; manufactured by Idemitsu Kosan Co., Ltd.) (10) Olefin resin component (j): PP-BC8
(Polypropylene (PP); manufactured by Nippon Polychem Co., Ltd.), crystallinity: Tm166 ° C., ΔH82 mJ / mg,
MFR 1.8 g / 10 min (11) Inorganic filler component (k): Chlorite (CR-33
0) (trademark; manufactured by Sankyo Seiko Co., Ltd.); MgO: 41%,
SiO ₂ : 25%, Al ₂ O ₃ : 20%, average particle size: 1
0.6 μm (12) Hindered Phenol / Phosphite / Lactone Composite Antioxidant Component (l): HP2215 (manufactured by Ciba Specialty Chemicals)

Examples 1 to 4 and Comparative Examples 1 to 6 Using the components in the amounts shown in Tables 1 and 2, the composition was put into a 20-liter pressure kneader, and the vapor pressure was 3.0 kg in gauge pressure. Kneading was performed for 10 minutes until the temperature reached 180 ° C./cm ² . Then, L / D = 20 having a rotary cutter at the tip, kneading temperature 140 ° C., screw rotation speed 8
Pelletized with a single screw extruder at 0 rpm. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Tables 1 and 2.

[0091]

[Table 1]

[0092]

[Table 2]

As is clear from Table 1, the thermoplastic elastomer compositions of the present invention of Examples 1 to 3 are not limited to the presence or absence of optional components (e) to (l). The composition also showed good properties. In Example 4, the bending fatigue property was 2.5 million times. Also,
The bending fatigue property of Example 3 was 5 million times or more.

In Example 1, part or all of the component (h) was replaced by Tuftec PJT-90C (styrene-butadiene / butylene-styrene copolymer manufactured by Asahi Kasei; SBBS, styrene content 30% by weight, weight). Average molecular weight (Mw): 110,000, number average molecular weight (M
n): 99,000, molecular weight distribution: 1.11, butadiene block hydrogenation rate: 75.1%, (1,2-butadiene hydrogenation rate 92.7%, 1,4-butadiene hydrogenation rate 61.0%)), and similarly good results were obtained. The hydrogenation rate is ¹ H-
It was measured by NMR measurement.

The method for measuring the hydrogenation rate of the conjugated diene block portion was as follows. A sample was taken in an NMR sample tube (5 mmφ), deuterated chloroform was added, and the sample was sufficiently dissolved. Nuclear magnetic resonance apparatus (NMR) manufactured by JEOL Ltd. room temperature using a GSX-400 type, at 400 MHz, 3029 times of integration ¹ H-
NMR measurement was performed.

On the other hand, as is clear from Table 2, Comparative Example 1
And 2 are those in which the compounding amount of the component (b) is out of the range of the present invention. If the component (b) is too small, the thermoplastic elastomer composition obtained will have poor moldability and oil resistance.
When the amount of the component (b) is too large, the resulting thermoplastic elastomer composition becomes extremely sticky, and peeling, deformation, and flow marks are likely to occur in the molded product. In addition, the deterioration of mechanical properties becomes remarkable. In Comparative Examples 3 and 4, the compounding amount of the component (c) was out of the range of the present invention. If the amount of the component (c) is too small, the compatibility of the component (b) with the component (a) and other compounds will not be sufficient, resulting in peeling of the surface layer and flow marks on the molded article made of the thermoplastic elastomer composition obtained. Moldability deteriorates. If the amount of component (c) is too large, the thermoplastic elastomer composition obtained will have poor moldability. In addition, the mechanical properties are reduced. In Comparative Examples 5 and 6, the compounding amount of the component (d) was out of the range of the present invention. If the amount of component (d) is too small, sufficient polar groups cannot be introduced and crosslinked, and the moldability and oil resistance of the resulting thermoplastic elastomer composition deteriorate. If the amount of component (d) is too large, the thermoplastic elastomer composition obtained will have poor moldability. Also, the stickiness becomes severe.

[0097]

Since the thermoplastic elastomer composition of the present invention is excellent in heat distortion resistance, oil resistance, extrusion moldability, injection moldability, etc., it is used as a material for interior / exterior members of automobiles, members for construction, members for home appliances and the like. In particular, since it is excellent in oil resistance to fuel oil, it can be used as a material for a portion where oil resistance is required, such as an engine peripheral member of an automobile or a fuel system peripheral member.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 53/02 C08L 53/02 (72) Inventor Takaaki Suka 3-11-5 Nihonbashihonmachi, Chuo-ku, Tokyo RIKEN TECHNOS CORPORATION Inner F-term (reference) 4J002 AC033 BB05W BB125 BB145 BB15W BP01X BP014 EH046 EL146 FD010 FD020 FD027 FD070 FD156 GB01 GC00 GG01 GJ02 GL00 GN00 GQ01 4J026 AA AC AC AC AC AC AC AC AC AC AC AC AC 27 AC27 DB12 AC12 AC15 AC07 DB27 AC23 AC18 AC27 AC23 AC02 AC11 AC02 DB23 AC16 AC02 AC11 AC02 DB23 AC16 AC02 AC11 AC02 AC23 AC02 AC11 AC02 AC11

Claims (11)

[Claims] 1. (a) Olefin-based copolymer rubber 100
A block copolymer 25 consisting of (b) at least two polymer blocks A mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound with respect to parts by weight. Thermoplastic elastomer obtained by melt-kneading a composition containing 400 parts by weight, (c) 1 to 50 parts by weight of liquid polybutadiene having a hydroxyl group at the terminal, and (d) 0.01 to 3 parts by weight of organic peroxide. Composition. 2. (e) Ester-based crosslinking aid 0.1 to 20
The thermoplastic elastomer composition according to claim 1, further comprising parts by weight. 3. The thermoplastic elastomer composition according to claim 1, further comprising (f) 0.1 to 5 parts by weight of an unsaturated glycidyl compound or a derivative thereof. 4. The thermoplastic elastomer composition according to claim 1, which further comprises (g) 0.1 to 5 parts by weight of an unsaturated carboxylic acid or a derivative thereof. 5. The (a) olefin-based copolymer rubber is D
Crystallinity of polyolefin by SC measurement is 20wt%
Below, Mooney viscosity (ML _{1 + 4} , test temperature 100 ° C)
Is 7 to 90, The thermoplastic elastomer composition according to any one of claims 1 to 4. 6. The aromatic vinyl compound of the block copolymer (b) is styrene, and the content of the styrene is from 20 to 20.
45 wt%, and the (b) block copolymer has a 5 wt% toluene solution viscosity at 25 ° C. (ASTM D-21
96) is 5-500 cps, The thermoplastic elastomer composition according to any one of claims 1-5. 7. The thermoplastic elastomer composition according to any one of claims 1 to 6, further comprising (h) 1 to 30 parts by weight of a hydrogenated block copolymer. 8. The thermoplastic elastomer composition according to claim 1, further comprising (i) 1 to 80 parts by weight of a softening agent for rubber. 9. The thermoplastic elastomer composition according to claim 1, further comprising (j) 3 to 150 parts by weight of an olefin resin. 10. The thermoplastic elastomer composition according to claim 1, further comprising (k) 1 to 150 parts by weight of an inorganic filler. 11. An automobile interior / exterior member, a building member, or a home appliance member obtained by molding the thermoplastic elastomer composition according to claim 1. Description: