JPH11335501A - Thermoplastic elastomer and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer which, not only prevents blocking of its ethylene-α-olefin-nonconjugated polyene copolymeric rubber, and has a high strength and a high elongation, but also is excellent in impact resistance as well as rubbery properties, and can further form a molded article having a good skin and an excellent appearance. SOLUTION: This is a thermoplastic elastomer comprising an ethylene-α- olefin-nonconjugated polyene copolymeric rubber (A) consisting of ethylene, a 3-20 C α-olefin and a nonconjugated polyene together with a polyolefin resin (B), and having the copolymeric rubber (A) at least party cross-linked in a shape of cross-linked particles, wherein the cross-linked particles of the copolymeric rubber (A) are dispersed, as a dispersed phase (an island phase) in the matrix phase (the sea phase) made of the polyolefin resin (B) providing an island-in-the-sea structure, and a part of the polyolefin resin (B) is dispersed in the cross-linked particles of the copolymeric rubber (A) with an average dispersed particle size of 0.5 μm or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic elastomer comprising an ethylene / α-olefin / non-conjugated polyene copolymer rubber and a polyolefin resin, and a method for producing the same.

[0002]

2. Description of the Related Art Ethylene / α-olefin / non-conjugated polyene copolymer rubber is excellent in ozone resistance, heat resistance, weather resistance, cold resistance, heat stability, etc., and is therefore used for covering automobile parts, electric wires, and building. It is widely used as a material for applications. However, the ethylene / α-olefin / non-conjugated polyene copolymer rubber easily blocks and sticks even when stored in a pellet form. Therefore, ethylene-α-
Olefin and non-conjugated polyene copolymer rubbers are stored in a low-temperature warehouse, and when manufacturing compounded rubber, special processes are required, such as the need for a pre-process of loosening the blocked rubber with a crusher before supplying it to the extruder. Equipment and equipment are required.

Further, in order to prevent blocking of ethylene / α-olefin / non-conjugated polyene copolymer rubber,
The rubber surface is also coated with an antiblocking agent, and a metal salt of a higher fatty acid or an inorganic filler such as talc is used as the antiblocking agent. However, metal salts of higher fatty acids tend to cause bleed-out and fogging, and inorganic fillers tend to absorb moisture and cause poor molding appearance.

[0004] By the way, olefin-based thermoplastic elastomers containing ethylene / α-olefin / non-conjugated polyene copolymer rubber as a main component are lightweight and easy to recycle. In particular, it is widely used as a substitute for vulcanized rubber for automobile parts, industrial machine parts, electronic / electric parts, building materials and the like. However, conventional olefin-based thermoplastic elastomers have a problem that rubber properties such as impact resistance and rubber elasticity are inferior to vulcanized rubber.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ethylene / α-olefin / non-conjugated polyene copolymer rubber as a main component, high strength and high elongation, impact resistance and rubber-like properties. An object of the present invention is to provide a thermoplastic elastomer which is excellent in properties and can obtain a molded article having good skin and excellent appearance. Another object of the present invention is to use ethylene / α-olefin / non-conjugated polyene copolymer rubber as a main component, have high strength and high elongation, and have excellent impact resistance and rubber-like properties, and furthermore, skin Thermoplastic elastomers that can obtain good molded products with excellent appearance,
An object of the present invention is to propose a method for producing a thermoplastic elastomer which can prevent the blocking of an ethylene / α-olefin / non-conjugated polyene copolymer rubber and can be produced easily and efficiently.

[0006]

SUMMARY OF THE INVENTION The present invention relates to the following thermoplastic elastomer and a method for producing the same. (1) An ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising (A) ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and (B) a polyolefin resin; At least a part of the olefin / non-conjugated polyene copolymer rubber (A) is a thermoplastic elastomer which is a crosslinked particle,
Sea-island where crosslinked particles of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) are dispersed as a dispersed phase (island phase) in a matrix phase (sea phase) composed of polyolefin resin (B) A part of the polyolefin resin (B) is dispersed in the crosslinked particles of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) with an average dispersed particle diameter of 0.5 μm or less. Thermoplastic elastomer. (2) The average dispersed particle diameter of the crosslinked particles of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is 0.5 μm.
m. The thermoplastic elastomer according to the above (1), which has a length of more than m and not more than 10 μm. (3) (A) an ethylene / α-olefin / non-conjugated polyene copolymer rubber composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and (B) a polyolefin resin, -Dynamically heat-treating a rubber compound (C) in which a polyolefin resin (B) is dispersed in an olefin / non-conjugated polyene copolymer rubber (A) with an average dispersed particle diameter of 3 μm or less in the presence of a crosslinking agent; The thermoplastic elastomer according to the above (1) or (2), which is obtained by performing (4) An ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising (A) ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and (B) a polyolefin resin; -Dynamically heat treating a rubber compound (C) in which a polyolefin resin (B) is dispersed in an olefin / non-conjugated polyene copolymer rubber (A) with an average dispersed particle diameter of 3 μm or less in the presence of a crosslinking agent. The crosslinked particles of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) are dispersed in a matrix phase (sea phase) composed of polyolefin resin (B). It has a sea-island structure dispersed as (island phase), and in the crosslinked particles of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A),
A thermoplastic elastomer in which a part of the polyolefin resin (B) is dispersed with an average dispersed particle size of 0.5 μm or less. (5) The above (1) to (5), wherein the content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is 40 to 95% by weight and the content of the polyolefin resin (B) is 60 to 5% by weight. The thermoplastic elastomer according to any of (4). (6) Kneading (A) an ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and (B) a polyolefin resin; A rubber compound (C) is prepared by dispersing a polyolefin resin (B) in an α-olefin / non-conjugated polyene copolymer rubber (A) with an average dispersed particle diameter of 3 μm or less, and then prepares the rubber compound (C) For producing a thermoplastic elastomer by dynamically heat-treating a thermoplastic elastomer in the presence of a crosslinking agent. (7) 60-97% by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and 40-3% by weight of a polyolefin resin (B) are kneaded to obtain a rubber compound (C).
The production method according to (6) above, wherein

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention comprises ethylene and
An ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained by random copolymerization of an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

The α-olefin is an α-olefin having 3 to 20 carbon atoms.
-Olefins, among them propylene, 1-butene,
Α-olefins having 3 to 10 carbon atoms such as 4-methyl-1-pentene, 1-hexene and 1-octene are preferred, and propylene and 1-butene are particularly preferred. That is, as the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention, ethylene / propylene /
Non-conjugated polyene copolymer rubber, ethylene / 1-butene
Non-conjugated polyene copolymer rubbers are preferred.

As the non-conjugated polyene, a cyclic or chain non-conjugated polyene is used. Examples of the cyclic non-conjugated polyene include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, and methyltetrahydroindene. Examples of the chain non-conjugated polyene include 1,4-hexadiene and 7-methyl-1,6.
-Octadiene, 8-methyl-4-ethylidene-1,7
-Nonadiene, 4-ethylidene-1,7-undecadiene and the like. These non-conjugated polyenes are used alone or in combination of two or more.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention comprises ethylene, α
The ethylene content is 50 to 90 mol%, preferably 50 to 85 mol%, more preferably 50 to 75 mol%, and the α-olefin content is 9 to the total of the olefin and the non-conjugated polyene monomer; It is desirable that the amount is from 0.5 to 49.5 mol%, preferably from 14.5 to 49.5 mol%, more preferably from 24.5 to 49.5 mol%.
The copolymerization amount of the non-conjugated polyene is from 1 to 4 in iodine value.
0, preferably 2 to 35, more preferably 3 to 30. When the ethylene content in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is low, for example, 50 to 75 mol%, the obtained thermoplastic elastomer has particularly good compression set at low temperature. Become.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention has a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 50 or more at 100 ° C.
Preferably it is 50-250.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention has an intrinsic viscosity [η] of 0.8 to 4 dl / g measured at 135 ° C. in decalin (decahydronaphthalene). , Preferably 1 to 3.5 d
l / g, more preferably 1.1 to 3 dl / g.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) may be a modified product obtained by graft copolymerization of an unsaturated carboxylic acid or a derivative thereof, for example, an acid anhydride. Further, the oil may be oil-extended with a known oil (softening agent) such as a process oil. Ethylene ・ α
-As the olefin / non-conjugated polyene copolymer rubber (A), an ethylene / propylene / non-conjugated diene copolymer rubber is most preferable.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) can be used alone or in combination of two or more. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having the above properties is described in “Polymer Production Process (published by Industrial Research Institute, Inc., pp. 309-33).
0) "and the like.

The polyolefin resin (B) used in the present invention
May be a crystalline resin or an amorphous resin, but a crystalline resin is preferred. Examples of the crystalline resin used as the polyolefin resin (B) in the present invention include a homopolymer or a copolymer of an α-olefin having 2 to 12 carbon atoms.

This polymerization mode may be any of random polymerization and block polymerization. In the case of a random copolymer, an α-olefin copolymer in which the smaller α-olefin structural unit is usually contained in an amount of 40 mol% or less, preferably 30 mol% or less is preferable. Examples of the α-olefin having 2 to 12 carbon atoms include ethylene, propylene, 1-butene,
Examples include 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like.

As the crystalline polyolefin resin (B), polypropylene and polybutene are preferred, and polypropylene is particularly preferred. Specific examples of polypropylene and polybutene include propylene homopolymer,
Copolymer of propylene and one or more α-olefins having 2 to 12 carbon atoms, homopolymer of 1-butene, copolymer of 1-butene and one or more α-olefins of 2 to 12 carbon atoms Is preferred. In the case of a copolymer, propylene or 1-
The content of the α-olefin copolymerized with butene is 1 to 30.
It is desirably in the range of 1 mol%, preferably 1 to 20 mol%. 230 ° C, 2.16 kg for polypropylene
The melt flow rate measured by load is 0.1 to 50 g /
It is desirably 10 minutes, preferably 0.3 to 30 g / 10 minutes.

In the present invention, the polyolefin resin (B)
Examples of the amorphous resin used include ethylene / cyclic olefin copolymer. The polyolefin (B) can be used alone or in combination of two or more.

The polyolefin resin (B) used in the present invention
It is desirable that the resin has a Vicat softening point (temperature) measured by ASTM D1525 of 100 ° C. or higher, preferably 110 ° C. or higher, more preferably 120 to 250 ° C.

The thermoplastic elastomer of the present invention contains the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and a polyolefin resin (B). At least a part, preferably most or all of the polymer rubber (A) is a thermoplastic elastomer which is crosslinked particles. And this thermoplastic elastomer has a phase structure. That is, in the thermoplastic elastomer of the present invention, crosslinked particles of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) are dispersed in a matrix phase (sea phase) composed of polyolefin resin (B). A part of the polyolefin resin (B) in the crosslinked particles of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having a sea-island structure dispersed as an And preferably a thermoplastic elastomer dispersed with an average dispersed particle size of 0.3 to 0.03 μm. The average dispersed particle diameter of the crosslinked particles of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) dispersed in the matrix phase composed of the polyolefin resin (B) is 0.5 μm.
Over 10 μm, preferably over 0.5 μm and 5 μm
m or less. The average dispersed particle size is
The section of the elastomer can be stained with a heavy metal and determined from a photograph taken with an electron microscope such as a transmission electron microscope.

The content of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and polyolefin resin (B) in the thermoplastic elastomer of the present invention is based on the total amount of both. The non-conjugated polyene copolymer rubber (A) is 40 to 95% by weight, preferably 45 to 90% by weight, and more preferably 55 to 90% by weight.
% By weight, the polyolefin resin (B) is 60 to 5% by weight,
Preferably 55 to 10% by weight, more preferably 45 to 45% by weight.
Preferably, it is 10% by weight. The content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is the total amount of crosslinked particles and uncrosslinked copolymer rubber. When the content of both components is in the above range,
Thermoplastic elastomers are particularly excellent in strength, elongation, impact resistance and rubbery properties.

The thermoplastic elastomer of the present invention may be used, if necessary, in addition to the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the polyolefin resin (B) as long as the object of the present invention is not impaired. Further, other rubbers or additives other than the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) may be contained as other components.

Examples of the other rubber include diene rubbers such as styrene / butadiene rubber (SBR), styrene / butadiene / styrene block copolymer rubber, nitrile rubber (NBR), natural rubber (NR), and butyl rubber (IIR). , Polyisobutylene rubber and hydrogenated products thereof. The content of the other rubber is 30% by weight or less, preferably 5% by weight, as the content in the thermoplastic elastomer.
It is desirably about 25% by weight.

Examples of the additives include known additives which are usually added to rubber, such as softeners, heat stabilizers, anti-aging agents, weather stabilizers, antistatic agents, fillers, coloring agents and lubricants. .

As the above-mentioned softening agent, a softening agent usually used for rubber is suitable, and specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tar; Coal tars such as coal tar pitch; castor oil, linseed oil,
Fatty oils such as rapeseed oil, soybean oil, and coconut oil; waxes such as tall oil, beeswax, carnauba wax, and lanolin; fatty acids such as ricinoleic acid, palmitic acid, and stearic acid or metal salts thereof; petroleum resins, cumarone indene resins And synthetic polymers such as atactic polypropylene and the like; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; and other examples include microcrystalline wax, liquid polybutadiene or a modified or hydrogenated product thereof, and liquid thiocol.

The thermoplastic elastomer of the present invention having the above-mentioned phase structure is obtained by kneading an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and a polyolefin resin (B). And the polyolefin resin (B) in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) has an average dispersed particle size of 3 μm or less, preferably 2 μm or less, and more preferably 1.5 μm or less. It can be prepared by preparing a dispersed rubber compound (C) and then dynamically heat treating the rubber compound (C) in the presence of a crosslinking agent. The term "dynamically heat-treating" refers to kneading the rubber compound (C) in a molten (melted) state. The average dispersed particle diameter can be determined from a photograph of a section of the rubber compound (C) stained with a heavy metal and taken with an electron microscope such as a transmission electron microscope.

The rubber compound (C) comprises a polyolefin resin (B) in a matrix phase (sea phase) comprising an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A).
Has a sea-island structure in which the particles of (a) are microscopically dispersed as a dispersed phase (island phase). The rubber compound (C) having such a phase structure is dynamically heat-treated in the presence of a crosslinking agent. As a result, the cross-linking reaction proceeds and the polyolefin resin (B) is decomposed and the phase state is changed, so that the ethylene / α-olefin / non-conjugated phase is contained in the matrix phase (sea phase) composed of the polyolefin resin (B). A sea-island structure is formed in which crosslinked particles of the polyene copolymer rubber (A) are dispersed as a dispersed phase (island phase). The polyolefin resin (B) is dispersed in the crosslinked particles of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) formed at this time.

In the rubber compound (C), the average dispersed particle diameter of the polyolefin resin (B) exceeds 3 μm, and the polyolefin resin (B) is composed of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A ) Is too good, for example, when the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the polyolefin resin (B) are compatible at the molecular level, the rubber compound (C) becomes Blocking tends to occur, and the strength, elongation, impact resistance and rubber properties of the resulting thermoplastic elastomer are reduced. Therefore, the types of the polyolefin resin (B) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) are selected within a range in which both are not compatible at the molecular level, and are dispersed at the average dispersed particle diameter. There is a need.

The aspect ratio (major axis / minor axis) of the dispersed particles of the polyolefin resin (B) in the compound (C) is desirably 5 or less, preferably 1 to 3. When the aspect ratio is 5 or less, the dispersion of the polyolefin resin (B) is good.

The content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the polyolefin resin (B) in the rubber compound (C) is based on the total amount of the ethylene / α-olefin and the polyolefin resin (B). The non-conjugated polyene copolymer rubber (A) is 60 to 97% by weight, preferably 70 to 95%
% By weight, 40 to 3% by weight of the polyolefin resin (B),
Preferably, it is 30 to 5% by weight. When the content is in the above range, the rubber compound (C) is difficult to block. The finally obtained thermoplastic elastomer is particularly excellent in strength, elongation, impact resistance and rubber properties.

An organic peroxide can be used as a cross-linking agent used in performing the dynamic heat treatment. Specific examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexane, 2,5-dimethyl
-2,5-di (tert-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
Examples include t-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.

Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert) are preferable in terms of odor and scorch stability. -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 is preferred, and 1,3-bis (tert-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane are most preferred.

The organic peroxide is used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the total of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), the polyolefin resin (B) and the other rubber. Preferably, it is used in a proportion of 0.2 to 2 parts by weight.

When the above-mentioned organic peroxide is used, a crosslinking aid may be added. Specific examples of the crosslinking assistant include divinyl compounds such as divinylbenzene;
Oxime compounds such as quinone dioxime and p, p'-dibenzoylquinone dioxime; nitroso compounds such as N-methyl-N-4-dinitrosoaniline and nitrosobenzene; trimethylolpropane-N, N'-m-phenyl Maleimide compounds such as range maleimide; and other examples include sulfur, diphenylguanidine, triallyl cyanurate and the like. Other cross-linking aids include polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate; vinyl butyrate,
Examples include polyfunctional vinyl monomers such as vinyl stearate.

When dynamically heat-treating using an organic peroxide, a uniform and mild crosslinking reaction can be expected by using the above-mentioned crosslinking aid in combination. Among the crosslinking assistants, divinylbenzene is most preferred. Divinylbenzene is easy to handle, has good compatibility with the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and polyolefin resin (B) which are the main components of the rubber compound (C), and has good organic compatibility. It has the effect of solubilizing peroxide and works as a dispersant for organic peroxide, so that a thermoplastic elastomer with a uniform cross-linking effect by dynamic heat treatment and a good balance between fluidity and physical properties can be obtained. .

The crosslinking aid is used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the total of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), the polyolefin resin (B) and the other rubber. Preferably, it is used in a proportion of 0.2 to 2 parts by weight. When the blending ratio of the crosslinking aid is within the above range, the obtained thermoplastic elastomer has physical properties due to heat history during processing and molding because the crosslinking aid does not remain as an unreacted raw material in the thermoplastic elastomer. Does not change, and is excellent in fluidity.

Rubber compound (C) in which polyolefin resin (B) is dispersed in ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) with an average dispersed particle diameter of 3 μm or less.
1) Ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and polyolefin resin (B) are mixed and kneaded in a molten state, and a shearing action (force) is applied to polyolefin resin (B). 2) adding a polyolefin resin (B) to a mixture comprising an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and an organic solvent, and kneading the mixture with the polyolefin resin (B). And a method of removing the solvent. By such a method, the morphology (phase morphology) of the polyolefin resin (B) in the rubber compound (C) can be achieved. However, when the temperature during kneading is low or the shearing energy is insufficient, the polyolefin resin (B) can be obtained. )) Tends to exceed 3 μm.

The preparation of the rubber compound (C) is preferably carried out with a kneading apparatus capable of giving a high shearing force.
Specifically, the mixing can be performed using a kneading device such as a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader, etc.), a single-screw or twin-screw extruder. It is preferred to prepare (C). By kneading with a twin screw extruder, the polyolefin resin (B) has an average dispersed particle diameter of 3 μm.
The dispersed rubber compound (C) can be easily prepared below.

For the preparation of the rubber compound (C), it is possible to use the total amount of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the polyolefin resin (B) to be finally used, Some can also be used. When a part is used, the remainder of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and / or the polyolefin resin (B) is mixed with the rubber compound (C) and the presence of a crosslinking agent Dynamic heat treatment below.

The preparation of the rubber compound (C) is carried out by preparing an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A)
And ethylene-α-olefin / non-conjugated polyene copolymer rubber (A) 60 to 97% by weight, preferably 70 to 95% by weight, and polyolefin resin (B) 40 to 3% by weight based on the total of polyolefin resin (B). %, Preferably 30 to 5% by weight. When the rubber compound (C) is dynamically heat-treated in the presence of a crosslinking agent to obtain a thermoplastic elastomer, a new polyolefin resin (B) is added, and the rubber compound (C) and the polyolefin resin (B) are added. Can be dynamically heat-treated in the presence of a crosslinking agent to obtain the thermoplastic elastomer of the present invention.

When other components are blended into the thermoplastic elastomer of the present invention, a rubber compound (C) is prepared by the above method, and then the other components are added to the rubber compound (C) and kneaded. It is preferable to prepare a rubber compound (C) containing other components. Mixing of other ingredients, mixing roll,
It can be performed using a kneading device such as an intensive mixer (for example, Banbury mixer, kneader, etc.), a single-screw or twin-screw extruder.

In the above method 1), kneading is preferably performed at a temperature not lower than the melting point or glass transition point of the polyolefin resin (B). As a specific method of the above 1), an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and a polyolefin resin (B) are melted at 100 to 300 ° C. for 10 seconds or more by a twin screw extruder. And a method of kneading. At this time, when the polyolefin resin (B) is a propylene homopolymer (B),
At a temperature of 200 ° C., the specific energy of the propylene homopolymer (B) is increased to 0.01 kW · hr / k in a twin-screw extruder.
It is desirable to knead the mixture in a molten state so as to give a g or more, preferably 0.02 kW · hr / kg or more.

As a specific method of the above 2), a mixture consisting of 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and 3 to 10 parts by weight of an organic solvent is extruded in a multistage venting method. The polyolefin resin (B) is introduced into the twin-screw extruder under an inert gas atmosphere while being introduced into the twin-screw extruder from the supply section of the extruder, and the mixture is kneaded with the polyolefin resin (B). ,
A method of removing the solvent and the like can be mentioned.

The dynamic heat treatment is carried out by adding the crosslinking agent and, if necessary, a crosslinking aid to the rubber compound (C) prepared as described above to obtain an ethylene / α-olefin / non-conjugated polyene copolymer. This is performed by kneading the rubber (A) and the polyolefin resin (B) in a molten state. This dynamic heat treatment can be performed using a kneading device such as a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader, etc.), a single-screw or twin-screw extruder, but a twin-screw extruder is preferable. The dynamic heat treatment is preferably performed in a non-open kneading apparatus in an inert gas such as nitrogen.

The dynamic heat treatment is preferably performed at a temperature at which the half life of the organic peroxide used is less than 1 minute.
The kneading temperature is usually 150 to 280 ° C, preferably 170 to 280 ° C.
240 ° C, and the kneading time is 1 to 20 minutes, preferably 1 to 5 minutes. The shearing force applied at the time of kneading is generally determined at a shear rate of 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 ⁴ sec ⁻¹ .

The crosslinking reaction proceeds by the dynamic heat treatment as described above, and the thermoplastic elastomer of the present invention having the above-mentioned phase structure is obtained. In addition, in the static vulcanization performed at the time of producing the vulcanized rubber, since the entire unvulcanized rubber compound is crosslinked, the obtained vulcanized rubber does not become thermoplastic, but the dynamic In the crosslinking by heat treatment,
The whole rubber compound (C) is not crosslinked, and is mainly composed of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A)
Is crosslinked and the decomposition of the polyolefin resin (B) proceeds, so that the obtained elastomer is thermoplastic.

The rubber compound (C) can be dynamically heat-treated following preparation or can be temporarily stored until dynamically heat-treated. Storage can be carried out at room temperature, and in this case, the rubber compound (C) is prevented from blocking, so that the pulverizing step can be omitted and the heat treatment can be performed dynamically as it is.

In the production method of the present invention, the rubber compound (C) in which the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the polyolefin resin (B) are kneaded and the polyolefin resin (B) is dispersed. Is prepared and then heat-treated dynamically to prevent blocking of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and to provide a rubber-like material such as strength, elongation, impact resistance and rubber elasticity. A thermoplastic elastomer having excellent properties can be easily and efficiently produced.

The thermoplastic elastomer of the present invention thus obtained has high strength and high elongation, and is excellent in rubber properties such as impact resistance and rubber elasticity. In addition, since it essentially does not contain unnecessary additives and fillers, the quality is good, and molded products obtained from thermoplastic elastomers, for example, extruded products, do not have bleed out of additives and moisture absorption by additives. Good skin and good appearance.

The thermoplastic elastomer of the present invention has the above-mentioned properties and is an olefin-based thermoplastic elastomer, so it is lightweight and easy to recycle.
Therefore, it can be used as an energy-saving and resource-saving elastomer, and can be widely used as a substitute for vulcanized rubber. Specifically, the thermoplastic elastomer of the present invention can be suitably used in the fields of automobile interior parts and exterior parts, electric / electronic parts, home appliance-related parts, civil engineering / building material-related parts, miscellaneous goods and daily necessities. .

[0051]

The thermoplastic elastomer of the present invention contains an ethylene / α-olefin / non-conjugated polyene copolymer rubber and a polyolefin resin, which have the above-mentioned specific phase structure, and therefore have high strength. Further, it has high elongation, and is excellent in impact resistance and rubber-like properties, and the molded article made of this thermoplastic elastomer has good skin and excellent appearance.

The process for producing a thermoplastic elastomer according to the present invention comprises kneading an ethylene / α-olefin / non-conjugated polyene copolymer rubber and a polyolefin resin,
A rubber compound is prepared by dispersing a polyolefin resin in an α-olefin / non-conjugated polyene copolymer rubber with an average dispersed particle size of 3 μm or less, and then dynamically heat-treating the rubber compound in the presence of a crosslinking agent. Therefore, the above-mentioned thermoplastic elastomer can be easily and efficiently produced by preventing blocking of the ethylene / α-olefin / non-conjugated polyene copolymer rubber.

[0053]

Next, an embodiment of the present invention will be described. The components used in each example are as follows.

(A-1) Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber: ethylene content; 73 mol% iodine value; 12 Mooney viscosity [ML _{1 + 4} (100 ° C.)]; -2) Ethylene propylene-5-ethylidene-2
-Oil extension product of norbornene copolymer rubber: ethylene content; 66 mol% iodine value; 22 Mooney viscosity [ML _{1 + 4} (100 ° C)]; 180 oil extension amount; 40 parts by weight oil per 100 parts by weight of oil; Paraffin-based process oil (Idemitsu Kosan P
W-380, trademark) (A-3) Ethylene propylene / 5-ethylidene-2
-Norbornene copolymer rubber: ethylene content; 81 mol% iodine value; 12 Mooney viscosity [ML _{1 + 4} (100 ° C)];

(A-4) Oil-extended ethylene-propylene-dicyclopentadiene copolymer rubber: ethylene content; 81 mol% iodine value; 12 Mooney viscosity [ML _{1 + 4} (100 ° C.)]; 50 parts by weight with respect to 100 parts by weight of rubber Oil; Paraffin-based process oil (P manufactured by Idemitsu Kosan Co., Ltd.)
W-380, trademark) (A-5) Ethylene propylene / 5-ethylidene-2
-Oil extension of norbornene copolymer rubber: ethylene content; 66 mol% iodine value; 22 Mooney viscosity [ML _{1 + 4} (100 ° C)]; 180 oil extension; 50 parts by weight oil per 100 parts by weight of oil; Paraffin-based process oil (Idemitsu Kosan P
W-380, trademark)

(B-1) Propylene homopolymer: MFR; 10 g / 10 min (B-2) Propylene / ethylene block copolymer: MFR; 10 g / 10 min Ethylene content: 8 mol% (B-3) propylene Ethylene block copolymer: MFR: 1.0 g / 10 min Ethylene content: 8 mol%

(D-1) Hydrogenated product of styrene / butadiene / styrene block copolymer: Styrene content; 30 wt% MFR; 0.3 g / 10 min. Hydrogenation amount based on unsaturated bond of butadiene polymer block; 8% (D-2) butyl rubber masterbatch pellets: butyl rubber [unsaturation; 0.7 mol%, Mooney viscosity [ML _{1 + 4} (100 ° C.)]; 45] and the ethylene / propylene block copolymer (B (D-3) Butyl rubber masterbatch pellet: butyl rubber [unsaturation degree: 0.7 mol%, Mooney viscosity [ML _{1 + 4} (100 ° C.)]] 45] and the propylene / ethylene block copolymer (B-3) blended at a ratio of 60/40 (weight ratio).

Example 1 << Production of rubber compound pellets >> A crumb-shaped ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (A-1) and a propylene homopolymer (B-1) were separately prepared. (A-1) / (B)
-1) = 80/20, and fed to a twin screw extruder, kneaded under the following conditions and rubber compound pellets (C-
1) was produced. Extruder: TEM-50, L / D = 44, manufactured by Toshiba Machine Screw rotation speed: 200 rpm

A section of the obtained rubber compound pellet (C-1) was stained with ruthenic acid, and the phase structure was observed with a transmission electron microscope.
Ethylidene-2-norbornene copolymer rubber (A-1)
The propylene homopolymer (B-1) was dispersed therein, and the average dispersed particle size was 0.5 μm. The rubber compound pellet (C-1) was placed in a 50 mmφ metal cylinder, and a 4 kg load was applied thereto from above.
After leaving at 0 ° C. for 7 days, the load was removed and the blocking state was evaluated according to the following criteria.
Met. << Evaluation of Blocking State Evaluation >> 1: Completely fixed 2: Strongly fixed and difficult to loosen by hand 3: Somewhat firmly fixed, but can be loosened by hand 4: fixed but can be loosened by hand relatively easily 5: not fixed or lightly fixed but easy to loosen by hand

<< Production of Thermoplastic Elastomer >> Next, 100 parts by weight of the obtained rubber compound pellet (C-1) and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane as a crosslinking agent were used. 0.4 parts by weight of divinylbenzene and 0.4 parts by weight of divinylbenzene as a crosslinking aid are sufficiently mixed with a Henschel mixer, supplied to the twin-screw extruder, and dynamically heat-treated under the same conditions as the twin-screw extruder. Then, a thermoplastic elastomer was produced.

A section of the obtained thermoplastic elastomer was stained with ruthenic acid, and the phase structure was observed with a transmission electron microscope. As a result, ethylene-propylene / 5-ethylidene-2 was incorporated into the propylene homopolymer (B-1). -Norbornene copolymer rubber (A-1) particles are dispersed, and propylene homopolymer (B-1) is further contained in ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (A-1) particles. Was dispersed. In addition, ethylene
The average dispersed particle diameter of the propylene / 5-ethylidene-2-norbornene copolymer rubber (A-1) particles is 3 μm, and the propylene homopolymer (B-
The average dispersed particle diameter of 1) was 0.3 μm or less. Further, the obtained thermoplastic elastomer was press-molded at 190 ° C. to produce a sheet having a thickness of 1 mm, according to JIS K630.
A tensile test and a compression set test were performed in accordance with No. 1. Table 1 shows the results.

Comparative Example 1 Crumb-like ethylene / propylene / 5-ethylidene-2
-The norbornene copolymer rubber (A-1) and the propylene homopolymer (B-1) are obtained by dividing (A-1) / (B-1) =
The mixture was supplied to a Banbury mixer so as to have a weight ratio of 80/20, and kneaded to prepare a rubber compound pellet (C-2).

The average dispersed particle size of the propylene homopolymer (B-1) in the obtained rubber compound pellet (C-2) was determined in the same manner as in Example 1, and found to be 4.2 μm. When the blocking properties of the obtained rubber compound pellets (C-2) were evaluated in the same manner as in Example 1, the rating was 3.

Next, the obtained rubber compound pellets (C-
2) 100 parts by weight, 2,5-dimethyl- as a crosslinking agent
2,5-di (tert-butylperoxy) hexane 0.4
Parts by weight, and divinylbenzene 0.4 as a crosslinking aid
Using a part by weight, heat treatment was performed dynamically in the same manner as in Example 1,
A thermoplastic elastomer was produced. Using the obtained thermoplastic elastomer, the average dispersed particle diameter of the particles was determined in the same manner as in Example 1, and a tensile test was performed. Table 1 shows the results. The thermoplastic elastomer of Comparative Example 1 was inferior in tensile strength and elongation as compared with that of Example 1.

Comparative Example 2 Crumb-like ethylene / propylene / 5-ethylidene-2
Example 1 using only -norbornene copolymer rubber (A-1)
In the same manner as in the above, fed to a twin-screw extruder, kneaded and pelletized (C-
3) was produced. When the blocking property of this pellet (C-3) was evaluated in the same manner as in Example 1, the rating was 1 and the blocking was easier than that of the rubber compound pellet of Example 1.

Example 2 Ethylene propylene 5-ethylidene-2 in the form of crumb
-The norbornene copolymer rubber (A-3) and the propylene homopolymer (B-1) are obtained by dividing (A-3) / (B-1) =
A rubber compound pellet (C-4) was produced in the same manner as in Example 1 at a weight ratio of 80/20.

The average dispersed particle size of the propylene homopolymer (B-1) in the obtained rubber compound pellet (C-4) was determined in the same manner as in Example 1, and it was 0.5 μm. When the blocking properties of the obtained rubber compound pellets (C-4) were evaluated in the same manner as in Example 1, the rating was 4.

Next, the obtained rubber compound pellets (C-
4) 100 parts by weight, 2,5-dimethyl- as a crosslinking agent
2,5-di (tert-butylperoxy) hexane 0.4
Parts by weight, and divinylbenzene 0.4 as a crosslinking aid
A heat treatment was dynamically performed from parts by weight in the same manner as in Example 1 to produce a thermoplastic elastomer. Using the obtained thermoplastic elastomer, the average dispersed particle size of the particles was determined in the same manner as in Example 1, and a tensile test and a compression set test were performed. Table 1 shows the results.

Comparative Example 3 Crumb-like ethylene / propylene / 5-ethylidene-2
-The norbornene copolymer rubber (A-3) and the propylene homopolymer (B-1) are obtained by dividing (A-3) / (B-1) =
A rubber compound pellet (C-5) was produced using a Banbury mixer at a weight ratio of 80/20 in the same manner as in Comparative Example 1.

The average dispersed particle size of the propylene homopolymer (B-1) in the obtained rubber compound pellet (C-5) was determined in the same manner as in Example 1, and found to be 4.5 μm. In addition, when the blocking property of the obtained rubber compound pellet (C-5) was evaluated in the same manner as in Example 1, the rating was 3.

Next, the obtained rubber compound pellets (C-
5) 100 parts by weight, 2,5-dimethyl- as a crosslinking agent
2,5-di (tert-butylperoxy) hexane 0.4
Parts by weight, and divinylbenzene 0.4 as a crosslinking aid
A heat treatment was dynamically performed from parts by weight in the same manner as in Example 1 to produce a thermoplastic elastomer. Using the obtained thermoplastic elastomer, the average dispersed particle size of the particles was determined in the same manner as in Example 1, and a tensile test and a compression set test were performed. Table 1 shows the results. The thermoplastic elastomer of Comparative Example 3 was inferior in tensile strength and elongation to those of Example 2.

Example 3 Crumb-form ethylene / propylene / 5-ethylidene-2
-Norbornene copolymer rubber (A-2) and propylene
(A-2) an ethylene block copolymer (B-2)
In the same manner as in Example 1, the mixture was kneaded with a twin-screw extruder so as to obtain a weight ratio of / (B-2) = 70/30 to produce a rubber compound pellet (C-6).

The average dispersed particle size of the propylene homopolymer (B-2) in the obtained rubber compound pellet (C-6) was determined in the same manner as in Example 1, and it was 0.5 μm. In addition, when the blocking properties of the obtained rubber compound pellets (C-6) were evaluated in the same manner as in Example 1, the rating was 4.

Next, the obtained rubber compound pellets (C-
6) 55 parts by weight, a hydrogenated product of a styrene / butadiene / styrene block copolymer (D-1) 15 parts by weight, a butyl rubber masterbatch pellet (D-2) 30 parts by weight,
Dynamically heat treating from 0.3 parts by weight of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane as a crosslinking agent and 0.3 parts by weight of divinylbenzene as a crosslinking aid in the same manner as in Example 1. Was carried out to produce a thermoplastic elastomer. Using the obtained thermoplastic elastomer, the average dispersed particle size of the particles was determined in the same manner as in Example 1, and a tensile test and a compression set test were performed. Table 1 shows the results.

[0075]

[Table 1]

[0076]

[Table 2]

Notes to Tables 1 and 2 * 1 Average dispersed particle diameter of component B: Average dispersed particle diameter of polyolefin resin particles dispersed in the rubber compound.
Unit is μm * 2 Crosslinking agent: 2,5-dimethyl-2,5-di (tert-
Butyl peroxy) hexane * 3 Cross-linking aid: divinylbenzene * 3 Cross-linking aid: divinylbenzene, the unit of blending amount is parts by weight * 4 Ethylene / α-olefin / non-conjugated polyene dispersed in elastomeric polyolefin resin The average dispersed particle diameter of the crosslinked polymer rubber particles, and the unit is μm * 5. The average dispersed particle diameter of the polyolefin resin particles dispersed in the crosslinked rubber particles of the ethylene / α-olefin / non-conjugated polyene copolymer rubber of the elastomer. Yes, unit is μ
m * 6 Tensile strength: conforms to JIS K6301 * 7 Elongation: conforms to JIS K6301 * 8 Compression set: conforms to JIS K6301

Example 4 << Production of Rubber Compound Pellets >>
Propylene / dicyclopentadiene copolymer rubber (A-
4) and propylene homopolymer (B-1) were separated using a separate quantitative feeder to obtain (A-4) / (B-1) = 8
The mixture was fed to a twin-screw extruder at a weight ratio of 2/18 and kneaded under the following conditions to prepare a rubber compound pellet (C-7). Extruder: TEM-50, L / D = 44 manufactured by Toshiba Machine Co., Ltd.-Revolution: 200 rpm

A section of the obtained rubber compound pellet (C-7) was stained with ruthenic acid, and the phase structure was observed with a transmission electron microscope. As a result, ethylene-propylene-dicyclopentadiene copolymer rubber (A In -4), the propylene homopolymer (B-1) was dispersed, and the average dispersed particle size was 0.5 μm.

<< Production of Thermoplastic Elastomer >> Next, 60 parts by weight of the obtained rubber compound pellet (C-7), 40 parts by weight of propylene homopolymer (B-1), and 2,5-dimethyl as a crosslinking agent 0.3 parts by weight of -2,5-di (tert-butylperoxy) hexane and 0.3 parts by weight of divinylbenzene as a crosslinking aid were sufficiently mixed with a Henschel mixer and supplied to the twin-screw extruder. Heat treatment was performed dynamically under the same conditions as the screw extruder to produce a thermoplastic elastomer.

A section of the obtained thermoplastic elastomer was stained with ruthenic acid, and the phase structure was observed with a transmission electron microscope. As a result, ethylene-propylene-dicyclopentadiene copolymer was mixed in the propylene homopolymer (B-1). The particles of the unified rubber (A-4) are dispersed, and the ethylene-propylene-dicyclopentadiene copolymer rubber (A
-4) Propylene homopolymer (B-1) was dispersed in the particles. The average dispersion particle diameter of the ethylene / propylene / dicyclopentadiene copolymer rubber (A-4) particles is 3 μm, and the average dispersion particle diameter of the propylene homopolymer (B-1) dispersed in the particles is 0.1 μm. It was 3 μm or less. -40 ° C according to JISK7110
An Izod impact strength test was conducted. Table 3 shows the results.

Comparative Example 4 49.2 parts by weight of a pellet-like ethylene-propylene-dicyclopentadiene copolymer rubber (A-4) and a propylene homopolymer (B-1) were prepared without preparing a rubber compound in advance. 50.8 parts by weight, 2,5-
Example 4 was prepared by using 0.3 parts by weight of dimethyl-2,5-di (tert-butylperoxy) hexane and 0.3 parts by weight of divinylbenzene as a crosslinking aid (the same composition ratio as the final composition of Example 4). Similarly, heat treatment was performed dynamically to produce a thermoplastic elastomer.

When the phase structure of the obtained thermoplastic elastomer was observed in the same manner as in Example 4, it was confirmed that the propylene homopolymer (B-1) was ethylene-propylene-dicyclopentadiene copolymer rubber as in Example 4. No structure dispersed in (A-4) was observed. Further, when an Izod impact strength test was conducted at −40 ° C. in the same manner as in Example 4, the impact strength was inferior to that of Example 4.
Table 3 shows the results.

Example 5 Ethyl propylene-5-ethylidene-2 in the form of crumb
-Norbornene copolymer rubber (A-5) and propylene
The ethylene block copolymer (B-3) was compared with (A-5) / (B-3) = 75 / using separate quantitative feeders.
The mixture was supplied to a twin-screw extruder at a weight ratio of 25, and kneaded in the same manner as in Example 4 to produce a rubber compound pellet (C-8).

Next, the obtained rubber compound pellet (C-
8) 80 parts by weight, 20 parts by weight of a butyl rubber masterbatch pellet (D-3), 0.2% of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane as a crosslinking agent.
4 parts by weight, and 0.1 parts of divinylbenzene as a crosslinking aid.
Four parts by weight were sufficiently mixed with a Hensiel mixer, supplied to the twin-screw extruder, and dynamically heat-treated under the same conditions as in Example 4 to produce a thermoplastic elastomer.

When the phase structure of the obtained thermoplastic elastomer was observed in the same manner as in Example 4, the propylene / ethylene block copolymer (B-3) was found to be ethylene / propylene / 5-ethylidene-2-norbornene copolymer. Rubber (A
-5) and has an average dispersed particle size of 0.3
μm or less. Further, a compression set test was carried out in accordance with JIS K6301, and an Izod impact test was carried out at -40 ° C. in accordance with JIS K7110. Table 3 shows the results.

Comparative Example 5 A crumb-like ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (A-5) (60 parts by weight) and a propylene / ethylene block copolymer were prepared without preparing a rubber compound in advance. (B-3) 20 parts by weight, butyl rubber masterbatch pellet (D-3) 20 parts by weight, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane 0.4 part by weight as a crosslinking agent, and A heat treatment was carried out dynamically from 0.4 parts by weight of divinylbenzene (the same composition ratio as the final composition of Example 5) as a crosslinking aid in the same manner as in Example 4 to produce a thermoplastic elastomer.

The phase structure of the obtained thermoplastic elastomer was observed in the same manner as in Example 4. As shown in Example 5, the propylene / ethylene block copolymer (B-3) was ethylene-propylene / 5-ethylidene- No structure dispersed in the 2-norbornene copolymer rubber (A-5) was observed. Further, a compression set test was carried out in accordance with JIS K6301, and an Izod impact test was carried out at -40 ° C. in accordance with JIS K7110. The compression set at -20 ° C was particularly inferior to Example 5. Table 3 shows the results.

[0089]

[Table 3] * 1 Average dispersed particle diameter of B component: Average dispersed particle diameter of polyolefin resin particles dispersed in a rubber compound, unit is μm * 2 Crosslinking agent: 2,5-dimethyl-2,5-di ( tert-butylperoxy) hexane, unit of blending amount is parts by weight * 3 Crosslinking aid: divinylbenzene, unit of blending amount is parts by weight * 4 Ethylene / α-olefin / dispersed in elastomeric polyolefin resin Average dispersed particle size of non-conjugated polyene copolymer rubber crosslinked particles * 5 Average dispersed particle size of polyolefin resin particles dispersed in elastomeric ethylene / α-olefin / nonconjugated polyene copolymer rubber crosslinked particles * 6 40 parts by weight of propylene homopolymer (B-1) was added to 60 parts by weight of the rubber compound (C-7), and dynamic heat treatment was performed.

Claims (7)

[Claims] (A) ethylene, α- having 3 to 20 carbon atoms
Ethylene / α consisting of olefin and non-conjugated polyene
An olefin / non-conjugated polyene copolymer rubber; and (B) a polyolefin resin, wherein at least a part of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is a crosslinked particle which is crosslinked. A crosslinked particle of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) in a matrix phase (sea phase) composed of a polyolefin resin (B), which is a plastic elastomer, and a dispersed phase (island phase) Having a sea-island structure dispersed in the crosslinked particles of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), wherein a part of the polyolefin resin (B) has an average dispersion of 0.5 μm or less. Thermoplastic elastomer dispersed in particle size. 2. The thermoplastic elastomer according to claim 1, wherein the average dispersed particle size of the crosslinked particles of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is more than 0.5 μm and 10 μm or less. (A) ethylene, α- having 3 to 20 carbon atoms
Ethylene / α consisting of olefin and non-conjugated polyene
-An olefin / non-conjugated polyene copolymer rubber; and (B) a polyolefin resin, wherein the polyolefin resin (B) has an average dispersed particle diameter of 3 µm in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). 3. The thermoplastic elastomer according to claim 1, which is obtained by dynamically heat-treating a rubber compound (C) dispersed below in the presence of a crosslinking agent. (A) ethylene, α- having 3 to 20 carbon atoms
Ethylene / α consisting of olefin and non-conjugated polyene
-An olefin / non-conjugated polyene copolymer rubber; and (B) a polyolefin resin, wherein the polyolefin resin (B) has an average dispersed particle diameter of 3 µm in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). A thermoplastic elastomer obtained by dynamically heat-treating a rubber compound (C) dispersed below in the presence of a cross-linking agent, wherein said thermoplastic elastomer is a thermoplastic elastomer (B) comprising a matrix phase (sea phase) Has a sea-island structure in which crosslinked particles of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) are dispersed as a dispersed phase (island phase); A thermoplastic elastomer in which a part of the polyolefin resin (B) is dispersed in the crosslinked particles of the polymer rubber (A) with an average dispersed particle diameter of 0.5 μm or less. 5. An ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having a content of 40 to 95% by weight,
5. The thermoplastic elastomer according to claim 1, wherein the content of the polyolefin resin (B) is 60 to 5% by weight. 6. (A) ethylene, α- having 3 to 20 carbon atoms
Ethylene / α consisting of olefin and non-conjugated polyene
An olefin / non-conjugated polyene copolymer rubber and (B) a polyolefin resin are kneaded, and the average dispersion particle diameter of the polyolefin resin (B) in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is kneaded. A method for producing a thermoplastic elastomer, comprising preparing a rubber compound (C) dispersed at 3 μm or less, and then dynamically heat-treating the rubber compound (C) in the presence of a crosslinking agent. 7. A rubber compound (C) obtained by kneading 60 to 97% by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and 40 to 3% by weight of a polyolefin resin (B). The production method according to claim 6, which is prepared.