JP2014208740A - Rubber composition pellet - Google Patents

Abstract

To provide a rubber composition pellet containing an ethylene / α-olefin / non-conjugated polyene copolymer which is less likely to be blocked and has good low-temperature characteristics. A rubber containing ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, a nonconjugated polyene (C), and an ethylene / α-olefin / nonconjugated polyene copolymer containing a structural unit. Composition pellet [I], (1) In the ethylene / α-olefin / non-conjugated polyene copolymer, a structural unit derived from ethylene (A) and a structural unit derived from α-olefin (B) The molar ratio [(A) / (B)] is 50/50 to 75/25, and (2) in the ethylene / α-olefin / nonconjugated polyene copolymer, (3) at least of polyethylene and polypropylene A rubber composition pellet comprising any one of them. [Selection figure] None

Description

  The present invention relates to a rubber composition pellet, and more particularly to a rubber composition pellet containing an ethylene / α-olefin / non-conjugated polyene copolymer and a polyolefin.

  In recent years, thermoplastic elastomers have been actively studied as recyclable rubber materials. Thermoplastic elastomers exhibit rubber elasticity like normal vulcanized rubber at room temperature, and the matrix phase plasticizes and flows at high temperatures, and can be handled in the same way as thermoplastic resins. Furthermore, energy saving and productivity improvement are possible compared with vulcanized rubber. Due to these characteristics, demand for thermoplastic elastomers is increasing mainly in the fields of automobiles, building materials, sporting goods, medical applications and industrial parts.

  Olefin-based thermoplastic elastomers are broadly classified into crosslinked and non-crosslinked types. From the viewpoint of tensile strength, elongation at break, rubber properties (for example, permanent elongation, compression set) and heat resistance, non-crosslinked types. Cross-linked olefinic thermoplastic elastomers are superior to these olefinic thermoplastic elastomers. This is widely known as described in detail in A. Y. Coran et al. (Rubber Chemistry and Technology, Volume 53 (1980), P141).

  Since the ethylene / α-olefin / non-conjugated polyene copolymer does not have an unsaturated bond in the main chain, it is superior in weather resistance, heat resistance, and ozone resistance as compared with a conjugated diene rubber. An ethylene / α-olefin / non-conjugated polyene copolymer, a rubber composition containing an ethylene / α-olefin / non-conjugated polyene copolymer, and a crosslinked product of the rubber composition utilize the above properties, It is widely used for rubber products such as industrial rubber products, electrical insulation materials, civil engineering materials, and rubberized fabrics.

  In recent years, thermoplastic elastomer compositions that do not require a vulcanization step have started to be used from the viewpoint of productivity, environmental friendliness, and weight reduction in place of the crosslinked rubber composition. Among them, the dynamically cross-linked olefin-based thermoplastic elastomer has many heat resistance and weather resistance, and is therefore widely used for automobile weather strip applications. Generally, a dynamically crosslinked olefin-based thermoplastic elastomer is produced by dynamically crosslinking a thermoplastic resin typified by polypropylene and an ethylene / α-olefin / nonconjugated polyene copolymer together with a crosslinking agent in an extruder. .

  The ethylene / α-olefin / non-conjugated polyene copolymer is usually used after being pelletized. In addition, a polyolefin such as polypropylene may be mixed with an ethylene / α-olefin / non-conjugated polyene copolymer to form an alloy and then pelletized. However, conventional ethylene / α-olefin / non-conjugated polyene copolymers sometimes have poor dispersibility with polypropylene or the like. In addition, rubber pellets obtained by alloying ethylene / α-olefin / non-conjugated polyene copolymers and polyolefins are highly adhesive, so they can be used in production and shipping processes and final product manufacturing and processing processes. It becomes difficult to supply and transport, and weighing becomes difficult. In addition, the pellets stick together during pellet storage and become a large lump, causing a so-called blocking phenomenon, which hardens in the storage tank and cannot be discharged, or hardens in a filled bag or container, making it difficult to use There is a problem that becomes. This blocking phenomenon becomes more prominent as the outside air temperature during storage is higher and the difference in temperature during storage is larger.

  As a method of preventing blocking of rubber pellets, a method of coating pellets with various fatty acids, a method of coating pellets with various fatty acid amides, a method of coating pellets with various waxes, and inorganic fine powders such as silica, talc and mica A method of coating the surface of the pellet with an anti-sticking agent has been proposed, such as a method of coating the pellet. However, in this method, since the anti-blocking agent is mixed into the resin processed product, the product physical properties are adversely affected, and the transparency, mechanical properties, adhesiveness or appearance are impaired, or the anti-blocking agent such as calcium stearate. Sometimes agglomerates in the molding machine, causing contamination of the apparatus.

  As a method for preventing blocking of rubber pellets, a method for increasing the ethylene content of an ethylene / α-olefin / nonconjugated polyene copolymer is known. However, this method has a problem that if the ethylene content is too high, the low-temperature characteristics are deteriorated.

  Patent Documents 1 to 3 are cited as documents relating to a technique for obtaining a thermoplastic elastomer containing an ethylene / α-olefin / nonconjugated polyene copolymer synthesized using vinylidene norbornene as the nonconjugated polyene.

  Patent Document 1 discloses a technique for obtaining an ethylene / α-olefin / non-conjugated polyene copolymer rubber pellet which is difficult to block, and is implemented as such an ethylene / α-olefin / non-conjugated polyene copolymer. The examples disclose only ethylene / α-olefin / nonconjugated polyene copolymers synthesized using vinylidene norbornene as the nonconjugated polyene, using 5-ethylidene-2-norbornene as the nonconjugated polyene. For the ethylene / α-olefin / non-conjugated polyene copolymer synthesized in this manner, only data with poor blocking resistance is disclosed.

  Patent Documents 2 and 3 disclose a technique for introducing vinylidene norbornene to improve the crosslinkability of an ethylene / α-olefin / non-conjugated polyene copolymer. There is no description regarding blocking when the polyene copolymer is pelletized.

WO2004 / 083299 JP 2010-241897 A Japanese National Patent Publication No. 11-507696

  The present invention relates to a rubber pellet containing an ethylene / α-olefin / non-conjugated polyene copolymer having good dispersibility with polyolefin and polyolefin and having good low temperature characteristics and hardly causing blocking, and a thermoplastic elastomer using the same The purpose is to provide.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an ethylene / α-olefin / nonconjugated polyene copolymer in which the proportion of structural units derived from ethylene is in a specific range and satisfies specific parameter conditions. Has been found to have good dispersibility with polyolefin, and rubber pellets containing this copolymer and polyolefin have excellent low-temperature characteristics and anti-blocking properties, thus completing the present invention.

That is, the present invention
Ethylene (A), α-olefin having 3 to 20 carbon atoms (B), non-conjugated polyene (C) containing only one partial structure represented by the following general formula (I) or (II) in the molecule,

（ただし、（Ｉ）は環状オレフィンの部分構造である。）

(However, (I) is a partial structure of cyclic olefin.)

および、一般式（Ｉ）および（II）からなる群から選ばれる部分構造を合計で分子中に２つ以上含む非共役ポリエン（Ｄ）に由来する構造単位を含むエチレン・α−オレフィン・非共役ポリエン共重合体を含有するゴム組成物ペレット［Ｉ］であって、
（１）前記エチレン・α−オレフィン・非共役ポリエン共重合体において、エチレン（Ａ）に由来する構造単位とα−オレフィン（Ｂ）に由来する構造単位とのモル比[（Ａ）/（Ｂ）]が、５０／５０〜７５／２５であり、
（２）前記エチレン・α−オレフィン・非共役ポリエン共重合体において、下記式（i）で表されるＢ値が１．０５以下であり、

And ethylene / α-olefin / non-conjugated containing structural units derived from non-conjugated polyene (D) containing two or more partial structures selected from the group consisting of general formulas (I) and (II) in the molecule. A rubber composition pellet [I] containing a polyene copolymer,
(1) In the ethylene / α-olefin / non-conjugated polyene copolymer, the molar ratio of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) [(A) / (B )] Is 50/50 to 75/25,
(2) In the ethylene / α-olefin / non-conjugated polyene copolymer, the B value represented by the following formula (i) is 1.05 or less,

（式（i）中、［Ｅ］および［Ｘ］は、エチレンに由来する構造単位および炭素原子数３〜２０のα−オレフィンに由来する構造単位のモル分率をそれぞれ表し、［ＥＸ］は、エチレン・炭素原子数３〜２０のα−オレフィンのダイアッド連鎖分率を表す。）

(In formula (i), [E] and [X] represent the molar fraction of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms, respectively, and [EX] , Represents the dyad chain fraction of ethylene / α-olefin having 3 to 20 carbon atoms.)

(3) A rubber composition pellet [I] containing at least one of polyethylene and polypropylene.
The rubber composition pellet [I] preferably contains 1 to 50 parts by weight of at least one of polyethylene and polypropylene.
The rubber composition pellet [I] preferably contains 10 to 30 parts by weight of polypropylene.

Another invention is a thermoplastic elastomer obtained by dynamically crosslinking the rubber composition pellet [I] and the thermoplastic resin [II].
Another invention is a method for producing a thermoplastic elastomer in which the rubber composition pellet [I] and the thermoplastic resin [II] are supplied to an extruder and dynamically crosslinked.

  In the rubber pellet of the present invention, blocking is difficult to occur. For this reason, the rubber pellet of the present invention does not become difficult to supply and transport to the apparatus or to be weighed in the production and shipping process, final product manufacturing and processing process, and is hardened in the storage tank. , It can not be discharged, it does not harden in a filled bag or container, and it will not be difficult to use.

  Since the rubber pellet of the present invention has the above-mentioned performance, when producing a thermoplastic elastomer using this rubber pellet, it is not necessary to blend a thermoplastic resin with the rubber pellet in advance to prevent blocking. These can be separately supplied to a kneading apparatus such as an extruder and dynamically cross-linked to enable efficient production of a thermoplastic elastomer.

  Moreover, the low temperature characteristic is favorable for the rubber pellet of this invention. In the rubber pellet of the present invention, the dispersibility between the ethylene / α-olefin / non-conjugated polyene copolymer and the polyolefin is good.

<Rubber composition pellet [I]>
The rubber composition pellet [I] of the present invention contains ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a partial structure represented by the following general formula (I) or (II) in the molecule. A non-conjugated polyene (C) containing only one of

（ただし、（Ｉ）は環状オレフィンの部分構造である。）

(However, (I) is a partial structure of cyclic olefin.)

および、一般式（Ｉ）および（II）からなる群から選ばれる部分構造を合計で分子中に２つ以上含む非共役ポリエン（Ｄ）に由来する構造単位を含むエチレン・α−オレフィン・非共役ポリエン共重合体を含有するゴム組成物ペレット［Ｉ］であって、
（１）前記エチレン・α−オレフィン・非共役ポリエン共重合体において、エチレン（Ａ）に由来する構造単位とα−オレフィン（Ｂ）に由来する構造単位とのモル比[（Ａ）/（Ｂ）]が、５０／５０〜７５／２５であり、
（２）前記エチレン・α−オレフィン・非共役ポリエン共重合体において、下記式（i）で表されるＢ値が１．０５以下であり、

And ethylene / α-olefin / non-conjugated containing structural units derived from non-conjugated polyene (D) containing two or more partial structures selected from the group consisting of general formulas (I) and (II) in the molecule. A rubber composition pellet [I] containing a polyene copolymer,
(1) In the ethylene / α-olefin / non-conjugated polyene copolymer, the molar ratio of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) [(A) / (B )] Is 50/50 to 75/25,
(2) In the ethylene / α-olefin / non-conjugated polyene copolymer, the B value represented by the following formula (i) is 1.05 or less,

（式（i）中、［Ｅ］および［Ｘ］は、エチレンに由来する構造単位および炭素原子数３〜２０のα−オレフィンに由来する構造単位のモル分率をそれぞれ表し、［ＥＸ］は、エチレン・炭素原子数３〜２０のα−オレフィンのダイアッド連鎖分率を表す。）

(In formula (i), [E] and [X] represent the molar fraction of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms, respectively, and [EX] , Represents the dyad chain fraction of ethylene / α-olefin having 3 to 20 carbon atoms.)

(3) A rubber composition pellet [I] containing at least one of polyethylene and polypropylene.
The ethylene / α-olefin / non-conjugated polyene copolymer contained in the rubber composition pellet [I] is at least a structural unit derived from ethylene (A), a structural unit derived from the α-olefin (B), A structural unit derived from a conjugated polyene (C) and a structural unit derived from the non-conjugated polyene (D).

  The rubber composition pellet [I] that satisfies the above conditions has a high melting point of the ethylene / α-olefin / non-conjugated polyene copolymer and has a microcrystalline structure, and therefore has a high hardness, so that blocking occurs. Hateful. For this reason, the rubber composition pellet [I] does not become difficult to be supplied or transported to the apparatus or difficult to be metered in the production and shipping process and the final product manufacturing and processing process. It will not harden and become unable to be discharged or hardened in a filled bag or container.

(C-C20 α-olefin (B))
Examples of the α-olefin (B) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1 -Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene and the like. Of these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferable. These α-olefins may be used alone or in combination of two or more.

  The ethylene / α-olefin / non-conjugated polyene copolymer includes a structural unit derived from at least one α-olefin (B) having 3 to 20 carbon atoms, and has two or more carbon atoms. A structural unit derived from 3 to 20 α-olefin (B) may be included.

Such an α-olefin has relatively low raw material cost and excellent copolymerizability, and rubber composition pellets containing an ethylene / α-olefin / non-conjugated polyene copolymer have excellent mechanical properties and good properties. This is preferable because it shows flexibility.
(Nonconjugated polyene (C) containing only one partial structure represented by the general formula (I) or (II) in the molecule)

  The non-conjugated polyene (C) includes one partial structure represented by the general formula (I) in the molecule, and does not include the partial structure represented by the general formula (II) in the molecule. Or a non-conjugated polyene that contains one partial structure represented by the general formula (II) in the molecule and does not contain the partial structure represented by the general formula (I) in the molecule.

  The partial structure represented by the general formula (I) is a cyclic olefin partial structure. That is, the partial structure represented by the general formula (I) has two carbon atoms adjacent to each other constituting a ring of the cyclic olefin and connected by a double bond, and one for each of the two carbon atoms. It is a structure composed of an atomic group containing two hydrogen atoms bonded to each other.

  For example, in the case of 5-ethylidene-2-norbornene (ENB), one partial structure represented by the above general formula (I) is contained in one molecule, and thus corresponds to the non-conjugated polyene (C). On the other hand, in the case of dicyclopentadiene (DCPD), two partial structures represented by the above general formula (I) are included in one molecule, and therefore correspond to the non-conjugated polyene (D) described later. In the case of vinylidene norbornene, it contains one partial structure represented by the above general formula (I) in one molecule and one partial structure represented by the above general formula (II) in one molecule. This corresponds to the non-conjugated polyene (D).

Examples of the non-conjugated polyene (C) containing only one partial structure represented by the general formula (I) or (II) in the molecule include fats having vinyl groups (CH ₂ ═CH—) at both molecular ends. Family polyenes are not included. Examples of the non-conjugated polyene (C) include the following aliphatic polyenes and alicyclic polyenes.

  Specific examples of the aliphatic polyene include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene, 3- Methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl -1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl -1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl -1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl -1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl -1,6-nonadiene, 7-methyl- , 7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1 , 5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1 , 6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1 , 7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1 , 6-Undecadiene, 9-methyl-1,8-undecadiene And the like. In the present invention, these aliphatic polyenes can be used singly or in combination of two or more. Preferably, 7-methyl-1,6-octadiene is used.

  Examples of the alicyclic polyene include an alicyclic portion having one carbon / carbon double bond (unsaturated bond) and a carbon atom constituting the alicyclic portion bonded by a carbon / carbon double bond. And polyenes composed of chain-like moieties (ethylidene, propylidene, etc.), and specific examples include 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene- Examples include 2-norbornene, and 5-ethylidene-2-norbornene (ENB) is preferably used. Specific examples of the other alicyclic polyenes include 2-methyl-2,5-norbornadiene and 2-ethyl-2,5-norbornadiene.

The ethylene / α-olefin / non-conjugated polyene copolymer contains at least one structural unit derived from the non-conjugated polyene (C), and is derived from two or more types of the non-conjugated polyene (C). A structural unit may be included.
(Non-conjugated polyene (D) containing two or more partial structures selected from the group consisting of the general formulas (I) and (II) in the molecule)

  The non-conjugated polyene (D) contains two or more partial structures represented by the general formula (I) in the molecule, and the non-conjugated polyene (D) does not contain the partial structure represented by the general formula (II) in the molecule. Polyene, a non-conjugated polyene containing two or more partial structures represented by the above general formula (II) in the molecule and not containing a partial structure represented by the above general formula (I) in the molecule, or the above general formula ( A non-conjugated polyene containing one or more partial structures represented by I) in the molecule and one or more partial structures represented by the general formula (II) in the molecule.

Examples of the non-conjugated polyene (D) include an alicyclic portion having a carbon / carbon double bond (unsaturated bond) and a chain portion bonded to a carbon atom constituting the alicyclic portion, and a vinyl group. And an alicyclic polyene having a chain portion and an aliphatic polyene having a vinyl group at both molecular ends. Specific examples include 5-alkenyl-2-norbornene such as 5-vinyl-2-norbornene (VNB) and 5-allyl-2-norbornene; 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, tetracyclo [ 4,4,0,1 ^2.5 , 1 ^7.10 ] alicyclic polyenes such as deca-3,8-diene; aliphatic polyenes such as α, ω-diene such as 1,7-octadiene and 1,9-decadiene Can be mentioned.

  Among these, 5-vinyl-2-norbornene (VNB), 5-alkenyl-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, 1,7-octadiene, and 1,9-decadiene are preferable, and 5-vinyl 2-norbornene (VNB) is particularly preferred.

The ethylene / α-olefin / non-conjugated polyene copolymer may contain a structural unit derived from two or more kinds of the non-conjugated polyene (D).
When the ethylene / α-olefin / non-conjugated polyene copolymer contains a structural unit derived from a non-conjugated polyene (D) such as VNB, the rubber composition pellet [I] becomes more difficult to block. This is because when a non-conjugated polyene (D) such as VNB is used, when copolymerized with a metallocene catalyst described later, long chain branching increases, and the elastic modulus due to the low shear region increases, whereby the rubber composition pellets Since deformation of [I] is suppressed, it is considered that blocking becomes difficult.

  In the ethylene / α-olefin / non-conjugated polyene copolymer, the molar ratio of the content of structural units derived from the non-conjugated polyene (C) and the content of structural units derived from the non-conjugated polyene (D) [( C) / (D)] is preferably 85/15 to 99.5 / 0.5, more preferably 90/10 to 99.5 / 0.5, and still more preferably 95/5 to 99. 0.5 / 0.5. It is suitable from the viewpoint that deformation of the rubber composition pellet [I] is suppressed when the molar ratio is within the above range.

  The content of the structural unit derived from the non-conjugated polyene contained in the ethylene / α-olefin / non-conjugated polyene copolymer is the total structural unit contained in the ethylene / α-olefin / non-conjugated polyene copolymer. It is preferable that it is 0.5-4.5 mol% with respect to it, More preferably, it is 1.0-4.5 mol%, More preferably, it is 2.0-4.5 mol%. When the content of the structural unit derived from the non-conjugated polyene is within the above range, it is preferable from the viewpoint of rubbery properties (for example, permanent elongation, compression set). The content of structural units derived from the non-conjugated polyene means the total content of structural units derived from all non-conjugated polyenes contained in the ethylene / α-olefin / non-conjugated polyene copolymer. To do. When the ethylene / α-olefin / non-conjugated polyene copolymer contains a non-conjugated polyene (C) and the non-conjugated polyene (D) as the non-conjugated polyene, the content is the non-conjugated polyene (C). It means the sum of the content of structural units derived from and the content of structural units derived from the non-conjugated polyene (D).

The content of the structural unit derived from the non-conjugated polyene can be determined by ¹³ C-NMR.
The rubber composition pellet [I] containing the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the requirements (1) to (3). Hereinafter, requirements (1) to (3) will be described.

(Requirement (1))
Molar ratio [(A) / (B) of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) contained in the ethylene / α-olefin / non-conjugated polyene copolymer. ] Is 50/50 to 75/25. The molar ratio [(A) / (B)] is preferably 50/50 to 70/30, more preferably 55/45 to 65/35. When the molar ratio is within the above range, it is preferable from the viewpoint that the rubber composition pellets are hardly blocked and the low temperature characteristics are improved.
The molar ratio can be determined by ¹³ C-NMR.

(Requirement (2))
In the ethylene / α-olefin / non-conjugated polyene copolymer, the B value represented by the following formula (i) is 1.05 or less. The B value is preferably 1.03 or less, more preferably 1.00 or less.

（式（i）中、［Ｅ］および［Ｘ］は、エチレンに由来する構造単位および炭素原子数３〜２０のα−オレフィンに由来する構造単位のモル分率をそれぞれ表し、［ＥＸ］は、エチレン・炭素原子数３〜２０のα−オレフィンのダイアッド連鎖分率を表す。）

(In formula (i), [E] and [X] represent the molar fraction of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms, respectively, and [EX] , Represents the dyad chain fraction of ethylene / α-olefin having 3 to 20 carbon atoms.)

  In the formula (i), [E] is the molar fraction of structural units derived from ethylene in the ethylene / α-olefin / nonconjugated polyene copolymer, that is, the ethylene / α-olefin / nonconjugated polyene copolymer. Is a molar ratio of structural units derived from ethylene contained in the ethylene / α-olefin / non-conjugated polyene copolymer to all structural units contained in [X] is a mole fraction of structural units derived from an α-olefin having 3 to 20 carbon atoms in the ethylene / α-olefin / nonconjugated polyene copolymer, that is, the ethylene / α-olefin / nonconjugated polyene. It is the molar ratio of structural units derived from an α-olefin having 3 to 20 carbon atoms contained in the ethylene / α-olefin / non-conjugated polyene copolymer with respect to all structural units contained in the copolymer.

[EX] represents an α-olefin dyad chain fraction having 3 to 20 ethylene-carbon atoms.
In addition, the said B value can be calculated | required by < ¹³ > C-NMR according to the method as described in an Example.

  The B value is an index indicating the randomness of the copolymer. When the B value is 1.0, the randomness is the highest, the smaller the value, the higher the blockiness, and the higher the value, the higher the alternation.

  When the B value is within the above range, it is preferable in terms of excellent blocking resistance. Further, the closer the B value is to 1.0, the better the randomness and the better the low-temperature characteristics.

(Requirement (3))
The rubber composition pellet [I] contains at least one of polyethylene and polypropylene. When rubber composition pellet [I] contains at least any one of polyethylene and polypropylene, it is suitable from the viewpoint of improving blocking resistance.

  From the above viewpoint, the rubber composition pellet [I] contains 1 to 50 parts by weight of at least one of polyethylene and polypropylene with respect to 100 parts by weight of the ethylene / α-olefin / nonconjugated polyene copolymer. Preferably, 1 to 30 parts by weight is included, and more preferably 5 to 25 parts by weight.

  The rubber composition pellet [I] preferably contains 10 to 30 parts by weight of polypropylene with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer from the above viewpoint. It is more preferable to include parts by weight, and it is more preferable to include 15 to 25 parts by weight.

  The ethylene / α-olefin / non-conjugated polyene copolymer is prepared by using a specific metallocene catalyst to produce ethylene (A), α-olefin (B), non-conjugated polyene (C), non-conjugated polyene (D) and the like. It can be obtained by polymerization.

  The metallocene catalyst has, for example, a structure represented by the following formula (α) or (β), preferably the following general formula (i), more preferably the following formulas (ii), (iii), (iv), ( v) or (vi) having a structure. Among these, a metallocene catalyst having a structure represented by (iii) is particularly preferable.

（式（α）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子または炭素原子数１〜６のアルキル基であり、Ｒ¹およびＲ²の少なくとも１つは水素原子ではない。

(In formula (α), R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one of R ¹ and R ² is not a hydrogen atom.

R ^{3 to} R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^{1 to} R ⁶ may be bonded to each other to form a ring.
M is titanium.

Y is -O-, -S-, -NR ^* -, -PR ^* -.
Z ^{* _{is, SiR * 2, CR * 2}} , SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, a CR ^* ₂ SiR ^* _2, or GeR ^* _2.

Each R ^* is independently a hydrogen atom, a hydrocarbyl group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, or a halogenated aryl group, and when R ^* is not hydrogen, R ^* is up to 20 It has atoms other than hydrogen atoms. May be two R where Z has ^* (when R ^* is not hydrogen atom) may form a ring, R ^* may form a ring having the R ^* and Y having the Z ^*.

p is 0, 1 or 2.
q is zero or one.
However, when p is 2, q is zero, M is in the +4 oxidation state, and each X is independently methyl or benzyl.

  When p is 1, q is zero, M is in the +3 oxidation state, X is 2- (N, N-dimethyl) aminobenzyl, or M is in the +4 oxidation state, and X is 1,3-butadienyl.

  When p is 0, q is 1, M is a formal oxidation state of +2, and X ′ is 1,4-diphenyl-1,3-butadiene, 2,4-hexadiene, or 1,3-pentadiene. It is. )

（式（β）中、Ｒは、それぞれ独立に、ヒドロカルビル、ハロヒドロカルビル、シリル、ゲルミルおよびこれらの組み合わせから選択される基または水素原子であり、該基が含有する水素原子以外の原子の数は２０個以下である。

(In the formula (β), each R is independently a group or hydrogen atom selected from hydrocarbyl, halohydrocarbyl, silyl, germyl and combinations thereof, and the number of atoms other than hydrogen atoms contained in the group is 20 or less.

M is titanium, zirconium or hafnium.
Y is -O-, -S-, -NR ^* -or -PR ^* -.
R ^* is a hydrogen atom, hydrocarbyl group, hydrocarbyloxy group, silyl group, halogenated alkyl group or halogenated aryl group, and when R ^* is not hydrogen, R ^* represents up to 20 non-hydrogen atoms. contains.

Z is a divalent group containing boron or a group 14 element and containing nitrogen, phosphorus, sulfur or oxygen, and the divalent group has 60 or less atoms other than hydrogen atoms. is there.
X is independently an anionic ligand having 60 or less atoms (excluding a cyclic ligand having a delocalized π bond) when a plurality of X are present.

X ′ is a neutral linking compound having 20 or less atoms.
p is 0, 1 or 2;
q is 0 or 1.

  However, when p is 2 and q is 0, M is in the +4 oxidation state, X is halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amide, di (hydrocarbyl) phosphide, hydrocarbyl sulfide, silyl group, An anionic ligand selected from a halo-substituted derivative, a di (hydrocarbyl) amino-substituted derivative, a hydrocarbyloxy-substituted derivative and a di (hydrocarbyl) phosphino-substituted derivative, wherein the number of atoms other than the hydrogen atom of X is 20 or less It is.

  When p is 1 and q is 0, M is in the +3 oxidation state and X is selected from allyl, 2- (N, N-dimethylaminomethyl) phenyl and 2- (N, N-dimethyl) aminobenzyl. Or M is in the +4 oxidation state and X is a divalent derivative of a conjugated diene, and M and X together form a metallocyclopentene group.

  And when p is 0 and q is 1, M is in the +2 oxidation state, X ′ is a neutral conjugated or non-conjugated diene optionally substituted with one or more hydrocarbyl groups; Has no more than 40 carbon atoms and forms a π complex with M. )

（式（ｉ）中、Ｒ' は、水素原子、ヒドロカルビル基、ジ（ヒドロカルビルアミノ）基またはヒドロカルビレンアミノ基を表し、それらの基の炭素原子数は２０以下である。

(In formula (i), R ′ represents a hydrogen atom, a hydrocarbyl group, a di (hydrocarbylamino) group or a hydrocarbyleneamino group, and these groups have 20 or less carbon atoms.

R "represents a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom.
M represents titanium.
Y is, -O -, - S -, - NR * -, - PR * -, - represents a NR ₂ ^* or -PR ₂ ^*.

Z ^* is, Z ^{* _{is, -SiR * 2 -, - CR}} * 2 -, - SiR * 2 SiR * 2 -, - CR * 2 CR * 2 -, - CR * = CR * -, - CR * 2 SiR ^* _2- or -GeR ^* _2- is represented.
R ^* each independently represents a hydrogen atom; or at least one group selected from the group consisting of a hydrocarbyl group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group and a halogenated aryl group. the stands, said group comprises an atom to atom number 2 to 20, Z ^* 2 one R ^* which has (when R ^* is not hydrogen) is optionally may form a ring, with the Z ^* R ^* and the Y is R ^* having may form a ring optionally.

X represents a monovalent anionic ligand group having up to 60 atoms excluding the class of ligands that are cyclic delocalized π-binding ligand groups.
X ′ represents a neutral linking group having up to 20 atoms.
X "represents a divalent anionic ligand group having up to 60 atoms.

p represents 0, 1 or 2, q represents 0 or 1, and r represents 0 or 1.
However, when p is 2, q and r are 0 and M is in the +4 oxidation state (or when Y represents -NR ^* ₂ or -PR ^* ₂ , M is in the +3 oxidation state) X) is a halide group, hydrocarbyl group, hydrocarbyloxy group, di (hydrocarbyl) amide group, di (hydrocarbyl) phosphide group, hydrocarbyl sulfide group and silyl group, derivatives in which these groups are halogen-substituted, these groups Represents an anionic ligand selected from di (hydrocarbyl) amino substituted derivatives, derivatives in which these groups are hydrocarbyloxy substituted, and derivatives in which these groups are di (hydrocarbyl) phosphino substituted, and up to 30 It has atoms other than hydrogen atoms.

  However, when r is 1, p and q represent 0, M is an oxidation state of +4, and X ″ is selected from the group consisting of a hydrocarbazyl group, an oxyhydrocarbyl group, and a hydrocarbylene dioxy group. And has up to 30 atoms other than hydrogen atoms.

  However, when p is 1, q and r represent 0, M is an oxidation state of +3, X is an allyl group, 2- (N, N-dimethylamino) phenyl group, 2- (N, It represents an stabilizing anionic ligand group selected from the group consisting of (N-dimethylaminomethyl) phenyl group and 2- (N, N-dimethylamino) benzyl group.

Provided that when p and r are 0, q represents 1, M is an oxidation state of +2, and X ′ is a neutral conjugated diene or neutral, optionally substituted with one or more hydrocarbyl groups Wherein X ′ has up to 40 carbon atoms and forms a π-complex with M. )
In the general formula (i), any one of the following (1) to (4) is preferable.

(1) p is 2, q and r are 0, M is an oxidation state of +4, and X independently represents methyl, benzyl or halide.
(2) q and q are 0, r is 1, M is an oxidation state of +4, and X ″ represents a 1,4-butadienyl group that forms a metallocyclopentene ring with M.

(3) p is 1, q and r are 0, M is an oxidation state of +3, and X represents 2- (N, N-dimethylamino) benzyl.
(4) p and r are 0, q represents 1, M is an oxidation state of +2, and X ′ represents 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

  In any of the above embodiments (1) to (4), R ″ more preferably represents a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

上記式（ｉｉ）は、（ｔ−ブチルアミド）ジメチル（η⁵−２−メチル−ｓ−インダセン−１−イル）シランチタニウム（ＩＩ）２，４−ヘキサジエンである。

The above formula (ii) is (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silane titanium (II) 2,4-hexadiene.

上記式（ｉｉｉ）は、（ｔ−ブチルアミド）−ジメチル（η⁵−２−メチル−ｓ−インダセン−１−イル）シランチタニウム（II）１，３−ペンタジエン（別名：［Ｎ−（１，１−ジメチルエチル）−１，１−ジメチル−１−［（１，２，３，３Ａ，８Ａ−η）−１，５，６，７−テトラヒドロ−２−メチル−Ｓ−インダセン−１−ｙｌ］シランアミネート（２−）−κＮ］［（１，２，３，４−η）−１，３−ペンタジエン］−チタニウム）である。

The above formula (iii) is obtained from (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene (also known as [N- (1,1 -Dimethylethyl) -1,1-dimethyl-1-[(1,2,3,3A, 8A-η) -1,5,6,7-tetrahydro-2-methyl-S-indacene-1-yl] Silane aminate (2-)-κN] [(1,2,3,4-η) -1,3-pentadiene] -titanium).

上記式（ｉｖ）は、（ｔ−ブチルアミド）−ジメチル（η⁵−２，３−ジメチルインデニル）シランチタニウム（ＩＩ）１，４−ジフェニル−１，３−ブタジエンである。

The above formula (iv) is (t-butylamido) -dimethyl (η ⁵ -2,3-dimethylindenyl) silane titanium (II) 1,4-diphenyl-1,3-butadiene.

上記式（ｖ）は、（ｔ−ブチル−アミド）−ジメチル（η⁵−２，３−ジメチル−ｓ−インダセン−１−イル）シランチタニウム（ＩＶ）ジメチルである。

The above formula (v) is (t-butyl-amido) -dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silane titanium (IV) dimethyl.

上記式（ｖｉ）は、（ｔ−ブチルアミド）−ジメチル（η⁵−２−メチル−ｓ−インダセン−１−イル）シラン−チタニウム（ＩＶ）ジメチルである。

The above formula (vi) is (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silane-titanium (IV) dimethyl.

  When a metallocene catalyst having a structure represented by the above formula (iii) is used, in the polymerization reaction for obtaining an ethylene / α-olefin / nonconjugated polyene copolymer, the nonconjugated polyenes (C) and (D) Copolymerizability is particularly excellent. For this reason, the ethylene / α-olefin / non-conjugated polyene copolymer polymerized using the metallocene-based catalyst having the structure represented by the formula (iii) is, for example, a 2-vinyl-2-norbornene (VNB) Heavy bonds can be efficiently incorporated into the polymer and long chain branching can be introduced at a high rate.

  Further, the ethylene / α-olefin / non-conjugated polyene copolymer having a narrow molecular weight distribution and composition distribution and having an extremely uniform molecular structure can be prepared. Therefore, the formation of gel-like irregularities on the surface of the rubber molded body, which is a concern with the generation of long-chain branches, is significantly suppressed. As a result, the rubber molded body formed from the composition containing such an ethylene / α-olefin / non-conjugated polyene copolymer is excellent in the surface appearance and free from shape retention because it does not contain gel-like particles. Since it is excellent, production stability is also good.

  The metallocene catalyst having the structure represented by the above formulas (i) to (vi) can be prepared using a well-known synthesis method. For example, it is disclosed in International Publication No. 98/49212 pamphlet. If necessary, a lower oxidation state complex (metallocene catalyst) can be produced using a reducing agent. Such a method is disclosed in USSN 8 / 241,523.

The method for producing the ethylene / α-olefin / non-conjugated polyene copolymer preferably has a step of obtaining the following polymerization reaction solution.
The step of obtaining a polymerization reaction liquid means using an aliphatic hydrocarbon as a polymerization solvent, in the presence of the above-described metallocene catalyst, preferably a metallocene catalyst having a structure represented by the above formula (iii) in the presence of ethylene ( A), α-olefin (B), non-conjugated polyene (C) and non-conjugated polyene (D) are copolymerized, and the concentration of ethylene / α-olefin / non-conjugated polyene copolymer is 8 to 18% by weight, preferably Is a step of obtaining a polymerization reaction solution of 8.5 to 18.0% by weight.

  By setting the concentration of the ethylene / α-olefin / non-conjugated polyene copolymer to the polymerization solvent within the above range, an ethylene / α-olefin / non-conjugated polyene copolymer satisfying the above requirements (1) to (3) is obtained. It can be suitably obtained. When the concentration of the ethylene / α-olefin / non-conjugated polyene copolymer with respect to the polymerization solvent exceeds 18% by weight, the viscosity of the polymerization solution is too high, and the solution may not be stirred uniformly, which may make the polymerization reaction difficult. is there.

  Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Examples of the aliphatic hydrocarbon include pentane, hexane, and heptane. Among these, hexane is preferable from the viewpoint of separation and purification from the obtained ethylene / α-olefin / nonconjugated polyene copolymer.

  As such a production method, a reaction with a stirrer using the above catalyst as a main catalyst, an organoaluminum compound such as a boron compound and / or a trialkyl compound as a cocatalyst, and an aliphatic hydrocarbon such as hexane as a solvent. A continuous method or a batch method using a vessel is mentioned.

Examples of boron compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, di (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis ( Pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium N-tris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (penta Fluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium Tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2, 3,4,6-tetrafluorophenyl) borate, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Dimethyl (t-butyl) ammonium tetrakis (2,3, Alkyl ammonium salts such as 4,6-tetrafluorophenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate;
Trisubstituted phosphonium such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate salt;
Disubstituted compounds such as diphenyloxonium tetrakis (pentafluorophenyl) borate, di- (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, di (2,6-dimethylphenyl) oxonium tetrakis (pentafluorophenyl) borate Oxonium salts prepared;
Disubstituted sulfonium salts such as diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate ;
And trityltetrakis (pentafluorophenyl) boron (V) ((C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ ).

Examples of the organoaluminum compound include triisobutylaluminum.
The reaction temperature can be raised to 100 ° C. because the catalyst is not deactivated even at high temperatures.
The polymerization pressure ranges from over 0 to 8 MPa (gauge pressure), preferably over 0 to 5 MPa (gauge pressure).

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 10 minutes to 3 hours. It is.

Further, in the copolymerization, a molecular weight regulator such as hydrogen can be used.
The molar ratio [(A) / (B)] of the charge of ethylene (A) and the α-olefin (B) is preferably 25/75 to 95/5, more preferably 25/75 to 90/10. is there.

  The molar ratio [(C) / (D)] of the non-conjugated polyene (C) and the non-conjugated polyene (D) is preferably 90/10 to 99.5 / 0.5, more preferably 95. / 5 to 99.5 / 0.5.

The molar ratio [(A) / (C)] of the charge of ethylene (A) and the non-conjugated polyene (C) is preferably 65/35 to 99/1, more preferably 65/35 to 98/2. .
The molar ratio [(A) / (D)] of the charge of ethylene (A) and the non-conjugated polyene (D) is preferably 95.00 / 5.00 to 99.95 / 0.05, more preferably 97. 50 / 2.50 to 99.95 / 0.05.

Polymerization using the above catalyst is preferable because non-conjugated polyene and the like are copolymerized at a high conversion rate, and an appropriate amount of long chain branching can be introduced into the resulting copolymer.
The rubber composition pellet [I] may contain other components according to the purpose in addition to the ethylene / α-olefin / non-conjugated polyene copolymer and at least one of polyethylene and polypropylene.

Examples of other components include various additives such as a softener, an inorganic filler, a reinforcing agent, an anti-aging agent (stabilizer), a processing aid, an activator, and a hygroscopic agent.
The rubber composition pellet [I] can also contain a rubber component other than the ethylene / α-olefin / non-conjugated polyene copolymer. The content of the ethylene / α-olefin / non-conjugated polyene copolymer in the rubber composition pellet [I] is preferably 20% by weight or more, more preferably 30 to 90% by weight.

The rubber composition pellet [I] is an extruder equipped with a pelletizer containing the ethylene / α-olefin / non-conjugated polyene copolymer, at least one of polyethylene and polypropylene, and other components as required. Etc. can be used for kneading and granulating. In the rubber composition pellet [I], dispersibility between the ethylene / α-olefin / non-conjugated polyene copolymer and polypropylene or the like is good.
The exemplified additives will be described in detail below.

(Softener)
When the rubber composition pellet [I] contains a softening agent, it is preferable from the viewpoint of easy kneading using a kneading apparatus such as an extruder.

  The softening agent can be appropriately selected depending on its use, and it may be used alone or in combination of two or more. Specific examples of the softener include process oil (for example, “Diana Process Oil PS-430” (trade name; manufactured by Idemitsu Kosan Co., Ltd.)), lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petroleum jelly, and the like. Petroleum softeners; coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as beeswax, carnauba wax and lanolin Fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate or the like; naphthenic acid, pine oil, rosin or derivatives thereof; terpene resin, petroleum resin, atactic polypropylene, Synthetic polymer materials such as malon indene resin; dioctyl phthalate, diocti Adipate, ester softeners such as dioctyl sebacate and the like; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, hydrocarbon-based synthetic lubricating oil, tall oil, and the like sub (factice). Of these, petroleum softeners are preferred, and process oils are particularly preferred.

  When the rubber composition pellet [I] contains a softening agent, the amount of the softening agent is usually 2 to 100 weights with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer. Parts, preferably 10 to 100 parts by weight.

(Inorganic filler)
The inorganic filler can be appropriately selected depending on the application, and may be used alone or in combination of two or more. Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. Of these, heavy calcium carbonate is preferred. As heavy calcium carbonate, commercially available “Whiteon SB” (trade name; Shiraishi Calcium Co., Ltd.) and the like can be used.

  When the rubber composition pellet [I] contains an inorganic filler, the compounding amount of the inorganic filler is usually 2 to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer. 50 parts by weight, preferably 5 to 50 parts by weight. When the blending amount is within the above range, the kneading processability of the thermoplastic elastomer produced using the rubber composition pellet [I], and the mechanical properties of the rubber molded product obtained from the thermoplastic elastomer (for example, tensile strength) , Rubber elasticity, etc.).

(Reinforcing agent)
Reinforcing agents can be appropriately selected depending on the application, and may be used alone or in combination of two or more. Specific examples of the reinforcing agent include “Asahi # 55G” and “Asahi # 50HG” (trade name; manufactured by Asahi Carbon Co., Ltd.), “Seast (trade name)” series: V, SO, SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, etc. carbon black (manufactured by Tokai Carbon Co., Ltd.), carbon black surface-treated with a silane coupling agent, silica, activated calcium carbonate , Fine powder talc, fine powder silicic acid and the like. Of these, carbon blacks such as “Asahi # 55G”, “Asahi # 50HG”, “Seast V”, and “Seast SO” are preferable.

  When the rubber composition pellet [I] contains a reinforcing agent, mechanical properties such as tensile strength, tear strength, and wear resistance of the thermoplastic elastomer produced using the rubber composition pellet [I] may be improved. is there.

  When the rubber composition pellet [I] contains a reinforcing agent, the compounding amount of the reinforcing agent is usually 30 to 200 weights with respect to 100 parts by weight of the ethylene / α-olefin / nonconjugated polyene copolymer. Parts, preferably 50 to 180 parts by weight, more preferably 70 to 160 parts by weight. When the blending amount is within the above range, the kneading processability of the thermoplastic elastomer produced using the rubber composition pellet [I], the mechanical properties of the rubber molded product obtained from the thermoplastic elastomer (for example, strength, Flexibility) and compression set.

(Anti-aging agent (stabilizer))
By blending an antioxidant (stabilizer) with the rubber composition pellet [I], a thermoplastic elastomer produced using the rubber composition pellet [I] and a rubber molded body formed from the thermoplastic elastomer It is possible to extend the life. As such an anti-aging agent, conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents and the like can be used.

More specifically, as an anti-aging agent, an aromatic secondary amine anti-aging agent such as phenylbutylamine, N, N-di-2-naphthyl-pphenylenediamine; dibutylhydroxytoluene, tetrakis [methylene (3,5- Di-t-butyl-4-hydroxy) hydrocinnamate] phenolic antioxidants such as methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide and the like Thioether-based antioxidants; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, distearylthiodipropionate, etc. And sulfur-based antioxidants.

  These anti-aging agents can be used singly or in combination of two or more. In the case where the rubber composition pellet [I] contains an anti-aging agent, the blending amount of the anti-aging agent is the rubber component (ethylene / α-olefin / non-conjugated polyene copolymer contained in the rubber composition pellet [I]). Rubber component other than coalescence and copolymer) is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, more preferably 0.7 to 5.0 parts per 100 parts by weight. Parts by weight. When the blending amount of the anti-aging agent is within the above range, it is preferable that no bloom is generated on the surface of the rubber composition pellet [I] and further no vulcanization inhibition occurs.

(Processing aid)
As processing aids, those generally blended into rubber as processing aids can be widely used.

Specific examples of the processing aid include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, esters and the like. Of these, stearic acid is preferred.

  When the rubber composition pellet [I] contains a processing aid, the blending amount of the processing aid is determined according to the rubber component (ethylene, α-olefin, non-conjugated polyene co-polymer contained in the rubber composition pellet [I]). The amount is usually 10 parts by weight or less, preferably 8.0 parts by weight or less, more preferably 5.0 parts by weight or less with respect to 100 parts by weight of the rubber component other than the coalescence and the copolymer. When the amount of the processing aid is within the above range, it is preferable that no bloom occurs on the surface of the rubber composition pellet [I] and further vulcanization inhibition does not occur.

(Active agent)
The activator can be appropriately selected depending on its use, and may be used alone or in combination of two or more. Specific examples of the activator include di-n-butylamine, dicyclohexylamine, monoelaanolamine, “Acting B” (trade name; manufactured by Yoshitake Pharmaceutical Co., Ltd.), and “Acching SL” (trade name; Yoshitake Pharmaceutical Co., Ltd.) Amines such as diethylene glycol, polyethylene glycol, lecithin, triarylate melilate, zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids (specifically, “Struktol activator 73”, “Struktol IB 531”, “ Activators such as Struktol FA541 (trade name; manufactured by Schill & Seilacher), etc .; Zinc peroxide preparations such as “ZEONET ZP” (trade name; manufactured by Nippon Zeon Co., Ltd.); Kutadecyltrimethylammonium bromide, synthesis Hydrotalcite, special four (Specifically, "Alucard 2HTF" (trade name; manufactured by Lion Akzo Co., Ltd.), and the like) ammonium compounds and the like. Of these, “Arcade 2 HTF” is preferable.

  When the rubber composition pellet [I] contains an activator, the compounding amount of the activator is the rubber component (the ethylene / α-olefin / non-conjugated polyene copolymer contained in the rubber composition pellet [I] and Rubber component other than the copolymer) is usually 0.2 to 10 parts by weight, preferably 0.3 to 5 parts by weight, more preferably 0.5 to 4 parts by weight with respect to 100 parts by weight.

(Hygroscopic agent)
The hygroscopic agent can be appropriately selected depending on the application, and one type may be used alone, or two or more types may be used. Specific examples of the hygroscopic agent include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, white carbon and the like. Of these, calcium oxide is preferred.

  When the rubber composition pellet [I] contains a hygroscopic agent, the blending amount of the hygroscopic agent is the rubber component (the ethylene / α-olefin / non-conjugated polyene copolymer contained in the rubber composition pellet [I] and Rubber component other than the copolymer) is usually 0.5 to 15 parts by weight, preferably 1.0 to 12 parts by weight, and more preferably 1.0 to 10 parts by weight with respect to 100 parts by weight.

In addition to the rubber composition pellet [I], other additives usually used for rubber can be arbitrarily blended within a range not impairing the object of the present invention.
The rubber composition pellet [I] is selected from 2 to 100 parts by weight of a softener and 2 to 50 parts by weight of an inorganic filler with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer. It is preferable from the viewpoint of the moldability of the thermoplastic elastomer obtained from the rubber composition pellet [I] to contain at least one additive.

<Thermoplastic elastomer>
A thermoplastic elastomer is obtained by dynamically crosslinking the rubber composition pellet [I] and the thermoplastic resin [II]. Since this thermoplastic elastomer has the rubber composition pellet [I], it is excellent in low temperature characteristics.

  In the present invention, dynamic crosslinking refers to carbon contained in at least the ethylene / α-olefin / non-conjugated polyene copolymer by kneading rubber composition pellets [I] and thermoplastic resin [II] in a molten state. -This means that a part of the carbon double bond is cross-linked. In order to perform dynamic crosslinking suitably, it is preferable to add a crosslinking agent to the rubber composition pellet [I] and the thermoplastic resin [II] to perform dynamic crosslinking.

(Thermoplastic resin [II])
Although there is no limitation in particular as thermoplastic resin [II], Usually, the C2-C20 alpha-olefin homopolymer or copolymer is used. The thermoplastic resin [II] may be a resin composed of one kind of polymer or a resin composed of two or more kinds of polymers.

  When the thermoplastic resin [II] is a copolymer of an α-olefin having 2 to 20 carbon atoms, it is obtained using at least two kinds of α-olefins having 2 to 20 carbon atoms as monomers. A copolymer of at least one α-olefin having 2 to 20 carbon atoms and a monomer containing a vinyl group (excluding an α-olefin) (also referred to as a vinyl monomer). It may be.

  Specific examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1- Eikosen etc. are mentioned.

Specific examples of the thermoplastic resin [II] include the following (co) polymers.
(1) Ethylene homopolymer (the production method may be either a low pressure method or a high pressure method)
(2) Ethylene-based random copolymer (3) having a structural unit derived from ethylene and a structural unit derived from a vinyl monomer such as an α-olefin having 3 to 20 carbon atoms and / or vinyl acetate or ethyl acrylate. ) Propylene homopolymer (4) Propylene-based random random copolymer (5) Propylene-derived random copolymer having propylene-derived structural units and other structural units derived from other C2-C20 α-olefins of 10 mol% or less Propylene-based block copolymer (6) 1-butene homopolymer (7) 1-butene-derived composition having a structural unit and 30 mol% or less of another structural unit derived from an α-olefin having 2 to 20 carbon atoms Butene-based random copolymer (8) 4-methyl-1-pentene monomer having a unit and 10 mol% or less of other structural unit derived from α-olefin having 2 to 20 carbon atoms Polymer (9) 4-methyl-1-pentene random copolymer having a structural unit derived from 4-methyl-1-pentene and another structural unit derived from other α-olefin having 2 to 20 carbon atoms Polymer As the thermoplastic resin [II], a propylene-based polymer is preferably used. (3) Propylene homopolymer, (4) Propylene-derived constitutional unit, and other α-olefin having 2 to 20 carbon atoms A propylene-based random random copolymer having a structural unit derived from 10 mol% or less, (5) a structural unit derived from propylene, and a structural unit derived from another α-olefin having 2 to 20 carbon atoms of 30 mol% or less. It is more preferable to use at least one propylene-based polymer selected from propylene-based block copolymers.

  As the thermoplastic resin [II], the melt flow rate (MFR: ASTM D 1238, 230 ° C., load 2.16 kg) measured with a load of 2.16 kg at 230 ° C. is usually 0.1 to 100 g / 10 min. Is in the range of 0.3 to 60 g / 10 min.

(Crosslinking agent)
From the viewpoint of rubber elasticity of the resulting thermoplastic elastomer, it is preferable to dynamically crosslink the rubber composition pellet [I] and the thermoplastic resin [II] by adding a cross-linking agent. The amount of the crosslinking agent added is preferably 0.1 to 30 parts by weight, and more preferably 0.2 to 20 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer.

  Examples of the cross-linking agent include cross-linking of rubbers such as organic peroxides, phenol resins, sulfur compounds, hydrosilicon compounds, amino resins, quinones or derivatives thereof, amine compounds, azo compounds, epoxy compounds, and isocyanates. The crosslinking agent generally used in that case is mentioned. Among these crosslinking agents, organic peroxides and phenol resins are particularly preferable.

  When the crosslinking agent is an organic peroxide, specific examples thereof include dicumyl peroxide, di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, 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, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like.

  Of these, 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane in terms of reactivity, odor, and scorch stability 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, etc., bifunctional organic peroxidation having two peroxide bonds (—O—O—) in one molecule Among them, 2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane are most preferable.

These organic peroxides may be used alone or in combination of two or more.
When an organic peroxide is used as the crosslinking agent, it is preferable to further blend the following crosslinking aid.

  Preferred examples of the crosslinking aid when an organic peroxide is used as the crosslinking agent include quinone dioxime-based crosslinking aids such as sulfur and p-quinonedioxime; acrylics such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. Cross-linking aids; allylic cross-linking aids such as diallyl phthalate and triallyl isocyanurate; other maleimide cross-linking aids; divinylbenzene and the like. The compounding quantity of a crosslinking adjuvant is 0.5-10 mol normally with respect to 1 mol of organic peroxide to be used, Preferably it is 0.5-7 mol, More preferably, it is 1-5 mol.

  When the crosslinking agent is a phenol resin, specific examples thereof include alkylphenol formaldehyde resins, brominated alkylphenol formaldehyde resins, methylolated alkylphenol resins, brominated methylolated alkylphenol resins, and the like. As these phenol resins, alkylphenol formaldehyde resins and brominated alkylphenol formaldehyde resins are preferred.

These phenol resins may be used alone or in combination of two or more.
The phenol resin can be produced by a usual method, for example, by condensing an alkyl-substituted phenol or an unsubstituted phenol with an aldehyde, preferably formaldehyde, in an alkaline medium. As another method for producing a phenol resin, a method for producing a phenol resin by condensing bifunctional phenol dialcohols can be mentioned. Moreover, as a phenol resin, a commercially available phenol resin can also be used.

  Commercially available products of the above-mentioned phenol resins include tackolol 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), tackolol 250-I (brominated alkylphenol formaldehyde resin having a bromination rate of 4%, manufactured by Taoka Chemical Industry), tackolol 250- III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Co., Ltd.), PR-4507 (manufactured by Gunei Chemical Industry Co., Ltd.), Vulkaresat 510E (manufactured by Hoechst), Vulkaresat 532E (manufactured by Hoechst), Vulcaresen E (manufactured by Hoechst), Vulkaren 105E (manufactured by Hoechst), Vulcaresen 130E (manufactured by Hoechst), Vulcaresol 315E (manufactured by Hoechst), Amber ol ST 137X (manufactured by Rohm & Haas), Sumilite Resin PR-22193 (manufactured by Sumitomo Durez), Symform-C-100 (manufactured by Anchor Chem.), Symform-C-1001 (manufactured by Anchor Chem.), Tamanol 531 (Manufactured by Arakawa Chemical Co., Ltd.), Schenectady SP1059 (manufactured by Schenectady Chem.), Schenectady SP1045 (manufactured by Schencchemy Chem.), CRR-0803 (manufactured by U.C.C.), Schemadyy SP1055 (manufactured by Schemady Chem.) Schenectady SP1056 (manufactured by Schenectady Chem.), CRM-0803 (manufactured by Showa Union Synthesis Co., Ltd.), Vulkadur A (Ba Yer), etc., among them, Tacrol 201 (alkylphenol formaldehyde resin) and Tacrol 250-I (brominated alkylphenol formaldehyde resin having a bromination rate of 4%) are preferable.

(Method for producing thermoplastic elastomer)
The thermoplastic elastomer can be obtained by dynamically cross-linking the rubber composition pellet [I] and the thermoplastic resin [II], if necessary, by supplying an additive to the kneading apparatus. . Hereinafter, a method for producing a thermoplastic elastomer using the rubber composition pellet [I] and the thermoplastic resin [II] will be described. When a crosslinking agent is blended, the rubber composition pellet [I] and the thermoplastic resin are described. What is necessary is just to add a crosslinking agent to [II] suitably.

  When producing the thermoplastic elastomer by dynamically crosslinking the rubber composition pellet [I] and the thermoplastic resin [II], either a non-open type kneading device or an open type kneading device may be used. It is preferable to use a non-open type kneading apparatus.

The dynamic crosslinking is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature at the time of dynamic crosslinking is usually 150 to 270 ° C, preferably 170 to 250 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is, 10～50,000Sec ^-1 shear rate, preferably in the range of 100~20,000sec ^-1.

  As the kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single-screw or twin-screw extruder, and the like can be used, but a non-open type apparatus is preferable, and a twin-screw extruder is particularly preferable.

  When the rubber composition pellet [I] and the thermoplastic resin [II] are supplied to the kneading apparatus, the rubber composition pellet [I] and the thermoplastic resin [II] are blended in advance, and both are mixed into the kneading apparatus. The rubber composition pellets [I] and the thermoplastic resin [II] can be supplied separately to the kneading apparatus without being previously blended.

  Conventional rubber pellets are easy to block, so in order to prevent blocking of the rubber pellets, measures such as pre-alloying the rubber pellets and thermoplastic resin to prepare the pellets and supplying them to the kneader are taken. It was. In contrast, the rubber composition pellet [I] according to the present invention is less likely to block as described above. For this reason, when manufacturing a thermoplastic elastomer using the rubber composition pellet [I] according to the present invention, it is necessary to alloy the rubber composition pellet [I] with a thermoplastic resin in advance in order to prevent blocking. However, these can be separately supplied to a kneading apparatus and dynamically crosslinked, and an efficient thermoplastic elastomer can be produced.

  The rubber composition pellet [I] and the thermoplastic resin [II] are pre-alloyed and supplied to the kneading apparatus because the rubber composition pellet [I] and the thermoplastic resin [ II] is prepared, and the elastomer mixed raw material is melt-kneaded, pelletized, and then supplied to the kneading apparatus. On the other hand, the rubber composition pellets [I] and the thermoplastic resin [II] are separately supplied to the kneading apparatus without being alloyed in advance. The elastomer mixed raw material is prepared before the supply to the kneading apparatus. This means that both are supplied separately to the kneading apparatus. When the rubber composition pellet [I] and the thermoplastic resin [II] are separately supplied to the kneading apparatus without being previously blended, the rubber composition pellet [I] and the thermoplastic resin [II] are supplied to the kneading apparatus. After that, it is blended while being melt-kneaded in the kneading part of the kneading apparatus.

  For example, when the rubber composition pellets [I] and the thermoplastic resin [II] are supplied to the extruder without pre-blending, the first hopper that introduces the raw material into the cylinder of the extruder is separated from the first hopper. Two second hoppers for supplying raw materials to one hopper are provided, and the rubber composition pellet [I] and the thermoplastic resin [II] are put in different second hoppers, respectively, and the rubber composition pellet [I] and The thermoplastic resin [II] is supplied from each second hopper to the first hopper so as to have a predetermined supply speed, blended in the first hopper, introduced into the cylinder, and dynamic crosslinking is performed. be able to.

<Molded body>
A molded body can be formed from the thermoplastic elastomer. Various molded articles can be obtained from the thermoplastic elastomer. A molded body can be formed only from the thermoplastic elastomer, or a molded body can be formed from a mixture of the thermoplastic elastomer and an additive.

  The additive is not particularly limited, and various additives such as a softener, an inorganic filler, a reinforcing agent, an anti-aging agent (stabilizer), a processing aid, an activator, a hygroscopic agent, a foaming agent, and a foaming aid. An agent can be used.

For example, examples of the molded body include automotive exterior materials such as automotive glass run channels and window frame materials, automotive interior materials such as skin materials, and building materials and gaskets.
The molded body may be a foam such as a weatherstrip sponge or a sponge material for interior skin. Such a foam can be obtained by foaming a mixture of the thermoplastic elastomer and an additive containing a foaming agent using at least a foaming agent as an additive. In addition, the mixture of the thermoplastic elastomer and the additive using the foaming aid as an additive together with the foaming agent is preferable because foaming can be particularly suitably performed.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
Table 1 shows the compositions and physical property values of the ethylene / α-olefin / non-conjugated polyene copolymers (EPDM-1) and (EPDM-2) used in Examples and Comparative Examples.
The method for measuring the composition and physical properties is shown below.

[Composition of ethylene / α-olefin / non-conjugated polyene copolymer]
Using an ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., the measurement temperature was 120 ° C., ODCB-d4 was used as a measurement solvent, the number of integration was 512 times, and the ¹ H spectrum was measured. The composition of the ethylene / α-olefin / non-conjugated polyene copolymer was measured.

[B value]
B value is the following formula (from the structural unit derived from ethylene, the structural unit derived from α-olefin having 3 to 20 carbon atoms, and the dyad chain fraction of ethylene and α-olefin having 3 to 20 carbon atoms) i).

式（i）中、［Ｅ］および［Ｘ］は、エチレンに由来する構造単位および炭素原子数３〜２０のα−オレフィンに由来する構造単位のモル分率をそれぞれ表し、［ＥＸ］は、エチレン・炭素原子数３〜２０のα−オレフィンのダイアッド連鎖分率を表す。Ｂ値およびダイアッド分率については、Seger, M. R.および Maciel, G. E.のAnal. Chem. 2004, 76, 5734-5747に基づき測定した。

In formula (i), [E] and [X] represent the mole fraction of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms, respectively, and [EX] It represents the dyad chain fraction of ethylene / α-olefin having 3 to 20 carbon atoms. The B value and dyad fraction were measured based on Seger, MR and Maciel, GE Anal. Chem. 2004, 76, 5734-5747.

[Mooney viscosity]
The Mooney viscosities (ML _{1 + 4} (100 ° C.), ML _{1 + 4} (125 ° C.)) are in accordance with JIS K6300 under the conditions of 100 ° C. and 125 ° C. and Mooney viscometer (SMV202 manufactured by Shimadzu Corporation). Type).

[Production Example 1] (Production of EPDM-1)
Continuously using a polymerization vessel having a volume of 300 L equipped with a stirring blade, ethylene as component [A], propylene as component [B], 5-ethylidene-2-norbornene (ENB) as component [C] and component [D ], A quaternary copolymerization reaction using 5-vinyl-2-norbornene (VNB) was conducted at 95 ° C.

  Using hexane (final concentration: 84.9% by weight) as a polymerization solvent, ethylene concentration was 3.6% by weight, propylene concentration was 9.6% by weight, ENB concentration was 1.9% by weight, and VNB concentration was 0.8%. The raw material was continuously supplied at 036% by weight.

While maintaining the polymerization pressure at 1.6 MPa, (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indacene-1) is a metallocene catalyst having a structure represented by the above formula (vi) as a main catalyst. -Yl) Silanetitanium (II) 1,3-pentadiene was continuously supplied to 0.00045 mmol / L. Further, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ as a cocatalyst was continuously 0.0023 mmol / L, and triisobutylaluminum (TIBA) as an organoaluminum compound was 0.23 mmol / L. Supplied.

  In this way, a copolymer rubber composed of ethylene, propylene, ENB and VNB was obtained in a solution state of 16.8% by weight. A small amount of methanol is added to the polymerization reaction liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the copolymer rubber (EPDM-1) is separated from the solvent by a steam stripping treatment, and then at 80 ° C. all day and night. It was dried under reduced pressure.

[Example 1]
An extruder equipped with a pelletizer containing 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer (EPDM-1) and 20 parts by weight of homopolypropylene (“E-111G” (trade name; Prime Polymer Co., Ltd.)) Was used for kneading and granulating under the following conditions to obtain rubber composition pellets. Dispersibility of the ethylene / α-olefin / non-conjugated polyene copolymer and homopolypropylene was good.
Extruder: Model VG-50-30 (manufactured by Tanabe Plastics Co., Ltd.)
・ Extruder speed: 25 rpm
・ Temperature: D / C4 / C3 / C2 / C1 / F = 260/260/240/200/140/50 ℃
・ Cutter rotation speed: 750 rpm
・ Water temperature: 15 ℃
-Die: φ6 · 2 holes · Cutter blade: 2 sheets The blocking resistance of the obtained rubber composition pellets was evaluated according to the following measurement method.

[Comparative Example 1]
Pelletization was attempted by the same operation as in Example 1 except that homopolypropylene was not used. However, it was blocked and could not be pelletized, and rubber composition pellets could not be obtained.

[Comparative Example 2]
Except for using ethylene / α-olefin / non-conjugated polyene copolymer (EPDM-2) instead of ethylene / α-olefin / non-conjugated polyene copolymer (EPDM-1) and not using homopolypropylene. In the same manner as in Example 1, rubber composition pellets were obtained. Dispersibility of the ethylene / α-olefin / non-conjugated polyene copolymer and homopolypropylene was good.
The blocking resistance of the obtained rubber composition pellets was evaluated according to the following measurement method.

[Blocking resistance evaluation method]
In a cylindrical jig having a diameter of about 50 mm, 50 g of the rubber composition pellet coated with 0.05 wt% of calcium stearate is placed, and a load of 4 kg is applied to the rubber composition pellet and left at 40 ° C. or 50 ° C. for 48 hours. did. The state of the rubber composition pellets after standing was observed with the naked eye, and the blocking resistance of the rubber composition pellets was evaluated based on the following scores. In the grades 2-5, it is evaluated that the rubber composition pellets are not blocked.
Score:
1: Completely fixed 2: Small lump remains but can be loosened by hand 3: Press firmly with hand to loosen to pellet shape 4: Easy to loosen to pellet shape by hand 5: No blocking at all

Claims (5)

Ethylene (A), α-olefin having 3 to 20 carbon atoms (B), non-conjugated polyene (C) containing only one partial structure represented by the following general formula (I) or (II) in the molecule,

(However, (I) is a partial structure of cyclic olefin.)

And ethylene / α-olefin / non-conjugated containing structural units derived from non-conjugated polyene (D) containing two or more partial structures selected from the group consisting of general formulas (I) and (II) in the molecule. A rubber composition pellet [I] containing a polyene copolymer,
(1) In the ethylene / α-olefin / non-conjugated polyene copolymer, the molar ratio of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) [(A) / (B )] Is 50/50 to 75/25,
(2) In the ethylene / α-olefin / non-conjugated polyene copolymer, the B value represented by the following formula (i) is 1.05 or less,

(In formula (i), [E] and [X] represent the molar fraction of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms, respectively, and [EX] , Represents the dyad chain fraction of ethylene / α-olefin having 3 to 20 carbon atoms.)
(3) A rubber composition pellet [I], comprising at least one of polyethylene and polypropylene.   The rubber composition pellets according to claim 1, comprising 1 to 50 parts by weight of at least one of polyethylene and polypropylene with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer. I].   The rubber composition pellet [I] according to claim 1, comprising 10 to 30 parts by weight of polypropylene with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer.   A thermoplastic elastomer obtained by dynamically crosslinking the rubber composition pellet [I] according to any one of claims 1 to 3 and the thermoplastic resin [II].   A method for producing a thermoplastic elastomer, wherein the rubber composition pellets [I] and the thermoplastic resin [II] according to any one of claims 1 to 3 are supplied to an extruder and dynamically crosslinked.