JP5204713B2 - Olefinic thermoplastic elastomer composition and use thereof - Google Patents

Description

  The present invention relates to an olefinic thermoplastic elastomer composition and use thereof, and more particularly, to an olefinic thermoplastic elastomer composition and use thereof which are excellent in tensile strength and rubber elasticity and can provide a molded article having a good appearance.

  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).

  However, even though it is a cross-linked olefin-based thermoplastic elastomer, its physical properties are added from a conventionally known vulcanized rubber such as natural rubber, SBR (Styrene-Butadiene Rubber), EPDM (Ethylene / Propylene / Diene with Methylene Linkage), etc. Compared to vulcanized rubber, although it is excellent in terms of workability and energy saving, it is still inferior in tensile strength and rubber elasticity.

Therefore, it is strongly desired to improve the tensile properties and rubber elasticity of the cross-linked olefin-based thermoplastic elastomer.
In recent years, regarding EPDM, which is one of the main raw materials for cross-linked olefinic thermoplastic elastomers, the molecular structure of EPDM obtained by synthesizing using a metallocene catalyst is higher than when using a conventional Ziegler catalyst. It has been reported that the material is uniform and exhibits excellent physical properties (see, for example, Non-Patent Document 1). Furthermore, since the metal residue derived from a catalyst can be reduced, long-term improvement in heat aging resistance is also expected.

  On the other hand, there has been reported a composition for improving the reactivity with peroxide by using EPDM copolymerized with vinylidene norbornene (VNB) and obtaining an olefinic thermoplastic elastomer having improved compression set (for example, Patent Document 1). However, with conventional Ziegler catalysts, VNB is not uniformly introduced, and it may be difficult to control long-chain branching formed during VNB copolymerization.

International Publication No. 1997/000288 Pamphlet

B. A. Harrington, M. G. Williams, “RUBBER WORLD” 2004, May, p.20-26

  An object of the present invention is to provide an olefinic thermoplastic elastomer composition that is excellent in tensile strength and rubber elasticity and can provide a molded article having a good appearance, and its use.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a copolymer rubber containing a structural unit derived from two specific types of dienes is excellent in cross-linking reactivity and molding processability. The present inventors have found that an olefinic thermoplastic elastomer composition obtained by dynamically crosslinking a composition containing a copolymer rubber is excellent in tensile strength and rubber elasticity, and completed the present invention.

That is, the olefinic thermoplastic elastomer composition (Y) of the present invention is crystalline polyolefin resin [I] 10 parts by weight or more and less than 60 parts by weight,
Ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, non-conjugated polyene (C) having one carbon / carbon double bond per molecule that can be polymerized by a metallocene catalyst, and metallocene Ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] containing structural units derived from nonconjugated polyene (D) having two carbon / carbon double bonds in one molecule that can be polymerized by a catalyst Composition obtained by dynamic crosslinking of rubber composition (X) containing more than 40 parts by weight and 90 parts by weight or less (the total amount of [I] and [II] is 100 parts by weight) (Y)
The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is:
(1) The molar ratio [(A) / (B)] of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) is 50/50 to 85/15,
(2) The sum total of the molar amount of the structural unit derived from the non-conjugated polyene (C) and the structural unit derived from the non-conjugated polyene (D) is 0.5 to 4.5 mol% in all the structural units,
(3) The intrinsic viscosity [η] measured in 135 ° C. decalin is 1.0 to 5.0 dl / g,
(4) The following formula (I) is satisfied.

Log {η ^* (0.01)} / Log {η ^* (10)}> 0.0753 × {apparent iodine value derived from non-conjugated polyene (D)} + 1.42 (I)
(In the formula, η ^* (0.01) represents a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η ^* (10) represents a viscosity (Pa · sec of 10 rad / sec at 190 ° C. )
It is preferable that the non-conjugated polyene (C) is 5-ethylidene-2-norbornene (ENB) and the non-conjugated polyene (D) is 5-vinyl-2-norbornene (VNB).

  The rubber composition (X) comprises 2 to 100 parts by weight of a softening agent relative to a total of 100 parts by weight of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. And at least one additive selected from 2 to 50 parts by weight of an inorganic filler.

  The rubber composition (X) contains 0.1 to 30 crosslinking agents with respect to a total of 100 parts by weight of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. It is preferably contained within the range of parts by weight.

The molded product of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).
The automotive exterior material of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).

The automotive glass run channel of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).
The automotive window frame material of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).

The automotive interior material of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).
The skin material of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).

The building material of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).
The gasket of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).

The foam of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).
The weatherstrip sponge of the present invention is formed from the olefinic thermoplastic elastomer composition (Y).

  The olefinic thermoplastic elastomer composition of the present invention has excellent tensile strength and rubber elasticity. Moreover, a molded article having a good appearance can be obtained using the composition. The thermoplastic elastomer composition of the present invention can be suitably used as materials for automobile exterior materials such as glass run channels and window frame materials for automobiles, automobile interior materials such as skin materials and weatherstrip sponges, and building materials and gaskets. it can.

Next, the present invention will be specifically described.
<Olefin-based thermoplastic elastomer (Y)>
The olefinic thermoplastic elastomer (Y) of the present invention comprises 10 parts by weight or more and less than 60 parts by weight of a crystalline polyolefin resin [I], ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a metallocene. Non-conjugated polyene (C) having one carbon / carbon double bond per molecule that can be polymerized by a catalyst and two carbon / carbon double bonds that can be polymerized by a metallocene catalyst per molecule The ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] containing a structural unit derived from the nonconjugated polyene (D) having more than 40 parts by weight and 90 parts by weight or less (total of [I] and [II] A composition (Y) obtained by dynamically cross-linking a rubber composition (X) containing an ethylene / α-olefin / non-conjugated polyene copolymer rubber. [II] (1) The molar ratio [(A) / (B)] of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) is 50/50 to 85/15. (2) The sum total of the molar amount of the structural unit derived from the non-conjugated polyene (C) and the structural unit derived from the non-conjugated polyene (D) is 0.5 to 4.5 mol% in the total structural units, (3) The intrinsic viscosity [η] measured in 135 ° C. decalin is 1.0 to 5.0 dl / g, and (4) satisfies the following formula (I).

Log {η ^* (0.01)} / Log {η ^* (10)}> 0.0753 × {apparent iodine value derived from non-conjugated polyene (D)} + 1.42 (I)
(In the formula, η ^* (0.01) represents a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η ^* (10) represents a viscosity (Pa · sec of 10 rad / sec at 190 ° C. )
In addition, in this specification, said (1)-(4) is also described as requirements (1)-(4), respectively.
First, each component contained in rubber composition (X) used in order to obtain the olefin type thermoplastic elastomer composition (Y) of this invention is demonstrated.

[Crystalline polyolefin resin [I]]
The crystalline polyolefin resin [I] used in the present invention is not particularly limited, but usually a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms is used. The crystalline polyolefin resin [I] may be a resin composed of one kind of polymer or a resin composed of two or more kinds of polymers.

  When the crystalline polyolefin resin [I] is a copolymer of an α-olefin having 2 to 20 carbon atoms, at least two kinds of α-olefins having 2 to 20 carbon atoms are used as monomers. The resulting copolymer may be a copolymer of at least one α-olefin having 2 to 20 carbon atoms and a monomer containing a vinyl group (excluding α-olefin) (also referred to as vinyl monomer). It may be a coalescence.

  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 crystalline polyolefin resin [I] 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 structural units derived from ethylene and structural units derived from vinyl monomers such as α-olefins having 3 to 20 carbon atoms and / or vinyl acetate and 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 α-olefins having 2 to 20 carbon atoms 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 homopolymer having a unit and 10 mol% or less of other structural units derived from α-olefin having 2 to 20 carbon atoms (9) 4-methyl-1-pentene random copolymer having a structural unit derived from 4-methyl-1-pentene and a structural unit derived from other α-olefin having 2 to 20 carbon atoms in an amount of 20 mol% or less As the crystalline polyolefin resin [I], it is preferable to use a propylene polymer, (3) a propylene homopolymer, (4) a structural unit derived from propylene, and another α-olefin having 2 to 20 carbon atoms. A propylene random random copolymer having a constitutional unit of 10 mol% or less, (5) a constitutional unit derived from propylene, and a constitutional unit derived from another α-olefin having 2 to 20 carbon atoms and 30 mol% or less. It is more preferable to use at least one propylene polymer selected from propylene block copolymers.

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

  The rubber composition (X) used in the present invention contains the crystalline polyolefin resin [I] and an ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] described later. Usually, the crystalline polyolefin resin [I] is 10 parts by weight or more and less than 60 parts by weight per 100 parts by weight in total of [I] and the later-described ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is contained in an amount of more than 40 parts by weight and 90 parts by weight or less, preferably 10 parts by weight or more and less than 45 parts by weight of the crystalline polyolefin resin [I]. Further, it contains an ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] described later in an amount of more than 55 parts by weight and 90 parts by weight or less.

[Ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]]
The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] used in the present invention is a carbon that can be polymerized by ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a metallocene catalyst. -Non-conjugated polyene (C) having one carbon double bond in one molecule and non-conjugated polyene (D) having two carbon-carbon double bonds polymerizable in a metallocene-based catalyst An ethylene / α-olefin / non-conjugated polyene copolymer rubber containing a structural unit derived from (1) 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 85/15, and (2) the structural unit derived from the non-conjugated polyene (C) and the structural unit derived from the non-conjugated polyene (D) The total molar amount is (3) The intrinsic viscosity [η] measured in 135 ° C. decalin is 1.0 to 5.0 dl / g, and (4) the following formula (I Is satisfied.

Log {η ^* (0.01)} / Log {η ^* (10)}> 0.0753 × {apparent iodine value derived from non-conjugated polyene (D)} + 1.42 (I)
(In the formula, η ^* (0.01) represents a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η ^* (10) represents a viscosity (Pa · sec of 10 rad / sec at 190 ° C. )

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] used in the present invention is a carbon that can be polymerized by ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a metallocene catalyst. -Non-conjugated polyene (C) having one carbon double bond in one molecule and non-conjugated polyene (D) having two carbon-carbon double bonds polymerizable in a metallocene-based catalyst A copolymer containing a structural unit derived from the above, usually comprising ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a carbon / carbon double bond that can be polymerized by a metallocene catalyst. Polymerization of non-conjugated polyene (C) having one in the molecule and non-conjugated polyene (D) having two carbon / carbon double bonds that can be polymerized by a metallocene catalyst in the presence of the metallocene catalyst This By obtained.

(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 rubber [II] contains at least one structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and two or more types. The structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms may be included.

  Such α-olefin has relatively low raw material cost and excellent copolymerizability, and ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] has excellent mechanical properties and good flexibility. This is preferred for the sake of illustration.

(Non-conjugated polyene (C) having one carbon / carbon double bond per molecule that can be polymerized by a metallocene catalyst)
Non-conjugated polyene (C) having one carbon / carbon double bond that can be polymerized by a metallocene catalyst in one molecule includes chain polyenes whose both ends are vinyl groups (CH ₂ ═CH—). I can't. Examples of the non-conjugated polyene (C) having one carbon / carbon double bond that can be polymerized by a metallocene catalyst in one molecule 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-propiene -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 -1,7-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, Examples include 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.

  The alicyclic polyene is composed of an alicyclic portion having one carbon / carbon double bond (unsaturated bond) and a chain portion having an internal olefin bond (carbon / carbon double bond). Specific examples thereof include 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene-2-norbornene, and the like. 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 rubber [II] is a non-conjugated polyene having one carbon / carbon double bond per molecule that can be polymerized by at least one metallocene catalyst ( A structural unit derived from a non-conjugated polyene (C) having a structural unit derived from C) and having one carbon-carbon double bond per molecule that can be polymerized by two or more metallocene catalysts. May be included.

(Non-conjugated polyene (D) having two carbon / carbon double bonds that can be polymerized by a metallocene catalyst in one molecule)
Specific examples of non-conjugated polyene (D) having two carbon / carbon double bonds per molecule that can be polymerized by a metallocene catalyst include 5-vinyl-2-norbornene (VNB), 5-allyl-2 5-alkenyl-2-norbornene such as norbornene; 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, tetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] deca-3,8-diene, etc. Alicyclic polyenes; α, ω-dienes such as 1,7-octadiene, 1,9-decadiene and the like.

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

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is a non-conjugated polyene having two carbon / carbon double bonds per molecule that can be polymerized by at least one metallocene catalyst ( A structural unit derived from a non-conjugated polyene (D) containing two structural units derived from D) and having two carbon / carbon double bonds per molecule that can be polymerized by two or more metallocene catalysts. May be included.

(Requirement (1))
Requirement (1) is the mole of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) in the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. The ratio [(A) / (B)] is 50/50 to 85/15, preferably 55/45 to 75/25.

When the molar ratio is within the above range, it is preferable from the viewpoints of flexibility and mechanical properties of the obtained ethylene / α-olefin / nonconjugated polyene copolymer rubber [II].
The molar ratio can be determined by ¹³ C-NMR.

(Requirement (2))
Requirement (2) is the molarity of the structural unit derived from the nonconjugated polyene (C) and the structural unit derived from the nonconjugated polyene (D) in the ethylene / α-olefin / nonconjugated polyene copolymer rubber [II]. The total amount is 0.5 to 4.5 mol%, preferably 1.5 to 4.0 mol%, more preferably 2.0 to 3.8 mol% in all structural units. It is.

It is preferable from the viewpoint of rubber elasticity and mechanical properties of the ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] that the total molar amount is within the above range.
The molar amount can be determined by ¹³ C-NMR.

  Further, the molar ratio of the structural unit derived from the non-conjugated polyene (C) and the structural unit derived from the non-conjugated polyene (D) of the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] ( (C) / (D)) is preferably 75/25 to 99.5 / 0.5.

(Requirement (3))
Requirement (3) is that the intrinsic viscosity [η] of the ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] measured in decalin at 135 ° C. is 1.0 to 5.0 dl / g, preferably Is assumed to be 1.5 to 4.0 dl / g.

When the intrinsic viscosity [η] is within the above range, it is preferable from the viewpoint of rubber elasticity and mechanical properties of the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II].
The intrinsic viscosity [η] can be determined by measuring according to ASTM D 1601.

(Requirement (4))
Requirement (4) is that the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] satisfies the following formula (I), preferably the following formula (I ′).

Log {η ^* (0.01)} / Log {η ^* (10)}> 0.0753 × {apparent iodine value derived from non-conjugated polyene (D)} + 1.42 (I)
Log {η ^* (0.01)} / Log {η ^* (10)}> 0.0753 × {apparent iodine value derived from non-conjugated polyene (D)} + 1.43 (I ′)
(In the above formulas (I) and (I ′), η ^* (0.01) represents a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η ^* (10) is at 190 ° C. (Represents a viscosity (Pa · sec) of 10 rad / sec.)

In the above formulas (I) and (I ′), Log {η ^* (0.01)} / Log {η ^* (10)} is obtained by using a viscoelasticity measuring apparatus to determine whether ethylene / α-olefin / nonconjugated polyene It can be determined by measuring η ^* (0.01) and η ^* (10) of the combined rubber [II].

Further, the apparent iodine value derived from the non-conjugated polyene (D) in the above formulas (I) and (I ′) can be determined by ¹ H-NMR and ¹³ C-NMR.
Hereinafter, ethylene, propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB, non-conjugated polyene (II) which are ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] are used. The copolymer obtained from D)) is taken as an example, and a method for determining the apparent iodine value derived from VNB (molecular weight 120.2) will be specifically shown.

First, each structural unit contained in ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] by ¹³ C-NMR (in this example, a structural unit derived from ethylene, a structural unit derived from propylene, a structural unit derived from ENB, % Of VNB-derived structural units). Next, the integrated value of the peak derived from ENB and the integrated value of the peak derived from the vinyl group of VNB are determined from the ¹ H-NMR spectrometer as follows.

1) [Integral value of peak derived from ENB]; (a), {(total of plural peaks around 4.7 to 5.3 ppm) −2 × (c)}
In addition, since the (a) peak and the (b) peak are detected together in a plurality of peaks near 4.7 to 5.3 ppm, (a) is calculated from the above formula.

2) [Integral value of peak derived from vinyl group of VNB]; (c) Sum of peaks in the vicinity of 5.5 to 6.0 ppm. In the above formulas 1) and 2), (a), (b) and ( c) shows (a), (b) and (c) in the following formulas (X) and (Y), respectively. )

得られた積分値を用いてＶＮＢ（非共役ポリエン（Ｄ））（分子量１２０．２）に由来するみかけのヨウ素価を以下の式より算出することができる。なお、ヨウ素の分子量は２５３．８１である。

The apparent iodine value derived from VNB (non-conjugated polyene (D)) (molecular weight 120.2) can be calculated from the following formula using the obtained integrated value. The molecular weight of iodine is 253.81.

Apparent iodine value derived from VNB (non-conjugated polyene (D)) = [integrated value of peak derived from vinyl group of VNB (non-conjugated polyene (D))] / [integrated value of peak derived from ENB] × [% By weight of ENB determined from ¹³ C-NMR spectrum meter] × 253.81 / 120.2

  When the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] satisfies the above formula (I), the olefin-based thermoplastic elastomer composition (Y ) The polymer derived from the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] contained therein has many long-chain branches. Having a lot of long chain branches is preferable because it exhibits excellent moldability and good rubber elasticity and mechanical properties due to the entanglement of side chains.

  On the other hand, when the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] does not satisfy the above formula (I), the extrusion processability of the resulting thermoplastic elastomer composition (Y) is poor, and the surface The appearance deteriorates, which is not preferable.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] has a Mooney viscosity [ML _{1 + 4} ] measured at 160 ° C. of preferably 40 to 160, more preferably 50 to 150.

The Mooney viscosity can be measured using a Mooney viscometer (SMV201 model manufactured by Shimadzu Corporation) under the condition of 160 ° C. in accordance with JIS K6300.
Further, a rule of thumb, a Mooney viscosity measured at 160 ° C. [ML 1 _{+ 4],} the Mooney viscosity measured at 100 ° C. [ML 1 _{+ 4],} observed correlation below, for example, at 160 ° C. When the measured Mooney viscosity [ML _{1 + 4} ] is 40, the Mooney viscosity [ML _{1 + 4} ] at 100 ° C. becomes 95.
{Mooney viscosity at 100 ° C. [ML _{1 + 4} ]} = 2.38 × {Mooney viscosity at 160 ° C. [ML _{1 + 4} ]}

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is synthesized using a metallocene catalyst having a structure represented by the following formula (α) or (β). The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is preferably represented by the following general formula (i), more preferably the following formula (ii), (iii), (iv), (v) or It is synthesized using a metallocene-based catalyst having a structure represented by (vi), particularly preferably (iii).

  By synthesizing using such a catalyst, an ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] satisfying the requirements (1) to (4) can be obtained.

（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。
Ｍは、チタン、ジルコニウムまたはハフニウムである。

(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 aspects (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-based catalyst having a structure represented by the above formula (iii) is used, in the polymerization reaction for obtaining the ethylene / α-olefin / nonconjugated polyene copolymer rubber [II], the nonconjugated polyene (C) and Particularly excellent in copolymerizability of (D). Therefore, ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] polymerized using a metallocene-based catalyst having a structure represented by the formula (iii) is, for example, 5-vinyl-2-norbornene (VNB). ) Can be efficiently incorporated into the polymer and long chain branching can be introduced at a high rate.

  Further, the obtained ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] has a narrow molecular weight distribution and composition distribution, and an ethylene / α-olefin / non-conjugated polyene copolymer rubber having an extremely uniform molecular structure [ II] can be prepared, the formation of gel-like spots 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 ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] does not contain gel-like particles, and thus has an excellent surface appearance. Production stability is also good because of excellent shape retention.

  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.

<Method for producing ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]>
The method for producing the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] preferably uses the metallocene catalyst described above, particularly the metallocene catalyst having the structure represented by the above formula (iii). The method for producing the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] preferably includes 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), the α-olefin (B), the non-conjugated polyene (C) and the non-conjugated polyene (D) are copolymerized, and the concentration of the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is This is a step of obtaining a polymerization reaction solution of 8 to 12% by weight, preferably 8.5 to 12.0% by weight.

  The ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] obtained by adjusting the concentration of the ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] to the polymerization solvent within the above range. Can satisfy the above requirement (4). In addition, when the concentration of the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] with respect to the polymerization solvent exceeds 12% by weight, the viscosity of the polymerization solution is too high. May be difficult.

  Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Examples of the aliphatic hydrocarbon include pentane, hexane, heptane, and the like, among these, separation from the obtained ethylene / α-olefin / nonconjugated polyene copolymer rubber [II], from the viewpoint of purification, Hexane is preferred.

  As such a production method, the above catalyst is used as a main catalyst, an organoaluminum compound such as a boron compound and / or a trialkyl compound is used as a cocatalyst, an aliphatic hydrocarbon such as hexane is used as a solvent, and a reactor equipped with a stirrer A continuous method or a batch method 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 (hereinafter also referred to as “TIBA”).
The reaction temperature can be raised to 100 ° C. because the catalyst is not deactivated even at high temperatures.

The polymerization pressure is in the range of more than 0 to -8 MPa (gauge pressure), preferably more than 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 80/20, more preferably 30/70 to 70/30. is there.

  The molar ratio ((C) / (D)) of the charge of the nonconjugated polyene (C) and the nonconjugated polyene (D) is preferably 85/15 to 99.5 / 0.5, more preferably 90. / 10 to 99/1.

The molar ratio ((A) / (C)) of the charge of ethylene (A) and the nonconjugated polyene (C) is preferably 70/30 to 99/1, more preferably 80/20 to 98/2. .
The molar ratio ((A) / (D)) of the charge of ethylene (A) and the non-conjugated polyene (D) is preferably 70/30 to 99.9 / 0.1, more preferably 80/20 to 99. .9 / 0.1.

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.
Next, the rubber composition (X) used for obtaining the olefinic thermoplastic elastomer composition (Y) of the present invention will be described.

[Rubber composition (X)]
The rubber composition (X) comprises 10 parts by weight or more and less than 60 parts by weight of the above-mentioned crystalline polyolefin resin [I] and more than 40 parts by weight of the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. 90 parts by weight or less (the total amount of [I] and [II] is 100 parts by weight).

In addition to the above [I] and [II], the rubber composition (X) may contain other components depending on the purpose.
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 (X) can also be blended with a rubber other than the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. The content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] in the rubber composition (X) is preferably 20% by weight or more, more preferably 30 to 90% by weight.

The rubber composition (X) comprises a crystalline polyolefin resin [I], an ethylene / α-olefin / non-conjugated polyene copolymer rubber [II], and other components contained as necessary, for example, a mixer It can be prepared by kneading at a desired temperature using a kneader known in the art such as a kneader or a roll. Since the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is excellent in kneadability, the rubber composition (X) can be prepared satisfactorily.
Examples of the additive are shown below.

(Softener)
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 mustard 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, dioctyl a Ester softeners such as dipate and dioctyl sebacate; other examples include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon-based synthetic lubricating oil, tall oil, and sub (factis). Of these, petroleum softeners are preferred, and process oils are particularly preferred.

  When the rubber composition (X) contains a softening agent, the amount of the softening agent is the sum of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. The amount is usually 2 to 100 parts by weight, preferably 10 to 100 parts by weight with respect 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 (X) contains an inorganic filler, the compounding amount of the inorganic filler is the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. Is usually 2 to 50 parts by weight, preferably 5 to 50 parts by weight based on 100 parts by weight. When the blending amount is within the above range, kneadability of the olefinic thermoplastic elastomer composition (Y), mechanical properties of the rubber molded body obtained from the olefinic thermoplastic elastomer composition (Y) (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.

In addition, when rubber composition (X) contains a reinforcing agent, mechanical properties such as tensile strength, tear strength, and wear resistance of the olefin-based thermoplastic elastomer composition (Y) may be improved.
When the rubber composition (X) contains a reinforcing agent, the compounding amount of the reinforcing agent is the sum of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. The amount is usually 30 to 200 parts by weight, preferably 50 to 180 parts by weight, and more preferably 70 to 160 parts by weight with respect to 100 parts by weight. When the blending amount is within the above range, the kneading processability of the olefinic thermoplastic elastomer composition (Y), the mechanical properties (for example, strength, flexibility, etc.) of the resulting rubber molded article and the compression set are excellent.

(Anti-aging agent (stabilizer))
By blending an anti-aging agent (stabilizer) with the rubber composition (X), the lifetime of the olefinic thermoplastic elastomer composition (Y) and the rubber molded body formed from the composition (Y) is lengthened. It is possible. 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 alone or in combination of two or more. When the rubber composition (X) contains an anti-aging agent, the blending amount of the anti-aging agent is rubber. Usually, 0.3 to 10 parts by weight with respect to 100 parts by weight of the components (ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] and rubber other than the rubber contained in the rubber composition (X)) , Preferably 0.5 to 7.0 parts by weight, more preferably 0.7 to 5.0 parts by weight. When the blending amount of the antioxidant is within the above range, there is no bloom on the surface of the resulting rubber composition (X), and vulcanization inhibition does not occur.

(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 (X) contains a processing aid, the blending amount of the processing aid is the rubber component (the ethylene / α-olefin / non-conjugated polyene copolymer contained in the rubber composition (X)). 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 [II] and other rubbers. When the blending amount of the processing aid is within the above range, there is no bloom on the surface of the rubber composition (X) to be obtained, 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 (X) contains an activator, the compounding amount of the activator is determined according to the rubber component (ethylene / α-olefin / non-conjugated polyene copolymer rubber contained in the rubber composition (X) [ II] and a rubber other than the rubber) is usually 0.2 to 10 parts by weight, preferably 0.3 to 5 parts by weight, and 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.

  In the case where the rubber composition (X) contains a hygroscopic agent, the blending amount of the hygroscopic agent is determined according to the rubber component (the ethylene / α-olefin / non-conjugated polyene copolymer rubber contained in the rubber composition (X) [ II] and a rubber other than the rubber) 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.

In addition, the additives usually used for rubber can be arbitrarily blended within a range not impairing the object of the present invention.
The rubber composition (X) includes 2 to 100 parts by weight of a softening agent with respect to 100 parts by weight in total of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. And at least one additive selected from 2 to 50 parts by weight of an inorganic filler is preferable from the viewpoint of moldability of the resulting olefinic thermoplastic elastomer composition (Y).

  Moreover, it is preferable that rubber composition (X) contains a crosslinking agent from a viewpoint of rubber elasticity of the olefin type thermoplastic elastomer composition (Y) obtained. When the rubber composition (X) contains a crosslinking agent, the crosslinking is carried out with respect to a total of 100 parts by weight of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. The agent is preferably contained within the range of 0.1 to 30 parts by weight, and more preferably within the range of 0.2 to 20 parts by weight.

  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, the rubber composition (X) preferably contains the following crosslinking aid.

  As a crosslinking aid preferable when using an organic peroxide as a crosslinking agent, for example, quinonedioxime-based crosslinking aids such as sulfur and p-quinonedioxime; ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and the like Acrylic crosslinking aids; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; other maleimide crosslinking 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.

The olefinic thermoplastic elastomer composition (Y) of the present invention is a composition obtained by dynamically crosslinking the above rubber composition (X).
In the present invention, dynamic crosslinking refers to a carbon / carbon double bond possessed by at least the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] by kneading the rubber composition (X) in a molten state. It is meant that a part of is crosslinked. In order to suitably perform dynamic crosslinking, the rubber composition (X) preferably contains the aforementioned crosslinking agent.

When dynamically crosslinking the rubber composition (X), either a non-open type device or an open type device may be used, but a non-open type device is preferably used.
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.

  The olefinic thermoplastic elastomer composition (Y) of the present invention is excellent in tensile strength, rubber elasticity, and the like, and is excellent in moldability, so that it can be used for various applications. As the reason why the olefinic thermoplastic elastomer composition (Y) of the present invention is excellent in tensile strength, rubber elasticity and the like and excellent in moldability, the present inventors have estimated as follows.

  The olefinic thermoplastic elastomer composition (Y) of the present invention comprises a sea phase derived from the crystalline polyolefin resin [I] contained in the rubber composition (X) and an ethylene / α-olefin / nonconjugated polyene copolymer. It is thought that it has an island phase derived from rubber [II]. The island phase is subjected to dynamic crosslinking when the olefinic thermoplastic elastomer composition (Y) is obtained from the rubber composition (X), so that the ethylene / α-olefin / nonconjugated polyene copolymer rubber [II] is used. It is considered to be formed from a copolymer rubber having a cross-linked structure derived therefrom. For this reason, the present inventors have estimated that the island phase is excellent in physical strength, and that the olefinic thermoplastic elastomer composition (Y) is excellent in tensile strength, rubber elasticity, and the like. Further, the sea phase is considered to be derived from the crystalline polyolefin resin [I], and it is considered that the phase does not have a crosslinked structure. For this reason, the present inventors estimated that the sea phase exhibits fluidity at a temperature of about 160 to 280 ° C., and that the olefinic thermoplastic elastomer composition (Y) is excellent in moldability.

<Molded body>
The molded product of the present invention is formed from an olefinic thermoplastic elastomer composition (Y). Since the olefinic thermoplastic elastomer composition (Y) is excellent in tensile strength, rubber elasticity and the like and excellent in moldability, various molded articles can be obtained.

  In addition, as a molded object of this invention, the molded object formed only from the said olefin type thermoplastic elastomer composition (Y) may be sufficient, and it is from the mixture of the said olefin type thermoplastic elastomer composition (Y) and an additive. It may be a formed body.

  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, the molded article of the present invention includes automotive exterior materials such as glass run channels and window frame materials for automobiles formed from the olefinic thermoplastic elastomer composition (Y), automotive interior materials such as skin materials, and building materials and gaskets. Is mentioned.

  Moreover, as a molded object of this invention, foams, such as a weatherstrip sponge and the sponge material for interior skins, may be sufficient. When the molded product of the present invention is a foam, at least a foaming agent is used as an additive, and a mixture of the olefinic thermoplastic elastomer composition (Y) and an additive containing a foaming agent is foamed. A foam is obtained. In addition, since the mixture of the said olefin type thermoplastic elastomer composition (Y) and additive which used the foaming adjuvant as an additive with the foaming agent can perform foaming especially suitably, it is preferable.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
The physical properties of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (ethylene / α-olefin copolymer rubber in Comparative Examples 3 and 6) used in Examples and Comparative Examples were measured as follows.

[Molar ratio of structural unit derived from ethylene (A) to structural unit derived from α-olefin (B), mol% of structural unit derived from non-conjugated polyene (C), and non-conjugated polyene (D) Mol% of structural units derived from
Molar ratio [(A) / (B)] of the structural unit derived from ethylene (A) of the ethylene / α-olefin / non-conjugated polyene copolymer rubber and the structural unit derived from α-olefin (B), The content (mol%) of the structural unit derived from the non-conjugated polyene (C) and the structural unit derived from the non-conjugated polyene (D) was determined by intensity measurement using a ¹³ C-NMR spectrometer.

Hereinafter, composition analysis of copolymer rubber by ¹³ C-NMR spectrum meter for ethylene / α-olefin / non-conjugated polyene copolymer rubber containing structural units derived from ethylene, propylene, ENB and VNB (copolymer) The molar amount of each structural unit contained in the rubber will be described.

The structure (composition) analysis of ethylene, propylene and ENB copolymer by ¹³ C-NMR spectrometer was carried out by CJ Carman, RA Harrington, and CE Wilkes, Macromolecules, 10, p 536-544 (1977), Masahiro Kakugo, Yukio. Naito, Kooji Mizunuma, and Tatsuya, Miyatake, Macromolecules, 15, p 1150-1152 (1982) and G. Van der Velden, Macromolecules, 16, p 85-89 (1983). In Harri Lasarov, Tuula T. Pakkanen, Macromol. Rapid Commun., 20, p 356-360 (1999) and Harri Lasarov *, Tuula T. Pakkanen, Macromol. Rapid Commun., 22, p 434-438 (2001) Based on.

First, the integrated value of each peak derived from 1) ethylene, 2) propylene, 3) ENB, and 4) VNB was determined by a ¹³ C-NMR spectrometer.
1) Ethylene: [Integral value of peak derived from ethylene chain + [Integral value of peak derived from ethylene-propylene chain] / 2],
2) Propylene: [Integral value of peak derived from propylene chain + [Integral value of peak derived from ethylene-propylene chain] / 2],
3) ENB: integrated value of peak derived from ENB-3 position, and 4) VNB: integrated value of peak derived from VNB-7 position.

  An outline of the structure derived from ENB and the structure derived from VNB is shown by the following structural formula. In addition, although the structure derived from VNB has a vinyl group at the terminal in the following structural formula, at least a part of the vinyl group is polymerized to form a long chain branch.

得られた積分値比より、それぞれのモル％を算出した。

Each mol% was calculated from the obtained integral value ratio.

[Apparent iodine value (IV) derived from non-conjugated polyene (D)]
The apparent iodine value (IV) derived from the non-conjugated polyene (D) of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is measured by ¹ H-NMR spectrometer, ¹³ C-NMR spectrometer and the following Obtained by the formula.

First, [molar ratio of structural unit derived from ethylene (A) and structural unit derived from α-olefin (B), mol% of structural unit derived from non-conjugated polyene (C), and non-conjugated polyene (D )), The structural units contained in the ethylene / α-olefin / non-conjugated polyene copolymer rubber by ¹³ C-NMR (in the production examples 1 to 3, the ethylene-derived structural units are derived from ethylene). % By weight of structural units, structural units derived from propylene, structural units derived from ENB, structural units derived from VNB).

In addition, weight% of each structural unit was converted from the mol% of each structural unit calculated | required by < ¹³ > C-NMR. In the conversion, the molecular weight of ethylene was 28.05, the molecular weight of propylene was 42.08, and the molecular weights of ENB and VNB were 120.2, respectively.

Subsequently, the integrated value of the peak derived from ENB and the integrated value of the peak derived from the vinyl group of VNB were determined from the ¹ H-NMR spectrometer as follows.
1) [Integral value of peak derived from ENB]; (a), {(total of plural peaks around 4.7 to 5.3 ppm) −2 × (c)}
In addition, since the (a) peak and the (b) peak are detected together in a plurality of peaks near 4.7 to 5.3 ppm, (a) is calculated from the above formula.

2) [Integral value of peak derived from vinyl group of VNB]; (c) Sum of peaks in the vicinity of 5.5 to 6.0 ppm. In the above formulas 1) and 2), (a), (b) and ( c) shows (a), (b) and (c) in the following formulas (X) and (Y), respectively. )

得られた積分値を用いてＶＮＢ（非共役ポリエン（Ｄ））（分子量１２０．２）に由来するみかけのヨウ素価を以下の式より算出した。なお、ヨウ素の分子量は２５３．８１である。

The apparent iodine value derived from VNB (non-conjugated polyene (D)) (molecular weight 120.2) was calculated from the following formula using the obtained integrated value. The molecular weight of iodine is 253.81.

Apparent iodine value derived from VNB (non-conjugated polyene (D)) = [integrated value of peak derived from vinyl group of VNB (non-conjugated polyene (D))] / [integrated value of peak derived from ENB] × [% By weight of ENB determined from ¹³ C-NMR spectrum meter] × 253.81 / 120.2
[Intrinsic viscosity [η]]
The intrinsic viscosity [η] (dL / g) of the ethylene / α-olefin / non-conjugated polyene copolymer rubber was measured in 135 ° C. decalin.

[Mooney viscosity [ML _{1 + 4} (160 ° C)]]
The Mooney viscosity [ML _{1 + 4} (160 ° C.)] of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is a Mooney viscometer (Shimadzu Corporation) under the condition of 160 ° C. in accordance with JIS K6300. SMV201 model).

[Frequency dependence of viscosity [η ^* ]]
The η ^* (0.01) and η ^* (10) of the ethylene / α-olefin / non-conjugated polyene copolymer rubber were measured using a viscoelasticity tester (model RDS-2) manufactured by Rheometric. Specifically, as a sample, a 2 mm-thick sheet obtained by pressing ethylene / α-olefin / non-conjugated polyene copolymer rubber at 190 ° C., which was formed into a disk shape having a diameter of 25 mm × 2 mm, The measurement was performed under the following conditions. Note that RSI Orchestrator (Rheometric) was used as data processing software.
Geometry: parallel plate,
Measurement temperature: 190 ° C.
Frequency: 0.01-500 rad / sec,
Distortion rate: 1.0%.

Under such conditions, the frequency dependence of the viscosity [η ^* ] is measured, and the viscosity [η ^* ] at 0.01 and 10 rad / sec is determined as η ^* (0.01) and η ^* (10), respectively. It was. Using the obtained numerical value, the value of Log {η ^* (0.01)} / Log {η ^* (10)} was calculated.

[Production Example 1]
Continuously using a 300 L polymerization vessel equipped with a stirring blade, ethylene, propylene as α-olefin (B), 5-ethylidene-2-norbornene (ENB) and non-conjugated polyene (non-conjugated polyene (C) ( A polymerization reaction of a quaternary copolymer composed of 5-vinyl-2-norbornene (VNB) as D) was carried out at 80 ° C.

  As a polymerization solvent, hexane (feed amount 56 L / h) is used, continuously, ethylene feed amount 5.3 Kg / h, propylene feed amount 5.6 Kg / h, ENB feed amount 1.6 Kg / h, The polymerization reactor was continuously fed so that the VNB feed amount was 0.12 Kg / h and the hydrogen feed amount was 10 NL / h.

While maintaining the polymerization pressure at 1.8 MPa and the polymerization temperature at 80 ° C., the main catalyst is a catalyst having a structure represented by the above formula (iii) [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 was continuously fed to a feed rate of 0.048 mmol / h. Further, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ is fed as a co-catalyst at a feed rate of 0.24 mmol / h, and triorganobutylaluminum (TIBA) is fed as an organoaluminum compound at a feed rate of 1.0 mmol / h. Each was continuously fed.

The catalyst having the structure represented by the above formula (iii) was obtained by synthesis according to the method described in International Publication No. 98/49212 pamphlet.
Thus, an ethylene / α-olefin / nonconjugated polyene copolymer rubber composed of ethylene, propylene, ENB and VNB was obtained in a 10.5 wt% solution state. After adding a small amount of methanol to the polymerization reaction liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and separating the ethylene / α-olefin / non-conjugated polyene copolymer rubber from the solvent by a steam stripping treatment, It dried under reduced pressure at 80 degreeC all day and night.

By the above operation, an ethylene / α-olefin / non-conjugated polyene copolymer rubber formed from ethylene, propylene, ENB and VNB was obtained at a rate of 5.2 kg / hour.
The apparent iodine value (IV) derived from the non-conjugated polyene (D) in the obtained ethylene / α-olefin / non-conjugated polyene copolymer rubber was 1.33 (g / 100 g).
Table 1 shows the polymerization conditions and the physical properties of the obtained ethylene / α-olefin / non-conjugated polyene copolymer rubber.

[Production Examples 2 to 4]
Except having changed into the polymerization conditions shown in Table 1, it carried out similarly to manufacture example 1, and obtained ethylene * alpha-olefin * nonconjugated polyene copolymer rubber.

The apparent iodine value (IV) derived from the nonconjugated polyene (D) in the obtained ethylene / α-olefin / nonconjugated polyene copolymer rubber is 0.93 (g / 100 g) (Production Example 2), 0 .93 (g / 100 g) (Production Example 3).
Table 1 shows the polymerization conditions and the physical properties of the obtained ethylene / α-olefin / non-conjugated polyene copolymer rubber.

[Production Example 5]
Copolymerization reaction of ethylene, propylene and 5-vinyl-2-norbornene (VNB) was continuously performed using a 15 L polymerization vessel equipped with a stirring blade.

Hexane was continuously supplied as a polymerization solvent from the upper part of the polymerization vessel at a rate of 5 L / hour, while the polymerization solution was continuously withdrawn from the lower part of the polymerization vessel so that the polymerization solution in the polymerization vessel was always 5 liters. As the catalyst, VOCl ₃ , Al (C ₂ H ₅ ) _1.5 Cl _1.5 was used. VOCl ₃ has a vanadium atom concentration of 0.50 mmol / L in the polymerization vessel, and Al (C ₂ H ₅ ) _1.5 Cl _1.5 has an aluminum atom concentration of 3.1 mmol / L in the polymerization vessel. Was continuously fed into the polymerization vessel.

  Monomer ethylene was continuously fed at a rate of 170 L / h and propylene at a rate of 375 L / h. VNB was continuously fed so that the concentration in the polymerization vessel was 0.84 g / L. Hydrogen was used as a molecular weight regulator, and this was supplied so that the hydrogen concentration in the polymer gas phase was 3.0 mol%. The copolymerization reaction was performed at a temperature of 40 ° C. by circulating cooling water through the outer jacket of the polymerization vessel while maintaining the polymerization pressure at 0.7 MPa.

  By such a reaction, an ethylene / α-olefin / non-conjugated polyene copolymer rubber formed from ethylene, propylene and VNB was obtained in a uniform solution state. A small amount of methanol was added to the polymerization reaction liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction. The copolymer rubber was separated from the solvent by a steam stripping treatment, and then dried under reduced pressure at 80 ° C. overnight. By the above operation, an ethylene / α-olefin / non-conjugated polyene copolymer rubber formed from ethylene, propylene and VNB was obtained at a rate of 234 g / hour.

The apparent iodine value (IV) derived from the non-conjugated polyene (D) in the obtained ethylene / α-olefin / non-conjugated polyene copolymer rubber was 1.33 (g / 100 g) (Production Example 5). It was.
Table 1 shows the physical properties of the obtained ethylene / α-olefin / non-conjugated polyene copolymer rubber.

[Production Example 6]
In Production Example 5, ethylene / α-olefin copolymer rubber was prepared in the same manner as in Production Example 5 except that ENB was continuously fed so that the concentration in the polymerization vessel was 7.6 g / L, and VNB was not fed. Got.

  Table 1 shows the physical properties of the obtained ethylene / α-olefin / non-conjugated polyene copolymer rubber.

〔実施例１〕
製造例１で得られたエチレン・α−オレフィン・非共役ポリエン共重合体ゴム５３．６ｗｔ％と、ポリプロピレン（プライムポリマー社製 Ｊ１０５、ＭＦＲ（ＡＳＴＭ Ｄ１２３８、２３０℃、荷重２．１６ｋｇ）＝１３ｇ／１０ｍｉｎ）２５ｗｔ％と、パラフィンオイル（出光社製 ＰＷ−３８０）２１．４ｗｔ％とをバンバリーミキサーを用いて、１２分間混練し、得られた混合物をロールに通してシート状にし、シートカッターで裁断して、角ペレットを製造した。

[Example 1]
Ethylene / α-olefin / non-conjugated polyene copolymer rubber 53.6 wt% obtained in Production Example 1 and polypropylene (J105, Prime Polymer Co., Ltd., J105, MFR (ASTM D1238, 230 ° C., load 2.16 kg)) = 13 g / 10 min) 25 wt% and paraffin oil (PW-380 manufactured by Idemitsu Co., Ltd.) 21.4 wt% are kneaded for 12 minutes using a Banbury mixer, and the resulting mixture is passed through a roll to form a sheet and cut with a sheet cutter. The square pellets were manufactured.

Next, 100 parts by weight of the square pellets, 0.3 part by weight of 2,5-di- (tert-butylperoxy) hexane, and 0.4 parts by weight of divinylbenzene were stirred and mixed with a Henschel mixer, and the resulting mixture was mixed. Using a twin screw extruder with L / D = 30 and screw diameter of 50 mm, extrusion was performed at 220 ° C. in a nitrogen atmosphere to produce pellets of a thermoplastic elastomer composition.
Furthermore, the physical properties of the thermoplastic elastomer composition were measured according to the following measuring method. The results are shown in Table 2.

[Example 2]
Example 1 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 2 In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

Example 3
Example 1 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 3 In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

Example 4
40.0 wt% of ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 and polypropylene (J105, Prime Polymer Co., Ltd., JFR, ASTM D1238, 230 ° C., load 2.16 kg) = 13 g / 10 min) 21.4 wt% and paraffin oil (PW-380, Idemitsu Co., Ltd., 38.6 wt%) were kneaded for 12 minutes using a Banbury mixer, and the resulting mixture was passed through a roll to form a sheet. A square pellet was manufactured by cutting.

Next, 100 parts by weight of the square pellets, 3.0 parts by weight of brominated alkylphenol resin (Takakiro 250-I manufactured by Taoka Chemical Co., Ltd.), 1.8 parts by weight of zinc oxide (type 2 zinc oxide manufactured by Shodo Chemical), phenol A system antioxidant (Ciba Japan Co., Ltd. Irganox 1010) 0.1 parts by weight and calcium oxide (Inoue Lime Co., Ltd. Vesta # 20) were sufficiently stirred and mixed with a Henschel mixer, and the resulting mixture was Using a twin screw extruder with L / D = 30 and screw diameter of 50 mm, extrusion was performed at 220 ° C. in a nitrogen atmosphere to produce pellets of a thermoplastic elastomer composition.
Furthermore, the physical properties of the thermoplastic elastomer composition were measured according to the following measuring method. The results are shown in Table 2.

Example 5
Example 4 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 2. In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

Example 6
Example 4 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 3. In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

[Comparative Example 1]
Example 1 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 4 In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

[Comparative Example 2]
Example 1 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 5 In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

[Comparative Example 3]
The same procedure as in Example 1 was conducted except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin copolymer rubber obtained in Production Example 6. A pellet of a thermoplastic elastomer composition was obtained. The results are shown in Table 2.

[Comparative Example 4]
Example 4 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was replaced with the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 4. In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

[Comparative Example 5]
Example 4 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was replaced with the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 5. In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

[Comparative Example 6]
Example 4 except that the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 1 was changed to the ethylene / α-olefin / non-conjugated polyene copolymer rubber obtained in Production Example 6. In the same manner, pellets of a thermoplastic elastomer composition were obtained. The results are shown in Table 2.

[Durometer A hardness (degree)]
Using a 50-t press, a sheet sample of 20 cm × 20 cm × 2 mm prepared from the pellets of the thermoplastic elastomer composition was used as a test sample, and JIS A hardness was measured with a durometer A hardness meter in accordance with JIS6253.

(Tensile properties)
Using a 50-ton press, a 20 cm × 20 cm × 2 mm sheet sample prepared from the pellets of the thermoplastic elastomer composition is used as a test sample, and a tensile test is performed in accordance with JIS6251 at a measurement temperature of 25 degrees and a tensile speed of 500 mm / min. Tensile modulus M100 to M300% (MPa), strength at break TB (MPa) and EB (%) were measured.

[Evaluation of extruded design surface condition]
The pellets of the prepared thermoplastic elastomer composition were extruded at 220 ° C. in a nitrogen atmosphere using a twin screw extruder with L / D = 30 and a screw diameter of 50 mm, and predetermined in a die shape having a width of 1.5 cm and a thickness of 2 mm. It was molded into the shape of The extruded design surface state of the obtained flat plate sample (3 cm width × 2 mm thickness × length 2 m) was evaluated in three stages according to the following criteria.
○: Excellent smoothness and good appearance.
Δ: Some irregularities are observed, and surface gloss is poor.
X: Many fine unevenness | corrugations are seen, and smoothness is scarce.

[Compression set [CS]]
A block sample was prepared from pellets of the thermoplastic elastomer composition and attached to a compression set mold. The specimen was compressed so that the height of the specimen was ¼ of that before applying the load, and the mold was set in a gear oven at 70 ° C. and 100 ° C. and heat-treated for 22 hours.

Next, the test piece was taken out from the mold, allowed to cool for 30 minutes, the height of the test piece was measured, and compression set [CS] (%) was calculated from the following formula.
Compression set [CS] (%) = {(t ₀ −t ₁ ) / (t ₀ −t ₂ )} × 100
t ₀ : Height of the test piece before the test.
t ₁ : Height after heat-treating the specimen and allowing it to cool for 30 minutes.
t ₂ : Height of the test piece attached to the measurement mold.

Claims (16)

Crystalline polyolefin resin [I] 10 parts by weight or more and less than 60 parts by weight;
Ethylene (A), α-olefin (B) having 3 to 20 carbon atoms, non-conjugated polyene (C) having one carbon / carbon double bond per molecule that can be polymerized by a metallocene catalyst, and metallocene Ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] containing structural units derived from non-conjugated polyene (D) having two carbon / carbon double bonds per molecule that can be polymerized by a catalyst Composition obtained by dynamically crosslinking rubber composition (X) containing more than 40 parts by weight and 90 parts by weight or less (the total amount of [I] and [II] is 100 parts by weight) (Y)
The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]
(1) The molar ratio [(A) / (B)] of the structural unit derived from ethylene (A) and the structural unit derived from α-olefin (B) is 50/50 to 85/15,
(2) The sum total of the molar amount of the structural unit derived from the non-conjugated polyene (C) and the structural unit derived from the non-conjugated polyene (D) is 0.5 to 4.5 mol% in all the structural units,
(3) The intrinsic viscosity [η] measured in 135 ° C. decalin is 1.0 to 5.0 dl / g,
(4) meet the following formula (I), the
The ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is synthesized using a metallocene catalyst having a structure represented by the following formula (iii): Things (Y).
Log {η ^* (0.01)} / Log {η ^* (10)}> 0.0753 × {apparent iodine value derived from non-conjugated polyene (D)} + 1.42 (I)
(In the formula, η ^* (0.01) represents a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η ^* (10) represents a viscosity (Pa · sec of 10 rad / sec at 190 ° C. )

In the presence of the metallocene catalyst having the structure represented by the above formula (iii), the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] uses an aliphatic hydrocarbon as a polymerization solvent. The ethylene (A), α-olefin (B), non-conjugated polyene (C) and non-conjugated polyene (D) are copolymerized, and the concentration of the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is The olefin-based thermoplastic elastomer composition (Y) according to claim 1, wherein the olefin-based thermoplastic elastomer composition (Y) is obtained by a method having a step of obtaining a polymerization reaction solution of 8% by weight or more. In the presence of the metallocene catalyst having the structure represented by the above formula (iii), the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] uses an aliphatic hydrocarbon as a polymerization solvent. The ethylene (A), α-olefin (B), non-conjugated polyene (C) and non-conjugated polyene (D) are copolymerized, and the concentration of the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II] is The olefin-based thermoplastic elastomer composition (Y) according to claim 1, wherein the olefin-based thermoplastic elastomer composition (Y) is obtained by a method having a step of obtaining 8 to 12% by weight of a polymerization reaction solution. The non-conjugated polyene (C) is 5-ethylidene-2-norbornene (ENB), and the non-conjugated polyene (D) is 5-vinyl-2-norbornene (VNB). The olefin type thermoplastic elastomer composition (Y) as described in any one of -3 . The rubber composition (X) comprises 2 to 100 parts by weight of a softening agent with respect to a total of 100 parts by weight of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. and at least one olefin-based thermoplastic elastomer composition according contain additives to any one of claims 1-4, characterized in being selected from 2 to 50 parts by weight of an inorganic filler (Y ). The rubber composition (X) contains 0.1 to 30 crosslinking agents with respect to a total of 100 parts by weight of the crystalline polyolefin resin [I] and the ethylene / α-olefin / non-conjugated polyene copolymer rubber [II]. It contains within the range of a weight part, The olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-5 characterized by the above-mentioned. The molded object formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . The exterior material for motor vehicles formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . The glass run channel for motor vehicles formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . The window frame material for motor vehicles formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . The interior material for motor vehicles formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . A skin material formed from the olefinic thermoplastic elastomer composition (Y) according to any one of claims 1 to 6 . The building material formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . The gasket formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . The foam formed from the olefin type thermoplastic elastomer composition (Y) as described in any one of Claims 1-6 . A weatherstrip sponge formed from the olefinic thermoplastic elastomer composition (Y) according to any one of claims 1 to 6 .