JPH11228751A - Olefin-based thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin-based thermoplastic elastomer composition which shows a high moldability and yields a molded part with a good rubber elasticity, tensile strength characteristic and appearance. SOLUTION: This composition is obtained by dynamically heating a blended product containing (A) from 10 to 60 pts.wt. crystalline polyolefin resin and (B) from 90 to 40 pts.wt. [the sum of components (A) and (B) is 100 pts.wt.] unsaturated olefin-based copolymer which comprises at least one α-olefin having a carbon number of from 2 to 20, a conjugated diene monomer of the formula [wherein R<1> and R<2> are each independently a hydrogen atom or an alkyl or aryl group having a carbon number of from 1 to 8, wherein at least one of R<1> and R<2> is a hydrogen atom] and, optionally, an aromatic vinyl compound, in the presence of an organic peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based thermoplastic elastomer composition, and more particularly to an olefin-based thermoplastic elastomer which is excellent in moldability and can provide a molded article excellent in rubber elasticity, tensile strength characteristics and the like. Composition.

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are lightweight and easy to recycle, so they are energy-saving and resource-saving elastomers, especially automotive parts, industrial machinery parts,
Widely used for electronic components and building materials. However, conventional olefin-based thermoplastic elastomers generally have a disadvantage that rubber elasticity is inferior to vulcanized rubber,
The improvement was strongly demanded.

[0003] As such an olefinic thermoplastic elastomer which is a substitute for a vulcanized rubber, a so-called completely crosslinked olefinic thermoplastic elastomer having a high degree of crosslinking has been hitherto described (for example, described in JP-B-55-18448). Thermoplastic elastomers) have been proposed, but fully crosslinked olefinic thermoplastic elastomers have better rubber elasticity than partially crosslinked olefinic thermoplastic elastomers, but they have better moldability or better moldability. Due to the problem of the appearance, the intended use was limited.

[0004] International Patent Application Publication: WO96 / 07
No. 681 describes a thermoplastic crosslinked product comprising an ethylene / styrene / ethylidene norbornene copolymer and polypropylene. However, this thermoplastic crosslinked product did not always have a sufficient balance of rubber elasticity, tensile strength, low-temperature properties and surface strength.

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and obtained by random copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a specific conjugated diene monomer. A blend containing an unsaturated olefin-based copolymer and a crystalline polyolefin resin, or an ethylene / α-olefin / non-conjugated polyene in addition to the unsaturated olefin-based copolymer and the crystalline polyolefin resin. A thermoplastic compound obtained by dynamically heat-treating a blend containing at least one component selected from the group consisting of a copolymer, a peroxide non-crosslinked hydrocarbon rubber and a softener in the presence of an organic peroxide. Elastomer compositions are found to be excellent in rubber elasticity, moldability, etc., and in such thermoplastic elastomer compositions,
The present inventors have also found that a composition containing a crystalline polyolefin resin is also excellent in rubber elasticity, moldability, and the like, and have completed the present invention.

[0006]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a molded article having excellent moldability and excellent rubber elasticity and tensile strength characteristics. It is an object of the present invention to provide an olefin-based thermoplastic elastomer composition that can be used.

[0007]

The first olefin-based thermoplastic elastomer composition according to the present invention comprises (A) a crystalline polyolefin resin: 10 to 60 parts by weight, and (B-1) at least one kind having 2 to 20 carbon atoms. Olefin copolymer of the formula (I) and a conjugated diene monomer represented by the following formula (I): 90 to 40 parts by weight [component (A)
And the total amount of (B-1) is 100 parts by weight)], and is dynamically heat-treated in the presence of an organic peroxide.

[0008]

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[In the formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and at least one of R ¹ and R ² is a hydrogen atom It is. Further, the second olefin-based thermoplastic elastomer composition according to the present invention comprises: (A) a crystalline polyolefin resin:
0 to 60 parts by weight of (B-2) at least one α-olefin having 2 to 20 carbon atoms, a conjugated diene monomer represented by the above formula (I), and an unsaturated vinyl compound Olefin-based copolymer: A blend containing 90 to 40 parts by weight [the total amount of the components (A) and (B-2) is 100 parts by weight] is dynamically mixed in the presence of an organic peroxide. It is characterized by being obtained by heat treatment.

[0010] The first olefinic thermoplastic elastomer composition according to the present invention may optionally contain the following component (C):
(D) and (E) can be included, and the three-component, four-component, and five-component thermoplastic elastomer compositions are as follows. (A) crystalline polyolefin resin: 10 to 60 parts by weight, (B-1) unsaturated olefin-based copolymer: 85 to 10 parts by weight, and (C) ethylene / α-olefin / non-conjugated polyene Copolymer: 1
５０50 parts by weight, (D) peroxide non-crosslinked hydrocarbon rubber: 1-20 parts by weight, and (E) softener: 1-40
A blend containing at least one component selected from the group consisting of parts by weight [the total amount of components (A), (B-1), (C), (D) and (E) is 100 parts by weight] Is dynamically heat-treated in the presence of an organic peroxide to obtain a thermoplastic elastomer composition.

The second olefin-based thermoplastic elastomer composition according to the present invention can contain the following components (C), (D) and (E) if necessary. The five-component and five-component thermoplastic elastomer compositions are as follows. (A) crystalline polyolefin resin: 10 to 60 parts by weight, (B-2) unsaturated olefin-based copolymer: 85 to 10 parts by weight, and
(C) an ethylene / α-olefin / non-conjugated polyene copolymer: 1 to 50 parts by weight, (D) a peroxide non-crosslinked hydrocarbon rubber: 1 to 20 parts by weight, and (E) a softener:
At least one component selected from the group consisting of 1 to 40 parts by weight [the total amount of components (A), (B-2), (C), (D) and (E) is 100 parts by weight]. A thermoplastic elastomer composition obtained by dynamically heat-treating a blend to be produced in the presence of an organic peroxide.

In the present invention, the (B-1) unsaturated olefin copolymer has a molar ratio of a constitutional unit derived from ethylene to a constitutional unit derived from an α-olefin having 3 to 20 carbon atoms. (Ethylene / α-olefin) is 99
(A) 1,2 adducts (including 3,4 adducts) and 1,4 adducts derived from the conjugated diene monomer in the copolymer Forms a double bond between the side chain and the main chain in the copolymer, and the double bond of the side chain derived from the 1,2 adduct (including the 3,4 adduct) and 1,4 Quantitative ratio of double bond of main chain derived from adduct (double bond of side chain derived from 1,2 adduct (including 3,4 adduct) / 1 main chain derived from 1,4 adduct) Double bond)
Is preferably 5/95 to 99/1, and the content of the structural unit derived from the (b) conjugated diene monomer is preferably 0.01 to 30 mol%. Particularly, the unsaturated olefin copolymer (B-1) has a 5-membered ring in the main chain thereof,
Quantitative ratio of heavy bond to 5-membered ring (total double bond of all adducts / 5
Is preferably 20/80 to 90/10.

The (B-2) unsaturated olefin-based copolymer has a molar ratio of a constitutional unit derived from ethylene to a constitutional unit derived from an α-olefin having 3 to 20 carbon atoms (ethylene / Α-olefin) is 99/1 to 4
The molar ratio of the total amount of the constituent units derived from ethylene and the constituent units derived from the α-olefin having 3 to 20 carbon atoms in the range of 0/60 to the constituent units derived from the aromatic vinyl compound [ (Ethylene + α-olefin) / aromatic vinyl compound] in the range of 99.5 / 0.5 to 50/50, and (a) 1,1 derived from the conjugated diene monomer in the copolymer. The diadduct (including the 3,4 adduct) and the 1,4 adduct form a double bond between the side chain and the main chain in the copolymer, and the 1,2 adduct (3,4 (Including adducts) and the main chain double bond derived from 1,4 adducts (1,2 adducts (3,4
Adduct), the double bond of the side chain derived from the 1,4 adduct) / 5/95 to 99/1
And the content of the structural unit derived from the (b) conjugated diene monomer is preferably 0.01 to 30 mol%. Particularly, in the main chain of the unsaturated olefin copolymer (B-2), 5
The total ratio of double bonds to 5-membered rings of all adducts (total double bonds of all adducts / 5-membered rings) is from 20/80 to
It is preferably 90/10.

The intrinsic viscosity [η] of the unsaturated olefin copolymers (B-1) and (B-2) measured in decalin at 135 ° C. is in the range of 0.1 to 10 dl / g. Is preferred.

The unsaturated olefin copolymers (B-1) and (B-2) have an iodine value of 1 to 50.
Is preferably within the range. (B-1) and (B-
As the conjugated diene monomer constituting the unsaturated olefin-based copolymer of 2), 1,3-butadiene or isoprene is preferably used.

The first olefinic thermoplastic elastomer composition according to the present invention comprises (A) a crystalline polyolefin resin: 10 to 60 parts by weight, (B-1) ethylene, an α-olefin having 3 to 20 carbon atoms. And an unsaturated olefin copolymer comprising a conjugated diene monomer represented by the formula (I): 90 to 40 parts by weight [components (A) and (B-1)
Olefin-based thermoplastic elastomer composition obtained by dynamically heat-treating a blend containing
The intrinsic viscosity [η], iodine value and ethylene content measured in decalin at 5 ° C. are the same as the intrinsic viscosity [η], iodine value and ethylene content of the (B-1) unsaturated olefin copolymer. An ethylene-α-olefin having an α-olefin having 3 to 20 carbon atoms within the range of ± 10% of each value and being identical to the α-olefin of the unsaturated olefin copolymer (B-1); A dynamically blended blend of the olefinic thermoplastic elastomer composition and the olefinic 5-ethylidene-2-norbornene copolymer (X) is dynamically heat-treated in the presence of an organic peroxide. Ethylene obtained
Compared with a thermoplastic elastomer composition containing an α-olefin / 5-ethylidene-2-norbornene copolymer (X),
The degree of oil swelling is preferably 90% or less.

Further, the second olefin-based thermoplastic elastomer composition according to the present invention comprises (A) a crystalline polyolefin resin: 10 to 60 parts by weight, (B-2) ethylene,
Unsaturated olefin copolymer comprising an α-olefin having 3 to 20 carbon atoms, a conjugated diene monomer represented by the above formula (I), and an aromatic vinyl compound: 90 to 40 parts by weight [component (A) A total amount of (B-2) and (B-2) is 100 parts by weight)], is dynamically heat-treated in the presence of an organic peroxide to obtain an olefin-based thermoplastic elastomer composition, The intrinsic viscosity [η] measured in decalin at 135 ° C., each value of the iodine value, the ethylene content and the aromatic vinyl compound content are the intrinsic viscosity [η] of the (B-2) unsaturated olefin copolymer, The α-olefin having 3 to 20 carbon atoms and the aromatic vinyl compound in the range of ± 10% of the respective values of the iodine value, the ethylene content and the aromatic vinyl compound content are not substituted with the unsaturated compound (B-2). Α- of functional olefin copolymer Using the same ethylene / α-olefin / 5-ethylidene-2-norbornene / aromatic vinyl compound copolymer (X) as the olefin and the aromatic vinyl compound, the same blending as the olefin-based thermoplastic elastomer composition Ethylene-α-olefin-5-ethylidene-2-norbornene obtained by dynamically heat treating the blend obtained in the presence of an organic peroxide.
It is preferable that the degree of oil swelling is 90% or less as compared with the thermoplastic elastomer composition containing the aromatic vinyl compound copolymer (X).

The third olefin-based thermoplastic elastomer composition according to the present invention comprises the first olefin-based thermoplastic elastomer composition as described above.
Alternatively, it is characterized by comprising 100 parts by weight of the second olefin-based thermoplastic elastomer composition and (F) a crystalline polyolefin resin: 5 to 200 parts by weight.

As the crystalline polyolefin resin (F), the same resin as the crystalline polyolefin resin (A) can be used.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The olefin-based thermoplastic elastomer composition according to the present invention will be specifically described below.

The first and second olefinic thermoplastic elastomer compositions according to the present invention comprise (A) a crystalline polyolefin resin, (B) a specific unsaturated olefinic copolymer, and optionally (C) A) a blend containing at least one component selected from the group consisting of ethylene / α-olefin / non-conjugated diene copolymer, (D) peroxide non-crosslinked hydrocarbon rubber and (E) softener. Obtained by dynamic heat treatment in the presence of peroxide.

First, each of these components will be described. (A) Crystalline polyolefin resin The (A) crystalline polyolefin resin used in the present invention includes a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms.

Specific examples of the α-olefin 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-tetradecene, 1-pentadecene,
1-hexadecene, 1-heptadecene, 1-octadecene, 1-
Nonadecene, 1-eicosene, and the like.

The α-olefin as described above is used alone,
Alternatively, two or more kinds can be used in combination. Specific examples of the crystalline polyolefin resin (A) include the following (co) polymers. (1) Ethylene homopolymer (manufacturing method may be either low-pressure method or high-pressure method) (2) Co-polymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate, ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10% or less of other α-olefin (5) Block copolymer of propylene and 30% or less of other α-olefin (6) 1-butene homopolymer (7) Random copolymer of 1-butene and 10 mol% or less of other α-olefin (8) 4-methyl-1-pentene homopolymer (9) 4 -Methyl-1-pentene and less than 20 mol% of other α
-Random copolymer with olefin The (A) crystalline polyolefin resin particularly preferably used in the present invention includes (3) propylene homopolymer,
(4) A random copolymer of propylene and 10% or less of other α-olefin, and (5) a block copolymer of propylene and 30% or less of other α-olefin.

The (A) crystalline polyolefin resin used in the present invention is a melt flow rate (MFR; ASTM D 1).
238, 230 ° C, load 2.16kg) 0.1 ~ 100g / 10
Min, preferably in the range of 0.3 to 60 g / 10 min.

(A) The crystalline polyolefin resin comprises:
(A) In a two-component thermoplastic elastomer composition comprising a crystalline polyolefin resin and an unsaturated olefin copolymer (B-1) or (B-2),
(A) 10 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the total amount of the crystalline polyolefin resin and the unsaturated olefin copolymer (B-1) or (B-2). Used in parts by weight.

In addition to (A) the crystalline polyolefin resin and the unsaturated olefin copolymer (B-1) or (B-2), (C) ethylene / α-olefin / non-conjugated polyene copolymer In a three-component, four-component, or five-component thermoplastic elastomer composition containing a polymer, (D) a peroxide non-crosslinked hydrocarbon rubber, or (E) a softener, (A) the crystalline polyolefin resin is With respect to 100 parts by weight of the total amount of component (A) and component (B-1) or (B-2), component (C), component (D) and component (E),
It is used in a proportion of 10 to 60 parts by weight, preferably 15 to 50 parts by weight.

(B) Unsaturated olefin copolymer The (B) unsaturated olefin copolymer used in the present invention includes a copolymer of (B-1) and (B-2). .

The unsaturated olefin copolymer (B-1) is a copolymer rubber comprising at least one α-olefin having 2 to 20 carbon atoms and a conjugated diene monomer.

The unsaturated olefin-based copolymer (B-2) is preferably composed of at least one α-olefin having 2 to 20 carbon atoms.
-A copolymer rubber composed of an olefin, a conjugated diene monomer, and an aromatic vinyl compound.

The α-olefin has 2 carbon atoms.
The number is not particularly limited as long as it is in the range of from 20 to 20, and may be linear or branched. As such α-olefin, specifically, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1
-Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl
-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among these,
Α-olefins having 3 to 12 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferably used.

These α-olefins may be used alone,
Alternatively, two or more kinds can be used in combination. Particularly when two kinds of the above α-olefins are used in combination,
Preferred is a combination of ethylene and an α-olefin having 3 to 5 carbon atoms.

The conjugated diene monomer is represented by the following formula (I).

[0034]

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In the formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and at least one of R ¹ and R ² is a hydrogen atom. is there.

Specific examples of such a conjugated diene monomer include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, and 1,3-butadiene. -
Phenyl-1,3-butadiene, 1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-
Pentyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and the like. Can be Among these, 1,3-butadiene and isoprene are particularly preferred because of their excellent copolymerizability. The conjugated diene monomers can be used alone or in combination of two or more.

As the aromatic vinyl compound, specifically, styrene, allylbenzene, 4-phenyl-1-butene, 3-phenyl-1-butene, 4- (4-methylphenyl) -1
-Butene, 4- (3-methylphenyl) -1-butene, 4- (2-
Methylphenyl) -1-butene, 4- (4-ethylphenyl)
-1-butene, 4- (4-butylphenyl) -1-butene, 5-phenyl-1-pentene, 4-phenyl-1-pentene, 3-phenyl-1-pentene, 5- (4-methylphenyl) -1-pentene, 4- (2-methylphenyl) -1-pentene, 3- (4-methylphenyl) -1-pentene, 6-phenyl-1-hexene,
5-phenyl-1-hexene, 4-phenyl-1-hexene, 3-
Phenyl-1-hexene, 6- (4-methylphenyl) -1-hexene, 5- (2-methylphenyl) -1-hexene, 4- (4-
Methylphenyl) -1-hexene, 3- (2-methylphenyl) -1-hexene, 7-phenyl-1-heptene, 6-phenyl-1-heptene, 5-phenyl-1-heptene, 4-phenyl
1-heptene, 8-phenyl-1-octene, 7-phenyl-1-
Octene, 6-phenyl-1-octene, 5-phenyl-1-octene, 4-phenyl-1-octene, 3-phenyl-1-octene, 10-phenyl-1-decene and the like can be mentioned. Of these aromatic vinyl compounds, styrene, allylbenzene and 4-phenyl-1-butene are preferred, and styrene and 4-phenyl-1-butene are particularly preferred.

These aromatic vinyl compounds can be used alone or in combination of two or more. In the present invention, a non-conjugated diene such as ethylidene norbornene and dicyclopentadiene and a non-conjugated triene can be copolymerized within a range not to impair the object of the present invention.

(B-1) The unsaturated olefin copolymer comprises a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a structural unit derived from a conjugated diene monomer.
Each has a double bond structure caused by a conjugated diene monomer and is randomly arranged and bonded, and the main chain has a substantially linear structure.

The (B-2) unsaturated olefin-based copolymer comprises a structural unit derived from an α-olefin having 2 to 20 carbon atoms, a structural unit derived from a conjugated diene monomer, and an aromatic unit. Structural units derived from a vinyl compound are randomly arranged and bonded to each other, have a double bond structure derived from a conjugated diene monomer, and have a substantially linear main chain. The fact that these copolymers have a substantially linear structure and do not substantially contain a gel-like crosslinked polymer means that these copolymers dissolve in an organic solvent and substantially contain insolubles. It can be confirmed by the absence. For example, when the intrinsic viscosity [η] is measured, it can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

The (B-1) unsaturated olefin-based copolymer used in the present invention has a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and further has 1,1 derived from a conjugated diene.
It preferably has a 2-adduct (including 3,4 adduct) and 1,4-adduct structural units, and in addition to these structural units, a 5-membered ring formed in the main chain ( (Cyclopentane ring). Such (B
-1) The unsaturated olefin-based copolymer may have a cyclopropane structural unit in addition to the above structural units.

The (B-2) unsaturated olefin copolymer used in the present invention has a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a structural unit derived from an aromatic vinyl compound. Further, it is preferable to have 1,2 adducts (including 3,4 adducts) and 1,4 adduct structural units derived from conjugated dienes, and in addition to these structural units,
It is particularly preferred to have a 5-membered ring (cyclopentane ring) formed in the main chain. This unsaturated olefin copolymer (B-2) may also have a cyclopropane structural unit in addition to the above structural units.

The unsaturated olefin copolymer (B) preferably used in the present invention has a molar ratio of a constitutional unit derived from ethylene to a constitutional unit derived from an α-olefin having 3 to 20 carbon atoms ( (Ethylene / α-olefin) is preferably from 99/1 to 40/60 (total 100), and considering the fact that the glass transition temperature Tg of the obtained copolymer can be lowered, the molar ratio is further increased. Is preferably 90/10 to 60/40 (total 100), and considering the relationship between activity and Tg, the molar ratio is more preferably 85/15 to 70/30 (total 100).
However, when it is used as an elastomer, it is more preferable.

Further, (B-
2) The unsaturated olefin-based copolymer has 2 to 20 carbon atoms.
The total amount of the constituent units derived from α-olefins, preferably the constituent units derived from ethylene and the carbon number of 3 to 2
Molar ratio [α-olefin / aromatic vinyl compound, preferably (ethylene + α-olefin) / aromatic] to the total amount of the structural units derived from the α-olefin of 0 and the structural unit derived from the aromatic vinyl compound Vinyl compound]
Is 99.5 / 0.5 to 50/50, preferably 99.0.
/1.0-70/30, more preferably 98.0 /
It is in the range of 2.0 to 85/15.

Further, the unsaturated olefin copolymer (B) has the following properties. (A) In the unsaturated olefin-based copolymer (B), 1,2 adducts (including 3,4 adducts) derived from the above conjugated diene monomer are in the side of the copolymer. A double bond is formed in the chain, and the 1,4 adduct forms a cis or trans double bond in the main chain of the copolymer.

In this copolymer, a double bond of a side chain derived from the above 1,2 adduct (including 3,4 adduct) and 1,1 adduct
The ratio of the double bond of the main chain derived from the 4-adduct (the double bond of the side chain derived from the 1,2 adduct / 1, the double bond of the main chain derived from the 4-adduct) is 5/95. To 99/1 (molar ratio), preferably 10/90 to 99/1. In the above formula (I), when R ¹ is a hydrogen atom and R ² is a conjugated diene monomer (for example, butadiene), which is a hydrogen atom or an alkyl group, the ratio is 12/88 to 90/10. More preferably, it is within the range. When R ¹ is an alkyl group and R ² is a hydrogen atom in the case of a conjugated diene monomer (for example, isoprene), the ratio is more preferably in the range of 20/80 to 90/10. . The presence of the double bond in the copolymer at such a ratio is desirable because the weather resistance, heat resistance, crosslinking efficiency, cold resistance, and modification efficiency of the copolymer are improved. (B) The content of the structural unit derived from the conjugated diene monomer is, for example, 0.01 to 30 mol%, preferably 0.1 to 15 mol%.
It is desirable that (C) a 5-membered ring (cyclopentane ring) formed in combination with at least two adjacent carbon atoms in the main chain of the copolymer in the main chain of the copolymer, The ratio of the double bond (total of double bonds derived from 1,2-, 3,4- and 1,4 adducts) and the 5-membered ring of the all adducts (the total Bond / five-membered ring) is from 20/80 to 90
/ 10 (molar ratio), and considering the balance between the glass transition temperature Tg and the iodine value of the obtained copolymer, 30/30 (molar ratio).
It is desirable that it be present in an amount such that it becomes 70 to 80/20 (molar ratio).

The five-membered ring which may be present in the unsaturated olefin copolymer (B) used in the present invention includes two types, cis and trans. Although the mechanism of the formation of the 5-membered ring is not clear, an oligomer chain or prepolymer formed by the reaction of an α-olefin (eg, ethylene) with a conjugated diene monomer (eg, 1,3-butadiene) It is thought that, for example, after a 1,2- or 3,4-addition of a conjugated diene to the chain, ethylene (α-olefin) is added, and a five-membered ring is formed by intramolecular cyclization.

It is presumed that the cyclopropane ring (3-membered ring) is formed by intramolecular cyclization after addition of 1,2 conjugated dienes typified by butadiene to an oligomer chain or a prepolymer chain. It is considered that the 5-membered ring and the cyclopropane ring contribute to the improvement of the compatibility of the copolymer.

The formed molar ratio of the cyclopropane ring to the 5-membered ring (cyclopropane ring / 5-membered ring) was 0.1 / 99.
It is preferably 9 to 50/50, more preferably 0.1 to 50/50.
/99.9 to 30/70.

(B) When the unsaturated olefin copolymer is ethylene / propylene / styrene / 1,3-butadiene, a hexachlorobutadiene solvent, 110 ° C., 100 ° C.
The 1,4-adduct and the five-membered ring structure were measured by a NMR spectrometer manufactured by JEOL Ltd. under the condition of MHz, and the obtained chart was analyzed by Makromol. Chem. 192, 2591-2601 (1.
It was identified using the chemical shift described in 991).

The following 1,2 adducts can be identified and quantified by ¹ H-NMR, ¹³ C-NMR and two-dimensional NMR of ¹ H and ¹³ C.

[0052]

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Table 1 below shows the chemical shifts.

[0054]

[Table 1]

Further, the following cyclopropane ring was identified and quantified by ¹³ C-NMR, ¹ H-NMR, and a C—H coupling constant specific to the cyclopropane ring in the same manner as described above.

[0056]

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Table 2 below shows the chemical shifts.

[0058]

[Table 2]

Styrene is available from Makromol. Chem. Phys.
197, 1071-1083 (1996) and Macromolecules. 28, 466.
Identification was performed using the chemical shift described in 5-4667 (1995). The ratio of each component and the quantitative ratio of the structure of the conjugated diene are ¹³ C
Determined from the peak area ratio of -NMR and / or ¹ H-NMR.

In the present invention, in the above copolymer,
Constituent units derived from conjugated diene monomers, ie, 1,2 adduct (including 3,4 adduct), 1,4 adduct, 5-membered ring (cyclopentane structure), and cyclopropane ring (3-membered ring)
Is 0.01 to 30 mol% in total, preferably 0.1 to 15 mol%.
Desirably, it is contained in an amount of mol%. The balance of the structural unit is ethylene, α-olefin having 3 to 20 carbon atoms,
And those derived from aromatic vinyl compounds such as styrene.

(B) The unsaturated olefin-based copolymer is
The intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.1 to 10 dl / g, preferably 1.0 to 5.0 dl.
/ G is desirable. The (B) unsaturated olefin copolymer generally has an iodine value of 1 to 50,
It is preferably in the range of 3 to 50, more preferably 5 to 40.

The unsaturated olefin copolymer (B) preferably has a melting point (Tm) of 12 as measured by DSC.
It is desirably 0 ° C or less, more preferably 110 ° C or less, further preferably 70 ° C or less, and particularly preferably 40 ° C or less. The glass transition temperature Tg measured by DSC is preferably 25 ° C. or lower, more preferably 10 ° C. or lower, and further preferably 0 ° C. or lower. In addition, GPC
Is preferably 3 or less.

In the present invention, the unsaturated olefin copolymer (B) preferably has at least one of the molar ratio of each structural unit, intrinsic viscosity [η] and iodine value within the above range, It is more preferable that two or more are in the above range, and in particular, the molar ratio of each structural unit, intrinsic viscosity [η]
It is preferred that all of the iodine values are within the above range.

(B) The unsaturated olefin-based copolymer is
Since the above conjugated diene monomer is used as a copolymer component, the crosslinking efficiency is increased, the crosslinking progresses tightly with a small amount of organic oxide, and the balance between moldability and rubber elasticity of the molded body is good. Become.

(B) Unsaturated olefin-based copolymer, particularly ethylene / C3 to C2 having a melting point (Tm) of 40 ° C. or less.
In the case of the olefin-based thermoplastic elastomer composition of the present invention containing an α-olefin / conjugated diene copolymer (B-1) of 0, the oil swelling degree, which is an index of crosslinking reactivity, measured by the following method is as follows. , The same intrinsic viscosity [η], the same iodine value, the same ethylene content and the same type of carbon number 3 to
Oil swelling measured on a thermoplastic elastomer composition containing an ethylene / α-olefin / 5-ethylidene-2-norbornene copolymer having 20 α-olefins (X: corresponding to component (C) described below) 90% of the degree
Or less, more preferably 85% or less.

Here, the “identical” intrinsic viscosity [η],
The iodine value and ethylene content are defined as ethylene / α-olefin / 5-ethylidene-2-norbornene copolymer (X)
[Η], iodine value and ethylene content of the ethylene / α-olefin / conjugated diene copolymer used in the present invention are within ± 10% of the intrinsic viscosity [η], iodine value and ethylene content of the copolymer. It is within.

Here, the case where the copolymer (B-1) was used as the unsaturated olefin-based copolymer (B) in the composition was shown, but ethylene-α-C 3 -C 20 was used. Olefin / conjugated diene / aromatic vinyl compound copolymer (B
The same applies to the composition using -2). However, the copolymer used as a reference for the degree of oil swelling was such that the content of the aromatic vinyl compound was ± of the content in the copolymer (B-2).
It is an ethylene / α-olefin / 5-ethylidene-2-norbornene / aromatic vinyl compound copolymer within a range of 10%.

The ethylene / α- used in the present invention
When a monomer other than the conjugated diene monomer such as a non-conjugated diene such as dicyclopentadiene or a non-conjugated polyene monomer such as a non-conjugated triene is copolymerized in the olefin / conjugated diene copolymer, Ethylene / α-olefin / monomer in which monomers other than this conjugated diene monomer are copolymerized
The 5-ethylidene-2-norbornene copolymer (X) shall be used.

As described above, the degree of oil swelling can be determined by (B)
As an unsaturated olefin-based copolymer and its comparative reference, for example, ethylene / α-olefin / 5-ethylidene
Using 2-norbornene copolymer (X), a thermoplastic elastomer composition is prepared at the same composition and resin temperature, and the composition is measured in the following manner.

A 2 × 10 × 10 mm test piece was punched out of a square plate molded from the thermoplastic elastomer composition, and the initial volume (V 0) was determined using a water immersion type volume meter. Next, the test piece was heated to 70 ° C. in JIS 1
After immersion in No. 3 oil for 3 days, the temperature is returned to room temperature, and the volume (V) of the test piece after swelling is similarly obtained. From these values, the oil swelling degree (ΔV) is calculated from the following equation.

ΔV (%) = {(V−V0) / V0} × 100 (B) For comparison reference, the oil swelling degree (ΔV1) of the thermoplastic elastomer composition containing the unsaturated olefin-based copolymer. Ethylene, α-olefin, 5-ethylidene-2-
The ratio to the oil swelling degree (ΔV2) of the norbornene copolymer (X) -containing thermoplastic elastomer composition [(Δ
V1 / ΔV2) × 100 (%)], the proportion of (B) the unsaturated olefin copolymer among the components other than (A) the crystalline polyolefin resin in the thermoplastic elastomer composition is increased. The tendency tends to decrease.

(B) The unsaturated olefin-based copolymer is
(A) In a two-component thermoplastic elastomer composition comprising a crystalline polyolefin resin and an unsaturated olefin copolymer (B-1) or (B-2),
(A) 90 to 40 parts by weight, preferably 50 to 85 parts by weight, based on 100 parts by weight of the total amount of the crystalline polyolefin resin and the unsaturated olefin copolymer (B-1) or (B-2). Used in parts by weight.

In addition to (A) the crystalline polyolefin resin and the unsaturated olefin copolymer (B-1) or (B-2), (C) ethylene / α-olefin / non-conjugated polyene copolymer In the case of a three-component, four-component, or five-component thermoplastic elastomer composition containing a polymer, (D) a peroxide non-crosslinked hydrocarbon rubber or (E) a softener, (B) an unsaturated olefin-based The copolymer has a total amount of 100 parts by weight of the component (A), the component (B-1) or (B-2), and at least one of the component (C), the component (D) and the component (E). On the other hand, 85 to 10 parts by weight,
It is preferably used in a proportion of 15 to 65 parts by weight.

(B) Production of unsaturated olefin copolymer
Unsaturated olefin copolymer to be used in forming the present invention,
The α-olefin having 2 to 20 carbon atoms and the formula (I)
Is obtained by copolymerization, preferably random copolymerization, of a conjugated diene monomer represented by the formula (1) and, if necessary, an aromatic vinyl compound in the presence of a metallocene catalyst shown below.

As such a metallocene catalyst, a transition metal complex (a) represented by the following formula (II) or (III):

[0076]

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[In the formulas (II) and (III), M is Ti, Zr,
Hp, Rn, Nd, Sm or Ru, Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, X ¹ and X ² are An anionic ligand or a neutral Lewis base ligand, Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is C, O, B, S, Ge , Si or Sn atom or a group containing these atoms. And 1 selected from the following components (b), (c) and (d):
At least one catalyst system consisting of one or more compounds is used. (B): a compound which reacts with the transition metal M in the component (a) to form an ionic complex. (C): an organoaluminum compound. (D): an alumoxane.

First, the transition metal complex (a) represented by the following formula (II) used in the present invention will be described.

[0079]

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In the formula (II), M is a transition metal of Group 4 of the periodic table or a lanthanide series, and specifically, Ti, Z
r, Hf, Rn, Nd, Sm, and Ru, preferably Ti, Zr, and Hf, and Cp1 is a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative group thereof bonded to M by π. X ¹ and X
² is an anionic ligand or a neutral Lewis base ligand, Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is carbon, oxygen, sulfur, Boron or an element of group 14 of the periodic table (for example, silicon, germanium or tin), preferably any of carbon, oxygen and silicon; Z may have a substituent; May form a fused ring.

More specifically, Cp1 is a ligand coordinated to a transition metal and is a ligand having a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof. The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

Z is C, O, B, S, Ge, Si,
It is an atom selected from Sn, and Z may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z may combine with each other to form a ring.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, which may be the same or different from each other, are hydrogen atoms or halogen atoms, or have 20 or less carbon atoms. A hydrocarbon group, a silyl group or a germyl group containing an atom, a silicon atom or a germanium atom.

Specific examples of the compound represented by the formula (II) include (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride, ((t-butylamide ) (Tetramethyl-
η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, (dimethyl (phenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamide) (tetra Methyl-η ⁵ -cyclopentadienyl) silylene) titanium dimethyl, (dimethyl (4-methylphenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamide) (η ^5-
Cyclopentadienyl) silylene) titanium dichloride,
(Tetramethyl (t-butylamide) (tetramethyl-η ⁵
-Cyclopentadienyl) disilylene) titanium dichloride.

In the present invention, a transition metal compound represented by the following formula (III) can also be used.

[0086]

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[In the formula (III), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru, preferably Ti, Z
r or Hf, Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or A neutral Lewis base ligand wherein Z is C, O, B, S, Ge, Si or Sn
It is an atom or a group containing these atoms. In the formula (III), the bonding group Z is preferably C, O, B, S, Ge,
It is preferably one atom selected from Si and Sn, and this atom may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z are bonded to each other to form a ring. May be.

Cp1 and Cp2 are ligands that coordinate to the transition metal, and include cyclopentadienyl group, indenyl group, 4,5,
A ligand having a cyclopentadienyl skeleton such as a 6,7-tetrahydroindenyl group or a fluorenyl group, and the ligand having a cyclopentadienyl skeleton includes an alkyl group, a cycloalkyl group, and a trialkylsilyl group. And a substituent such as a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, specifically, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid Group containing (-SO ₃ Ra, where Ra is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group), halogen Atoms, hydrogen atoms and the like.

The following is an example of a metallocene compound in which M is zirconium and contains two ligands having a cyclopentadienyl skeleton. Cyclohexylidene-bis (indenyl) dimethylzirconium, cyclohexylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene-bis ( Indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,
4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene -Bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthryl) -1
-Indenyl) zirconium dichloride and the like.

Further, metallocene compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified. Further, examples of the bridge type metallocene compound include a metallocene compound represented by the following formula [A]. The metallocene has the formula [A]:

[0092]

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[A] In the formula [A], M ¹ is a metal of Group IVB of the periodic table, and specifically, for example, titanium, zirconium,
Hafnium can be mentioned.

R ¹ and R ² may be the same or different, and each represents a hydrogen atom;
An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms; an aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms; An alkenyl group having 2 to 10 and preferably 2 to 4; an arylalkyl group having 7 to 40 and preferably 7 to 10 carbon atoms; an alkylaryl group having 7 to 40 and preferably 7 to 12 carbon atoms; 8 to 12 arylalkenyl groups or halogen atoms, preferably chlorine atoms.

R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, an optionally halogenated carbon number of 1 to 10, preferably 1 to 1. ~ 4 alkyl groups,
An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, -NR
¹⁰ ₂ , —SR ¹⁰ , —OSiR ¹⁰ ₃ , —SiR ¹⁰ ₃ or —PR ¹⁰ ₂ groups, wherein R ¹⁰ is a halogen atom, preferably a chlorine atom, or a group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
Or an alkyl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms
Is an aryl group.

R ³ and R ⁴ are particularly preferably hydrogen atoms. R ⁵ and R ⁶ may be the same or different and are preferably the same, and have the meanings described for R ³ and R ⁴ , provided that R ⁵ and R ⁶ are not hydrogen atoms. R ⁵ and R ⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or A trifluoromethyl group is exemplified, and a methyl group is preferred.

R ⁷ is as follows:

[0098]

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= BR ¹¹ , = AlR ¹¹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 11, =
CO, = PR ¹¹ or = P (O) R ¹¹ , where R
¹¹ , R ¹² and R ¹³ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably a methyl group, and a fluoroalkyl having 1 to 10 carbon atoms. A group preferably a CF ₃ group,
An aryl group having 6 to 10 carbon atoms, preferably a 6 to 8 carbon atom, a fluoroaryl group having 6 to 10 carbon atoms, preferably a pentafluorophenyl group, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably a methoxy group, 2 to 10 preferably 2 to 4 alkenyl groups, 7 to 40 preferably 7 to 10 arylalkyl groups, 8 to 40 preferably 8 to 12 arylalkenyl groups, or 7 to 40 carbon atoms the is an alkyl aryl group having 7 to 12, also "R ¹¹ and R ^12" or "R ¹¹ and R ¹³ ',
Each of them may form a ring together with the atoms to which they are bonded.

M ² is silicon, germanium or tin, preferably silicon or germanium. R ⁷ is = CR
^{11 R 12, = SiR 11 R} 12, = GeR 11 R 12, -O -, -
S -, = SO, it is preferred that = PR ¹¹ or = P (O) R ^11.

R ⁸ and R ⁹ may be the same or different and have the same meaning as described for R ¹¹ . m and n may be the same or different and are 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

Particularly preferred metallocenes satisfying the above conditions are shown in the following (i) to (iii).

[0103]

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[In the above formulas (i), (ii) and (iii), M ¹
Is Zr or Hf, R ¹ and R ² are a methyl group or a chlorine atom, R ⁵ and R ⁶ are a methyl group, an ethyl group or a trifluoromethyl group, and R ⁸ , R ⁹ , R
¹¹ and R ¹² have the meaning described above. Among the compounds represented by the formulas (i), (ii) and (iii), the following compounds are particularly preferred.

Rac-dimethylmethylenebis (indenyl)
Zirconium dichloride, rac-dimethylmethylenebis (2-methyl-1-indenyl) zirconium dichloride,
rac-diphenylmethylenebis (2-methyl-1-indenyl) zirconium dichloride, rac-ethylene (2-methyl
-1-indenyl) ₂ -zirconium-dichloride, rac-
Dimethylsilylene (2-methyl-1-indenyl) ₂ - Zirconium - dichloride, rac- dimethylsilylene (2-methyl-1-indenyl) ₂ - Zirconium - dimethyl, rac- ethylene (2-methyl-1 - indenyl) ₂ - Zirconium-dimethyl, rac-phenyl (methyl) silylene- (2-methyl-1
-Indenyl) ₂ -zirconium-dichloride, rac-diphenyl-silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-methylethylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, ra
c-Dimethylsilylene- (2-ethyl-1-indenyl) ₂ -zirconium-dichloride.

The metallocene can be produced by a conventionally known method (for example, see Japanese Patent Application Laid-Open No. 4-268307). In the present invention, a transition metal compound (metallocene compound) represented by the following formula [B] is used as a bridge type metallocene compound.
Can also be used.

[0107]

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[B] In the formula [B], M represents a transition metal atom belonging to Group IVB of the periodic table, and specifically, titanium, zirconium and hafnium.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group, specifically, halogen atom such as fluorine, chlorine, bromine, iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl , Dodecyl, eicosyl, norbornyl, alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, Propylphenyl, biphenyl, naphthyl,
A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as methylnaphthyl, anthracenyl, and phenanthryl; a halogenated hydrocarbon group in which a halogen atom is substituted on the hydrocarbon group; a monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; Dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trihydrocarbons such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl Substituted silyl, silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether, silicon-substituted alkyl group such as trimethylsilylmethyl, silicon-substituted aryl group such as trimethylsilylphenyl, etc. Oxygen-containing groups such as hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy. A sulfur-containing group such as a substituent in which the oxygen of the oxygen-containing group is substituted by sulfur; an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, a phenylamino group; A nitrogen-containing group such as an arylamino group or an alkylarylamino group such as diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; dimethylphosphino;
It is a phosphorus-containing group such as a phosphino group such as diphenylphosphino.

Of these, R ¹ is preferably a hydrocarbon group, particularly methyl, ethyl and propyl having 1 carbon atom.
It is preferably from 3 to 3 hydrocarbon groups. R ² is preferably hydrogen or a hydrocarbon group, particularly preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Among them, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R ³ and R ⁴ , R ⁴ and R ⁵ ,
At least one pair of R ⁵ and R ⁶ may form a monocyclic aromatic ring together with the carbon atom to which they are bonded.

When there are two or more types of hydrocarbon groups or halogenated hydrocarbon groups, the groups other than the group forming an aromatic ring may be combined with each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those described above for R ¹ and R ² . Examples of the ligand coordinated to M, including a monocyclic aromatic ring formed by combining at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ , are as follows. Some examples are shown below.

[0114]

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Among these, those represented by the above formula (1) are preferred. The aromatic ring is a halogen atom, having 1 to 1 carbon atoms.
It may be substituted with 20 hydrocarbon groups or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Examples of the halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms which are substituted on the aromatic ring include the same groups as those described above for R ¹ and R ^2. .

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. And specifically, R ¹ and R
² the same halogen atom, hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing groups can be exemplified.

Examples of the sulfur-containing group include the same groups as those described above for R ¹ and R ² and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate and trimethylbenzenesulfonate. Sulfonate groups such as phonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms,
Divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,-
^{_{SO 2 -, - NR 7 -}} , - P (R 7) -, - P (O)
^{(R 7) -, - BR} 7 - or -AlR ⁷ - [However,
R ⁷ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, Dimethyl-1,2-ethylene, 1,3-trimethylene,
Divalent having 1 to 20 carbon atoms such as alkylene groups such as 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene. A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n-
Alkyl silylenes such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, aryl Silylene group,
Tetramethyl-1,2-disilylene, tetraphenyl-1,2-
A divalent silicon-containing group such as an alkyldisilylene such as disilylene, an alkylaryldisilylene, or an aryldisilylene group; a divalent germanium-containing group obtained by substituting silicon of the divalent silicon-containing group with germanium; A divalent tin-containing group substituent in which silicon of the silicon-containing group is substituted with tin, and the like. R ⁷ is the same halogen atom as R ¹ or R ² , a hydrocarbon group having 1 to 20 carbon atoms, a carbon number 1
To 20 halogenated hydrocarbon groups.

Of these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable.
Of these, alkylsilylene, alkylarylsilylene, and arylsilylene are particularly preferred.

The following are specific examples of the transition metal compound represented by the above formula [B].

[0122]

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[0123]

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[0124]

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In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but may be an R-type or S-type.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the following reaction route using a conventional organic synthesis technique.

[0127]

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The transition metal compound used in the present invention can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [C] can also be used as the bridge type metallocene compound.

[0130]

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[C] In the formula [C], M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those in the above formula [B]. No.

Of R ³ , R ⁴ , R ⁵ and R ⁶ , R ³
Is preferably an alkyl group,
Preferably, R ³ and R ⁵ , or R ³ and R ⁶ are alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. Also, this alkyl group is
A halogen atom, which may be substituted with a silicon-containing group,
Examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ¹ and R ² .

Among the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl group are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, A chain alkyl group and a cyclic alkyl group such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; an arylalkyl group such as benzyl, phenylethyl, phenylpropyl and tolylmethyl; and the like, including a double bond and a triple bond May be.

Further, two groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

X ¹ , X ² , Y and R ⁷ are the same as those in the above formula [B]. Specific examples of the metallocene compound (transition metal compound) represented by the above formula [C] are shown below.

Rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,5,6-trimethyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2,4,5,6-tetramethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,5,6,7-pentamethyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-n-propyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-methyl-6-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-5-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4,6-di (i-propyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-
4,6-di (i-propyl) -7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-Dimethylsilylene-bis (2-methyl-4-sec-butyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6-di (sec-butyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-tert-butyl-7 -Methyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-cyclohexyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-benzyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-phenylethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyldichloromethyl-7-methyl-1-indenyl) zirconium dichloride , Rac-dimethylsilylene-bis (2-methyl-4-chloromethyl-7-
Methyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-methyl-4-trimethylsilylmethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-trimethylsiloxymethyl-7-methyl-1-indenyl) Zirconium dichloride, rac-diethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-di (i-propyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (n-butyl)
Silylene-bis (2-methyl-4-i-propyl-7-methyl-1
-Indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2-methyl-4-i-propyl)
-7-methyl-1-indenyl) zirconium dichloride,
rac-methylphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4,6
-Di (i-propyl) -1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2-methyl
-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-
Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-
Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium methyl Chloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (methanesulfonate), ra
c-dimethylsilylene-bis (2-methyl-4-i-propyl-7
-Methyl-1-indenyl) zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-bis (2-
Methyl-3-methyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-ethyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-phenyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride.

In the present invention, a transition metal compound in which zirconium metal in the above compounds is replaced with titanium metal or hafnium metal can also be used. The transition metal compound is usually used as a racemic compound, but may be used in R-form or S-form.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the same reaction route as described above using a conventional organic synthesis technique. The transition metal compound (metallocene compound) represented by the above formula [C] can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [D] can also be used as a bridge type metallocene compound.

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[D] In the formula [D], M, R ¹ , X ¹ , X ² and Y are
The same as in the case of the formula [B] or the formula [C] can be used.

Among them, R ¹ is preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl. X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

R ² represents an aryl group having 6 to 16 carbon atoms. Specific examples include phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl (perinaphthenyl), aceanthrenyl and the like. It is. Of these, phenyl and naphthyl are preferred. These aryl groups may be substituted with the same halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as in R ¹ .

Specific examples of the transition metal compound (metallocene compound) represented by the above formula [D] are shown below. rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl -Four
-(Α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-
Naphthyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (1-anthracenyl) -1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4- (2-anthracenyl) -1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-methyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-fluorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (pentafluorophenyl) -1-indenyl) Zirconium dichloride, ra
c-dimethylsilylene-bis (2-methyl-4- (p-chlorophenyl) -1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-methyl-4- (m-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-bromophenyl) -1 -Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o-tolyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (p-ethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (pi-propylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-methyl-4- (p-benzylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-methyl-4- (p-biphenyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-biphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-trimethylsilylphenyl) -1 -Indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (m-trimethylsilylphenyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-phenyl-1-indenyl)
Zirconium dichloride, rac-diphenylsilylene-bis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethyl Silylene-bis (2-n-propyl-4-phenyl-1-indenyl) zirconium dichloride, rac-
Diethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di- (i-propyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac- Di- (n-butyl) silylene-bis (2-methyl-4-phenyl-1-indenyl)
Zirconium dichloride, rac-dicyclohexylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac- Diphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2-methyl-4-
Phenyl-1-indenyl) zirconium dichloride, ra
c-Di (p-chlorophenyl) silylene-bis (2-methyl-4
-Phenyl-1-indenyl) zirconium dichloride,
rac-methylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-ethylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylgermylene-bis ( 2-methyl
-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethyltin-bis (2-methyl-4-phenyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-
Bis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl
-4-phenyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride SO ₂ M
e, rac-Dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride OSO ₂ Me
Such.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound represented by the formula [D] is described in Journa
l of Organometallic Chem. 288 (1985), pp. 63-67, EP-A-0,320,762 and examples, for example, as follows.

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The transition metal compound [D] is usually used as a racemic compound, but an R-form or an S-form can also be used. The metallocene compounds as described above can be used alone or in combination of two or more.

The metallocene compound as described above can be used by being supported on a particulate carrier. Such particulate supports include SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , M
gO, ZrO ₂ , CaO, TiO ₂ , ZnO, SnO ₂ ,
Inorganic carriers such as BaO and ThO, and organic carriers such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

Next, a metallocene catalyst is formed. (B): a compound which reacts with the transition metal M in the component (a) to form an ionic complex, that is, an ionized ionic compound. The compound and (d): alumoxane (aluminum oxy compound) will be described.

<(B) Ionized Ionic Compound> The ionized ionic compound is a compound which reacts with the transition metal M in the transition metal complex component (a) to form an ionic complex. Examples of the acidic compound include a Lewis acid, an ionic compound, a borane compound, and a carborane compound.

As the Lewis acid, a compound represented by BR ₃ (where R is a fluorine atom, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group or a fluorine atom). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
And tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

As the borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III)
And salts of metal borane anions.

Examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Salts of metal carborane anions such as nickelate (IV) are exemplified.

The ionized ionic compound as described above is
They can be used alone or in combination of two or more.
The organic aluminum oxy compound or the ionized ionic compound can be used by being supported on the above-mentioned particulate carrier.

In forming the catalyst, the following organic aluminum compound (c) may be used together with the organic aluminum oxy compound and / or the ionized ionic compound.

<(C) Organoaluminum Compound> As the (c) organoaluminum compound, a compound having at least one Al-carbon bond in a molecule can be used. Examples of such a compound include an organoaluminum compound represented by the following general formula.

(R ¹ ) m Al (O (R ² )) nHpXq (wherein R ¹ and R ² may be the same or different, and usually have 1 to 15, preferably 1 to 4 carbon atoms.) X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3, and m + n + p + q = 3
It is. <(D) Organoaluminum oxy compound (alumoxa)
Down)> (d) an organoaluminum oxy-compound may be a conventionally known aluminoxane, also JP-A 2-7868
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-7.

The conventionally known aluminoxane (alumoxane) is specifically represented by the following general formula.

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In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. m is an integer of 2 or more, preferably 5 to 40.

Here, the aluminoxane is represented by the formula (OAl (R
¹⁾ represented alkyloxy aluminum units and formula (OAl (R ²⁾ represented alkyloxy aluminum units (where they are in) is in), R ¹ and R ² are the same hydrocarbon group as R, R ¹ And R ² represent different groups.).

The organic aluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. In the present invention, as the olefin-based catalyst, the above-mentioned metallocene-based catalyst is preferably used.In some cases, other than the above-mentioned metallocene-based catalyst, the catalyst comprises a conventionally known solid titanium catalyst component and an organic aluminum compound. A titanium-based catalyst and a vanadium-based catalyst composed of a soluble vanadium compound and an organoaluminum compound can also be used.

In the present invention, an α-olefin having 2 to 20 carbon atoms, a conjugated diene monomer and, if necessary, an aromatic vinyl compound are usually copolymerized in a liquid phase in the presence of the above-mentioned metallocene catalyst. . In this case, a hydrocarbon solvent is generally used, but an α-olefin may be used as the solvent. The copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the concentration of the metallocene compound in the polymerization system is usually 0.00005 per liter of polymerization volume.
-1 mmol, preferably 0.0001-0.5 mmol.

The organic aluminum oxy compound has a molar ratio (Al / M) of aluminum atom (Al) to transition metal atom (M) in the metallocene compound of 1 to 1000.
It is used in such an amount that it becomes 0, preferably 10-5000.

The ionized ionic compound has a molar ratio of the ionized ionic compound to the metallocene compound (ionized ionic compound / metallocene compound) of 0.5 to 2
It is used in an amount such that it becomes 0, preferably 1 to 10.

When an organoaluminum compound is used, it is used in an amount of usually about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

The copolymerization reaction is usually carried out at a temperature of -20 to 15
0 ° C, preferably 0 to 120 ° C, more preferably 0 to
In the range of 100 ° C., the pressure is over 0 to 80 kg / cm
² , preferably above 0 and up to 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 10 minutes. 1.5 hours.

An α-olefin having 2 to 20 carbon atoms, a conjugated diene monomer and, if necessary, an aromatic vinyl compound are
The unsaturated olefin copolymer (B) having the specific composition as described above is supplied to the polymerization system in such an amount as to obtain the copolymer. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

When the α-olefin having 2 to 20 carbon atoms, the conjugated diene monomer and, if necessary, the aromatic vinyl compound are copolymerized as described above, (B) the unsaturated olefin-based copolymer becomes Is usually obtained as a polymerization solution containing the same. This polymerization liquid is treated by a conventional method to obtain (B) an unsaturated olefin copolymer.

In the present invention, when the olefin thermoplastic elastomer composition is produced from the (A) crystalline polyolefin resin and (B) the unsaturated olefin copolymer, the following (C) An ethylene / α-olefin / non-conjugated polyene copolymer, (D) a peroxide non-crosslinked hydrocarbon rubber, and (E) a softener may be blended.

(C) Ethylene / α-olefin / Non-conjugated
Polyene copolymer (C) The ethylene / α-olefin / non-conjugated polyene copolymer is a copolymer composed of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.

Here, as the α-olefin, specifically, propylene, 1-butene, 4-methyl-1-pentene,
Α-olefins such as 1-hexene and 1-octene, which are the same as the specific examples of the (B) α-olefin having 3 to 20 carbon atoms constituting the unsaturated olefin copolymer (B).

Specific examples of the non-conjugated polyene include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene, and non-conjugated trienes and tetraenes.

(C) The ethylene / α-olefin / non-conjugated polyene copolymer has a ratio of ethylene units to α-olefin units (ethylene / α-olefin, molar ratio) of 9
It is preferably in the range of 0/10 to 50/50.

Further, (C) ethylene / α-olefin /
Mooney viscosity of non-conjugated polyene copolymer [ML _{1 + 4} (1
00 ° C)] is usually 10 to 250, preferably 40 to 1
It is desirably in the range of 50, and the iodine value is preferably 40 or less.

(C) The ethylene / α-olefin / non-conjugated polyene copolymer is usually present in a crosslinked state in the olefin-based thermoplastic elastomer composition.

The (C) ethylene / α-olefin / non-conjugated polyene copolymer includes (A) a crystalline polyolefin resin, (B) an unsaturated olefin copolymer, and (C) an ethylene / α-olefin. A non-conjugated polyene copolymer,
It is used in an amount of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total of (D) the peroxide non-crosslinked hydrocarbon rubber and (E) at least one softener. When the ethylene / α-olefin / non-conjugated polyene copolymer (C) is blended in a proportion within the above range, an olefin-based thermoplastic elastomer composition having further excellent cold resistance can be obtained.

(D) Peroxide Non-crosslinked Hydrocarbon
The arm (D) peroxide non-crosslinked type hydrocarbon rubber in the presence of a peroxide (organic peroxide), be subjected to dynamic heat treatment in the decomposition temperature or higher, without crosslinking, the flowability A hydrocarbon-based rubbery substance that does not decrease. Specific examples include butyl rubber, polyisobutylene rubber, propylene / ethylene copolymer rubber having a propylene content of 50 mol% or more, and propylene / 1-butene copolymer rubber. Among them, butyl rubber or polyisobutylene rubber is particularly preferably used.

(D) Peroxide non-crosslinked hydrocarbon rubbers include (A) a crystalline polyolefin resin, (B) an unsaturated olefin copolymer, and (C) an ethylene / α-olefin / non-conjugated polyene. 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total amount of the copolymer, (D) the peroxide non-crosslinked hydrocarbon rubber and (E) at least one of the softener. Used in
When the peroxide non-crosslinked hydrocarbon rubber (D) is blended in a proportion within the above range, an olefin thermoplastic elastomer composition having more excellent moldability and appearance of a molded article can be obtained.

(E) Softener As the softener (E), a softener conventionally compounded in rubber is widely used, and specifically, process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt,
Petroleum softeners such as petrolatum; coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil; Waxes such as wax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid,
Fatty acids or fatty acid salts thereof, such as barium stearate, calcium stearate, and zinc laurate; petroleum resins,
Synthetic polymers such as coumarone indene resin and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate;
Other examples include microcrystalline wax, liquid polybutadiene or a modified or hydrogenated product thereof, and liquid thiochol.

(E) The softener comprises (A) a crystalline polyolefin resin, (B) an unsaturated olefin copolymer,
1 to 40 parts by weight based on 100 parts by weight of the total amount of (C) ethylene / α-olefin / non-conjugated polyene copolymer, (D) at least one of peroxide non-crosslinked hydrocarbon rubber and (E) softener. It is used in a proportion of 10 parts by weight, preferably 10 to 35 parts by weight. When the softening agent (E) is added at a ratio within the above range, an olefin-based thermoplastic elastomer composition having excellent fluidity during molding can be obtained. If the (E) softener is used in an amount larger than the above ratio, the mechanical properties of the obtained composition may be reduced.

The first and second olefinic thermoplastic resins
Production of Lastomer Composition In the present invention, in addition to (A) the crystalline polyolefin resin and (B) the unsaturated olefin copolymer, (C) ethylene / α-olefin /
When producing an olefin-based thermoplastic elastomer composition using at least one component selected from a non-conjugated polyene copolymer, (D) a peroxide non-crosslinked hydrocarbon-based rubber, and (E) a softener, each of these components is used. Is specifically used in the following combinations and amounts. (1) (A) crystalline polyolefin resin: 10 to 60 parts by weight,
15 to 50 parts by weight, (B) unsaturated olefin copolymer: 85 to 10 parts by weight, preferably 65 to 1 part by weight
5 parts by weight, and (C) an ethylene / α-olefin / non-conjugated polyene copolymer: 1 to 50 parts by weight, preferably 5
~ 40 parts by weight. (2) (A) crystalline polyolefin resin: 10 to 60 parts by weight,
15 to 50 parts by weight, (B) unsaturated olefin copolymer: 85 to 10 parts by weight, preferably 65 to 1 part by weight
5 parts by weight, and (D) a peroxide non-crosslinked hydrocarbon rubber: 1 to 20 parts by weight, preferably 5 to 15 parts by weight. (3) (A) crystalline polyolefin resin: 10 to 60 parts by weight,
15 to 50 parts by weight, (B) unsaturated olefin copolymer: 85 to 10 parts by weight, preferably 65 to 1 part by weight
5 parts by weight, and (E) softener: 1 to 40 parts by weight, preferably 10 to 35 parts by weight. (4) (A) crystalline polyolefin resin: 10 to 60 parts by weight,
15 to 50 parts by weight, (B) unsaturated olefin copolymer: 85 to 10 parts by weight, preferably 65 to 1 part by weight
5 parts by weight, (C) ethylene / α-olefin / non-conjugated polyene copolymer: 1 to 50 parts by weight, preferably 5 to 40 parts
Parts by weight, and (D) non-peroxide peroxide-based hydrocarbon rubber: 1 to 20 parts by weight, preferably 5 to 15 parts by weight. (5) (A) crystalline polyolefin resin: 10 to 60 parts by weight,
15 to 50 parts by weight, (B) unsaturated olefin copolymer: 85 to 10 parts by weight, preferably 65 to 1 part by weight
5 parts by weight, (D) non-peroxide peroxide-type hydrocarbon rubber: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, and (E) softener: 1 to 40 parts by weight, preferably 10 to 3 parts by weight.
5 parts by weight. (6) (A) crystalline polyolefin resin: 10 to 60 parts by weight,
15 to 50 parts by weight, (B) unsaturated olefin copolymer: 85 to 10 parts by weight, preferably 65 to 1 part by weight
5 parts by weight, (C) ethylene / α-olefin / non-conjugated polyene copolymer: 1 to 50 parts by weight, preferably 5 to 40 parts
Parts by weight, and (E) softener: 1 to 40 parts by weight, preferably 10 to 35 parts by weight. (7) (A) crystalline polyolefin resin: 10 to 60 parts by weight,
15 to 50 parts by weight, (B) unsaturated olefin copolymer: 85 to 10 parts by weight, preferably 65 to 1 part by weight
5 parts by weight, (C) ethylene / α-olefin / non-conjugated polyene copolymer: 1 to 50 parts by weight, preferably 5 to 40 parts
Parts by weight, (D) peroxide non-crosslinked hydrocarbon rubber:
1 to 20 parts by weight, preferably 5 to 15 parts by weight, and (E) softener: 1 to 40 parts by weight, preferably 10 to 35 parts
Parts by weight.

Incidentally, the total amount of each component in the above (1) to (7) is 100 parts by weight. The first and second olefin-based thermoplastic elastomer compositions according to the present invention may further contain SEBS, SEPS, hydrogenated S if necessary.
Additives such as styrene-based copolymers such as BR, resins such as polystyrene, polyester, and nylon, heat stabilizers, antistatic agents, weather stabilizers, anti-aging agents, fillers, coloring agents, and lubricants of the present invention. It can be blended within a range that does not impair the purpose.

The first and second olefin-based thermoplastic elastomer compositions according to the present invention are characterized in that a blend comprising (A) a crystalline polyolefin resin and (B) an unsaturated olefin-based copolymer is obtained by adding an organic peroxide It is a composition obtained by dynamically heat-treating in the presence of a product, and is an olefin-based thermoplastic elastomer composition in which the unsaturated olefin-based copolymer (B) is crosslinked. In some cases, (A) the crystalline polyolefin resin and (B) the unsaturated olefin-based copolymer are crosslinked.

The first and second olefinic thermoplastic elastomer compositions according to the present invention further comprise (A) a crystalline polyolefin resin and (B) an unsaturated olefinic copolymer, and further comprise (C) ethylene.・ Α-olefin ・
A blend containing at least one component selected from a non-conjugated polyene copolymer, (D) a peroxide non-crosslinked hydrocarbon-based rubber and (E) a softening agent is dynamically mixed in the presence of an organic peroxide. The composition obtained by the heat treatment is also included.
This composition comprises (B) unsaturated olefin copolymers, (C) ethylene / α-olefin / non-conjugated polyene copolymers, and (B) unsaturated olefin copolymers and (C) ) An olefinic thermoplastic elastomer composition crosslinked with an ethylene / α-olefin / non-conjugated polyene copolymer. In addition, (A) a crystalline polyolefin resin and (B) an unsaturated olefin copolymer, (A)
The crystalline polyolefin resin and (C) the ethylene / α-olefin / non-conjugated polyene copolymer may be crosslinked.

Here, in the present invention, "dynamically heat-treating" means kneading the above components in a molten state. Specific examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, and 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-butyl peroxybenzoate, tert-butyl perbenzoate,
tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert
-Butylcumyl peroxide.

Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-, in terms of odor and scorch stability. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene is preferred, and
Dimethyl-2,5-di- (tert-butylperoxy) hexane is most preferred.

The organic peroxide is composed mainly of (A) a crystalline polyolefin resin, (B) an unsaturated olefin copolymer, and (C) an ethylene / α-olefin / non- 0.05 to 2% by weight, and preferably 0.1 to 2% by weight, based on 100% by weight of the total amount with the conjugated polyene copolymer.
It is used in a proportion of 1.6% by weight.

In the present invention, a crosslinking aid can be used together with the organic peroxide. As a crosslinking aid,
Specifically, sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N ' peroxy crosslinking aids such as -m-phenylenedimaleimide; or divinylbenzene,
Multifunctional methacrylate monomers such as triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate; polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate Is mentioned.

By using such a crosslinking aid,
A uniform and mild crosslinking reaction can be expected. Among the crosslinking aids, divinylbenzene is most preferred. Divinylbenzene is easy to handle and is (A) a crystalline polyolefin resin, (B) an unsaturated olefin copolymer, and (C) an ethylene / α-olefin / non-conjugated polyene, which are the main components of the object to be crosslinked. Good compatibility with the copolymer,
In addition, it has a function of solubilizing organic peroxides and acts as a dispersant for organic peroxides, so the cross-linking effect of heat treatment is uniform, and an olefin-based thermoplastic elastomer composition that balances fluidity and physical properties Things are obtained.

The above-mentioned crosslinking assistant is preferably used in a proportion of 0.05 to 3% by weight, especially 0.1 to 2% by weight, based on the whole to-be-crosslinked product. If the compounding amount of the crosslinking assistant exceeds 3% by weight, the crosslinking reaction proceeds too quickly if the compounding amount of the organic peroxide is large, so that the obtained olefin-based thermoplastic elastomer composition has a low fluidity. On the other hand, when the compounding amount of the organic peroxide is small, the crosslinking auxiliary remains as an unreacted monomer in the olefin-based thermoplastic elastomer composition, and the olefin-based thermoplastic elastomer composition is processed and molded. In such a case, changes in physical properties due to heat history may occur. Therefore, the crosslinking aid is
Should not be overblended.

The dynamic heat treatment is carried out by using a kneading device such as a mixing roll, an intensive mixer (for example, a Banbury mixer or a kneader), or a single-screw or twin-screw extruder. preferable. The dynamic heat treatment is preferably performed in an inert gas such as nitrogen.

The temperature during the heat treatment is usually in the range from the melting point of the crystalline polyolefin resin (A) to 300 ° C.
The kneading time is preferably 1 to 10 minutes. The applied shearing force is 500 to 10,000 s at a shear rate.
It is desirably in the range of ec ^-1 .

The first and second olefin-based thermoplastic elastomer compositions according to the present invention comprise (B) an unsaturated olefin-based copolymer and optionally (C) ethylene / α.
-The olefin / non-conjugated polyene copolymer is cross-linked. Here, "crosslinked" means that the gel content measured by the following method is 20% or more. If the gel content is less than the above range, rubber elasticity tends to decrease.

[Measurement Method of Gel Content] As a sample, pellets of an olefin-based thermoplastic elastomer composition (size:
0.5 x 0.5 x 0.5 mm)
Immerse in 30 ml of cyclohexane at 23 ° C. for 48 hours in a closed container.

Next, the sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. From the weight of the dried residue, the weight of all cyclohexane-insoluble components (fillers, pigments, fibrous fillers, etc.) other than the polymer component, and the weight of (A) the crystalline polyolefin resin in the sample before cyclohexane immersion are determined. The subtracted value is referred to as “corrected final weight (Y)”.

On the other hand, the crosslinkable component of the sample, that is, (B)
Unsaturated olefin copolymer and (C) ethylene.
The total value of the weight of the α-olefin / non-conjugated polyene copolymer is defined as “corrected initial weight (X)”.

The gel content is calculated from these values by the following equation. Gel content [%] = (Y / X) × 100 Next, the third olefin-based thermoplastic elastomer composition according to the present invention will be described.

The third olefin-based thermoplastic elastomer composition according to the present invention comprises: the first or second olefin-based thermoplastic elastomer composition according to the present invention;
(F) A mixture with a crystalline polyolefin resin.

As the crystalline polyolefin resin (F), for example, the above-mentioned crystalline polyolefin resin (A) can be used. (F) The crystalline polyolefin resin is used in an amount of 5 to 200 parts by weight based on 100 parts by weight of the first or second olefin-based thermoplastic elastomer composition according to the present invention.
It is used in a proportion of 5 parts by weight, preferably 5 to 100 parts by weight. When the (F) crystalline polyolefin resin is used in the above ratio, the moldability of the obtained thermoplastic elastomer composition can be further improved. However,
If the amount of the crystalline polyolefin resin (F) exceeds 200 parts by weight, not only the inherent flexibility of the elastomer is impaired, but also the rubber elasticity tends to decrease.

When the first or second olefin-based thermoplastic elastomer composition according to the present invention is mixed with (F) a crystalline polyolefin resin, a conventionally known mixing method can be used. For example, a method of mechanically blending the olefin-based thermoplastic elastomer composition with the (F) crystalline polyolefin resin using an extruder, a kneader, or the like can be employed.

In such an olefin-based thermoplastic elastomer composition, no cross-linking occurs between (B) the unsaturated olefin-based copolymer and (F) the crystalline polyolefin resin, and (C) No cross-linking occurred between the ethylene / α-olefin / non-conjugated polyene copolymer and the (F) crystalline polyolefin resin.

The thermoplastic elastomer composition of the present invention comprises:
Since the crosslinking efficiency at the time of production is high, the molded article obtained from this composition does not unnecessarily decompose the (A) crystalline polyolefin resin or (B) the unsaturated olefin copolymer. Will have excellent physical properties.

[0207]

The olefin-based thermoplastic elastomer composition according to the present invention can provide a molded article excellent in moldability and excellent in rubber elasticity, tensile strength characteristics and appearance.

[0208]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0209]

[Synthesis Example 1] [Pre-activation of catalyst] In a glass container sufficiently purged with nitrogen, isopropylidenebisindenyl zirconium dichloride 16.0 synthesized by a known method.
mg of toluene and a 1.484 mmol / ml solution of methylalumoxane in toluene (hereinafter abbreviated as MAO).
Was added so that aluminum atoms became 22.57 mmol, and ultrasonic irradiation was performed at 23 ° C. for 15 minutes to prepare a catalyst solution. [Synthesis of ethylene / propylene / isoprene copolymer]
At room temperature, 177.2 ml of toluene, 60 ml of isoprene and 5500 ml of propylene (25 ° C., 1 atm) were added to a 2-liter autoclave which had been dried under reduced pressure and purged with nitrogen, followed by 1.0 mmol / ml of triisobutylaluminum. 0.3 ml of a toluene solution of
Ethylene was supplied under stirring, pressurized to 6 kg / cm ² -G, depressurized, and this pressurized depressurizing operation was repeated three times. Then, it was made to reach 20 degreeC under ethylene normal pressure. Thereafter, the system was pressurized with ethylene to a pressure of 6 kg / cm ² -G, and 1.52 ml of the catalyst solution prepared as described above was added to initiate copolymerization of ethylene, propylene and isoprene. At this time, the catalyst concentration was 0.01 isopropylidenebisindenyl zirconium dichloride to the whole system.
23 mmol / L and MAO was 7.5 mmol / L. During the polymerization, the internal pressure was maintained at 6 kg / cm ² -G by continuously feeding ethylene. After 30 minutes, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out and washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1 to transfer a catalyst residue to an aqueous phase. After allowing the contact mixed solution to stand, the aqueous phase is separated and removed, and further distilled water is used to remove the aqueous phase.
After washing with water, the polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, which was thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. Under nitrogen circulation,
It was dried at 130 ° C. and 350 mmHg for 12 hours.

The yield of the obtained ethylene-propylene-isoprene copolymer was 18.8 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.4 dl / g, the glass transition temperature Tg was -40 ° C., and iodine was used. The value is 15 g / 100 g, the ethylene content is 68.8 mol%, and the propylene content is 25.7.
Mol%, the ring structure is 3.5 mol%, and the 1,2 addition structure is 0.1 mol%.
05 mol%, 3,4 addition structure is 1.25 mol%, 1,4
0.7 mol% additional structure, 10 kg / mmol Z activity
r · hr.

Table 3 also shows the results.

[0212]

[Synthesis Example 2] [Pre-activation of catalyst] (Dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane) dichloride synthesized by a known method in a glass container sufficiently purged with nitrogen. 13.5 mg of titanium was weighed and introduced, and a 0.808 mmol / ml solution of methylalumoxane in toluene (hereinafter abbreviated as MAO) was used to make 22.05 mmol of aluminum atoms.
86 ml was added, and ultrasonic irradiation was performed at 23 ° C. for 15 minutes.
A catalyst solution was prepared. [Synthesis of ethylene / propylene / styrene / 1,3-butadiene copolymer] In a 2-liter autoclave dried under reduced pressure and purged with nitrogen, toluene 440.
6 ml were added, and then ethylene was added with stirring to 6 kg / cm ² -G
Then, the pressure was released, and this pressure-reducing operation was repeated three times. Then, under normal pressure of ethylene, 10 ml of styrene
(25 ° C, 1 atm), 13 ml of 1,3-butadiene (25
C., 1 atm) and 4400 ml of propylene (25 ° C., 1 atm) were added to reach 20 ° C. Thereafter, the inside of the system was pressurized with ethylene to a pressure of 6 kg / cm ² -G, and 3.11 ml of the catalyst solution prepared as described above was added to copolymerize ethylene, propylene, styrene and 1,3-butadiene. Started. At this time, the catalyst concentration was 0.01 mmol / L for (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium and 6.0 mmol / MAO for the entire system. L. During polymerization, the internal pressure is increased to 6 kg by continuously supplying ethylene.
/ Cm ² -G. After 15 minutes, the polymerization reaction was stopped by adding methyl alcohol. After depressurizing, take out the polymer solution, and add 5 ml of concentrated hydrochloric acid to 1 liter of water.
Was washed with an aqueous solution to which was added at a ratio of 1: 1 to transfer a catalyst residue to an aqueous phase. After allowing the contact mixed solution to stand, the aqueous phase is separated and removed, and further washed twice with distilled water.
The polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, which was thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. 130 under nitrogen flow
It dried at 350 degreeC and 350 mmHg for 12 hours.

The yield of the obtained ethylene / propylene / styrene / 1,3-butadiene copolymer was 9 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.1 dl / g, and the glass transition temperature Tg was − 44 ° C., iodine value 17.5 g / 1
00g, ethylene content 63.6 mol%, propylene content 23.7 mol%, styrene content 5.4 mol%, 5-membered ring structure 4.8 mol%, cyclopropane ring structure 0.1 mol%, The 1,2 addition structure is 0.5 mol%, the 1,4 addition structure is 1.9 mol%, and the activity is 7.2 kg / mmol Zr · hr.
Met.

Table 3 also shows the results.

[0215]

[Synthesis Example 3] In Synthesis Example 2, (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl)
Silane) dichloride titanium was replaced with isopropylidene-bis (indenyl) zirconium dichloride synthesized by a known method in the same manner as in Synthesis Example 2 to obtain an unsaturated olefin copolymer.

The obtained ethylene / propylene / styrene / 1,3-butadiene copolymer had an intrinsic viscosity [η] of 0.8 dl / g measured in decalin at 135 ° C., a glass transition temperature Tg of −41 ° C., The iodine value is 17 g / 100 g, the ethylene content is 65.1 mol%, the propylene content is 20.2 mol%, the styrene content is 7.8 mol%, the 5-membered ring structure is 4.4 mol%, and the cyclopropane ring structure is 0. 0.1 mol%, 1,2 addition structure is 0.4 mol%, 1,4 addition structure is 2.0 mol%
Met.

Table 3 also shows the results.

[0218]

[Table 3]

The melting point (Tm) and glass transition temperature (Tg) in Table 3 were determined in the following manner. That is, D
An SC endothermic curve is determined, and the temperature at the maximum peak position is defined as a melting point (Tm).

For the measurement, the sample was packed in an aluminum pan and 10 ° C.
/ Min at 200 ° C, hold at 200 ° C for 5 minutes, decrease to -150 ° C at 20 ° C / min,
It was determined from an endothermic curve when the temperature was raised at ° C / min.

Further, Mw / Mn in Table 3 was measured at 140 ° C. in an orthodichlorobenzene solvent by using GPC (gel permeation chromatography).

[0222]

Examples 1 to 3 and Comparative Examples 1 to 6
After kneading at 180 ° C. for 5 minutes in a nitrogen atmosphere using a Banbury mixer, the kneaded material is passed through a roll to form a sheet, and cut with a sheet cutter to form square pellets. Manufactured.

The square pellets, divinylbenzene (hereinafter, referred to as “DVB”), and 2,5-dimethyl-2,5- (tert-butylperoxy) hexane (hereinafter, referred to as “POX”) were used in amounts shown in Table 4 (see Table 4). Parts by weight) and stirred and mixed with a Henschel mixer.

Next, this mixture was extruded at a temperature of 220 ° C. under a nitrogen atmosphere using a twin screw extruder having an L / D of 40 and a screw diameter of 50 mm to obtain an olefin-based thermoplastic elastomer composition.

The gel content of the obtained olefin-based thermoplastic elastomer composition was determined by the method described above. In addition, compression set (compression condition 70) which is an index of rubber elasticity is used.
° C, 22 hours) and the tensile strength are in accordance with JIS K 6301.
Was measured by the method shown in Table 1.

Further, in order to evaluate the moldability of the olefin-based thermoplastic elastomer composition and the appearance of the molded product, a die (garbage die) of the ASTM-A method was attached to a single screw extruder having a screw diameter of 50 mm, and a cross section was obtained under the following conditions. A wedge-shaped molded body was extruded.

[Extrusion molding conditions] Set temperature: C1 / C2 / C3 / C4 / C5 / H / D = 1
60/180/200/220/220/220/20
0 ° C. Screw rotation speed: 45 rpm Screen mesh: 40/80/40 mesh The moldability and the appearance of the molded product are 1 to 5 by touching the side surface (skin) and the sharp edge (edge) of the molded product with a finger.
The evaluation (relative evaluation) was performed in a step (5: good, 1: bad).

The degree of oil swelling (ΔV) of each of the thermoplastic elastomer compositions was determined by the method described above. Table 4 shows the results.

<Raw Materials Used in Examples and Comparative Examples> (A) Crystalline polyolefin resin (A1) Propylene / ethylene block copolymer · MFR (ASTM D 1238, 230 ° C, 2.16 kg load) = 12 g
(B) Unsaturated olefin-based copolymer (B1) Ethylene-propylene-isoprene copolymer synthesized in Synthesis Example 1 (B2) Ethylene-propylene synthesized in Synthesis Example 2 Styrene / 1,3-butadiene copolymer (B3) Ethylene / propylene / styrene / 1,3-butadiene copolymer synthesized in Synthesis Example 3 (C) Ethylene / α-olefin / non-conjugated polyene copolymer ( C1) Ethylene propylene / 5-ethylidene-2-norbornene copolymer rubber Ethylene content = 73 mol% Iodine value = 18 Mooney viscosity [ML _{1 + 4} (100 ° C.) = 80 (C2) Ethylene propylene -5-ethylidene-2-norbornene copolymer-Ethylene content = 70 mol%-Iodine value = 15-Intrinsic viscosity [η] measured in decalin at 135C.
4 dl / g (C3) ethylene / propylene / 5-ethylidene-2-norbornene copolymer ・ ethylene content = 65 mol% ・ iodine value = 19 ・ intrinsic viscosity [η] measured in decalin at 135 ° C. = 2.
2dl / g (D) Peroxide non-crosslinked hydrocarbon rubber (D1) Butyl rubber-Unsaturation = 0.7 mol%-Mooney viscosity [ML _{1 + 8} (100 ° C) = 45 (E) Softener (E1) Mineral oil-based process oil [Idemitsu Kosan Co., Ltd.
Product name PW-380] (G) Ethylene / α-olefin / styrene / non-conjugated diene copolymer (G1) Ethylene / 1-octene / styrene / 5-ethylidene-2-norbornene copolymer ・ Constitution derived from ethylene Unit / Structural unit derived from 1-octene (molar ratio) = 90/10 ・ Total amount of structural units derived from ethylene and 1-octene / Structural unit derived from styrene (molar ratio) = 97
/ 3 ・ Iodine value = 8 ・ Mooney viscosity [ML _{1 + 4} (100 ° C)] = 96

[0230]

Example 4 Example 2 was repeated except that the unsaturated olefin copolymer of Synthesis Example 3 was replaced with the unsaturated olefin copolymer of Synthesis Example 2. Done. Table 4 shows the results.

[0231]

[Table 4]

Claims (14)

[Claims] (1) a crystalline polyolefin resin:
60 parts by weight and (B-1) at least one kind of carbon having 2 to 2
Unsaturated olefin copolymer comprising an α-olefin of 20 and a conjugated diene monomer represented by the following formula (I): 90 to 40 parts by weight [total of components (A) and (B-1) Amount is 100 parts by weight)].
An olefinic thermoplastic elastomer composition obtained by dynamically heat-treating in the presence of an organic peroxide; [In the formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and at least one of R ¹ and R ² is a hydrogen atom.] . (A) crystalline polyolefin resin: 10 to 10
60 parts by weight, and (B-2) at least one kind of carbon number 2
Unsaturated olefin copolymer comprising an α-olefin of 20, an conjugated diene monomer represented by the following formula (I), and an aromatic vinyl compound: 90 to 40 parts by weight [components (A) and (B- Olefin-based thermoplastic elastomer composition, which is obtained by dynamically heat-treating a blend containing 2) and 100 parts by weight] in the presence of an organic peroxide; 2] [In the formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and at least one of R ¹ and R ² is a hydrogen atom.] . (A) crystalline polyolefin resin: 10 to 10
60 parts by weight and (B-1) at least one kind of carbon having 2
And an unsaturated olefin copolymer composed of the conjugated diene monomer represented by the formula (I): 85 to 10 parts by weight, and (C) an ethylene-α-olefin. Non-conjugated polyene copolymer: 1 to 50
Parts by weight, (D) peroxide non-crosslinked hydrocarbon rubber:
1 to 20 parts by weight and (E) a softener: at least one component selected from the group consisting of 1 to 40 parts by weight [components (A), (B-1), (C), (D) and ( The total amount of E) is 100 parts by weight], and the mixture is dynamically heat-treated in the presence of an organic peroxide to obtain an olefin-based thermoplastic elastomer according to claim 1. Composition. (A) a crystalline polyolefin resin:
60 parts by weight and (B-2) at least one carbon atom having 2 carbon atoms
To -20, an unsaturated olefin copolymer comprising a conjugated diene monomer represented by the above formula (I) and an aromatic vinyl compound: 85 to 10 parts by weight, and (C) ethylene・ Α
-Olefin / non-conjugated polyene copolymer: 1 to 50 parts by weight, (D) peroxide non-crosslinked hydrocarbon rubber: 1 to
20 parts by weight and (E) a softener: at least one component selected from the group consisting of 1 to 40 parts by weight [components (A), (B-2), (C), (D) and (E) Is 100 parts by weight], and is dynamically heat-treated in the presence of an organic peroxide to obtain a thermoplastic elastomer composition according to claim 2. . 5. The unsaturated olefin copolymer (B-1) has a molar ratio of a constitutional unit derived from ethylene to a constitutional unit derived from an α-olefin having 3 to 20 carbon atoms (ethylene / Α-olefin) in the range of 99/1 to 40/60, and (a) a 1,2 adduct (including a 3,4 adduct) derived from the conjugated diene monomer in the copolymer. )
And a 1,4 adduct form a double bond between the side chain and the main chain in the copolymer, and the double bond of the side chain derived from the 1,2 adduct and the 1,4 adduct Quantitative ratio to the double bond of the main chain derived from (double bond of side chain derived from 1,2 adduct (including 3,4 adduct) /
Main chain double bond derived from 1,4 adduct)
The olefin-based thermoplastic elastomer composition according to claim 1 or 3, wherein the content of the structural unit derived from the (b) conjugated diene monomer is 0.01 to 30 mol%. Stuff. 6. The unsaturated olefin copolymer (B-2) has a molar ratio of a constitutional unit derived from ethylene to a constitutional unit derived from an α-olefin having 3 to 20 carbon atoms (ethylene / Α-olefin) is in the range of 99/1 to 40/60, and a structural unit derived from ethylene and α having 3 to 20 carbon atoms
-The molar ratio [(ethylene + α-olefin) / aromatic vinyl compound] of the total amount of the structural units derived from the olefin to the structural unit derived from the aromatic vinyl compound is 9
(A) a 1,2 adduct (including a 3,4 adduct) derived from the conjugated diene monomer in the copolymer; The 1,4 adduct forms a double bond between the side chain and the main chain in the copolymer, and the double bond of the side chain derived from the 1,2 adduct and the 1,4 adduct Ratio to the double bond of the main chain (double bond of side chain derived from 1,2 adduct (including 3,4 adduct) /
Main chain double bond derived from 1,4 adduct)
The olefin-based thermoplastic elastomer composition according to claim 2 or 4, wherein the content of the structural unit derived from the conjugated diene monomer is 0.01 to 30 mol%. Stuff. 7. The (B-1) unsaturated olefin copolymer has a molar ratio of a constitutional unit derived from ethylene to a constitutional unit derived from an α-olefin having 3 to 20 carbon atoms (ethylene / Α-olefin) in the range of 99/1 to 40/60, and (a) a 1,2 adduct (including a 3,4 adduct) derived from the conjugated diene monomer in the copolymer. )
And a 1,4 adduct form a double bond between the side chain and the main chain in the copolymer, and the double bond of the side chain derived from the 1,2 adduct and the 1,4 adduct Quantitative ratio to the double bond of the main chain derived from (the double bond of the side chain derived from the 1,2 adduct (including the 3,4 adduct) /
Main chain double bond derived from 1,4 adduct)
(B) the content of the structural unit derived from the conjugated diene monomer is 0.01 to 30 mol%, and (c)
The copolymer has a five-membered ring in the main chain, and 2
Quantitative ratio of heavy bond to 5-membered ring (total double bond of all adducts / 5
The olefin-based thermoplastic elastomer composition according to any one of claims 1, 3 and 5, wherein the number of the ring is from 20/80 to 90/10. 8. The unsaturated olefin-based copolymer (B-2) has a molar ratio of a structural unit derived from ethylene to a structural unit derived from an α-olefin having 3 to 20 carbon atoms (ethylene / Α-olefin) is in the range of 99/1 to 40/60, and a structural unit derived from ethylene and α having 3 to 20 carbon atoms
-The molar ratio [(ethylene + α-olefin) / aromatic vinyl compound] of the total amount of the structural units derived from the olefin to the structural unit derived from the aromatic vinyl compound is 9
(A) a 1,2 adduct (including a 3,4 adduct) derived from the conjugated diene monomer in the copolymer; The 1,4 adduct forms a double bond between the side chain and the main chain in the copolymer, and the double bond of the side chain derived from the 1,2 adduct and the 1,4 adduct Ratio to the double bond of the main chain (double bond of side chain derived from 1,2 adduct (including 3,4 adduct) /
Main chain double bond derived from 1,4 adduct)
(B) the content of the structural unit derived from the conjugated diene monomer is 0.01 to 30 mol%, and (c)
The copolymer has a five-membered ring in the main chain, and 2
Quantitative ratio of heavy bond to 5-membered ring (total double bond of all adducts / 5
The olefin-based thermoplastic elastomer composition according to any one of claims 2, 4 and 6, wherein the (member ring) is 20/80 to 90/10. 9. The intrinsic viscosity [η] of the unsaturated olefin copolymer (B-1) or (B-2) measured in decalin at 135 ° C. is in the range of 0.1 to 10 dl / g. The olefin-based thermoplastic elastomer composition according to any one of claims 1 to 8, wherein 10. The unsaturated olefin copolymer (B-1) or (B-2) has an iodine value in the range of 1 to 50. 3. The olefin-based thermoplastic elastomer composition according to 1.). 11. The conjugated diene monomer of the unsaturated olefin copolymer (B-1) or (B-2) is 1,3-
The olefin-based thermoplastic elastomer composition according to any one of claims 1 to 10, which is butadiene or isoprene. (A) a crystalline polyolefin resin: 10
To 60 parts by weight, (B-1) ethylene, an α-olefin having 3 to 20 carbon atoms, and the formula (I)
Unsaturated olefin copolymer comprising a conjugated diene monomer represented by the formula: 90 to 40 parts by weight [components (A) and (B)
-1) is a olefinic thermoplastic elastomer composition obtained by dynamically heat-treating a blend containing 100 parts by weight) in the presence of an organic peroxide. The intrinsic viscosity [η], iodine value, and ethylene content measured in the above are the respective values of the intrinsic viscosity [η], iodine value, and ethylene content of the (B-1) unsaturated olefin copolymer. Ethylene / α-olefin / 5, which is in the range of ± 10% and whose α-olefin having 3 to 20 carbon atoms is the same as the α-olefin of the unsaturated olefin copolymer (B-1). Ethylene obtained by dynamically heat-treating a blend of the same composition as the above-mentioned olefin-based thermoplastic elastomer composition, using a -ethylidene-2-norbornene copolymer (X), in the presence of an organic peroxide.・ Α-olefin ・ 5-d The olefin-based thermoplastic elastomer composition according to claim 1 or 3, wherein the degree of oil swelling is 90% or less as compared with the thermoplastic elastomer composition containing a silidene-2-norbornene copolymer (X). Stuff. 13. (A) a crystalline polyolefin resin: 10
And (B-2) ethylene, an α-olefin having 3 to 20 carbon atoms, a conjugated diene monomer represented by the above formula (I), and an unsaturated olefin-based copolymer comprising an aromatic vinyl compound. A polymer containing 90 to 40 parts by weight [the total amount of components (A) and (B-2) is 100 parts by weight)] is dynamically heat-treated in the presence of an organic peroxide. An olefinic thermoplastic elastomer composition obtained by the above method, wherein each of the intrinsic viscosity [η], iodine value, ethylene content and aromatic vinyl compound content measured in decalin at 135 ° C. is the (B-2) unsaturated Α-olefins having 3 to 20 carbon atoms in the range of ± 10% of each of intrinsic viscosity [η], iodine value, ethylene content and aromatic vinyl compound content of the functional olefin copolymer. Group vinyl compound is (B- 2) α- of unsaturated olefin copolymer
An ethylene / α-olefin / 5-ethylidene-2-norbornene / aromatic vinyl compound copolymer (X) which is the same as the olefin and the aromatic vinyl compound, respectively,
An ethylene / α-olefin / 5-ethylidene-2-norbornene / aromatic obtained by dynamically heat-treating a blend having the same composition as the olefin-based thermoplastic elastomer composition in the presence of an organic peroxide. Compared with the vinyl compound copolymer (X) -containing thermoplastic elastomer composition,
3. The oil swelling degree is 90% or less.
Or the olefin-based thermoplastic elastomer composition according to 4. 14. The olefinic thermoplastic elastomer composition according to claim 1, comprising: 100 parts by weight; and (F) a crystalline polyolefin resin: 5 to 200 parts by weight. An olefin-based thermoplastic elastomer composition.