JP2001011246A - Automotive interior skin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a skin material excellent in vacuum formability by using a composition obtained by crosslinking a crystalline polyolefin resin and an ethylene/α-olefin/nonconjugated polyene copolymer rubber by dynamic heat treatment. SOLUTION: The ethylene/α-olefin/nonconjugated polyene copolymer rubber is obtained by the random copolymerization of ethylene with a 3-20C α-olefin and a nonconjugated polyene in the presence of a metallocene catalyst, comprises ethylene units and α-olefin units in a molar ratio of 40/60 to 95/5, and has an iodine value of 1-50 and an intrinsic viscosity of 1.0-10 dl/g as measured in decalin at 135 deg.C. The skin material is made from a composition obtained by dynamically heat-treating a thermoplastic elastomer composition comprising 90-40 pts.wt. above copolymer rubber and 10-60 pts.wt. crystalline polyolefin under conditions of the formula. In the formula, T is the resin temperature ( deg.C) at the exit of the die of an extruder; X is the diameter (mm) of the extruder screw; Y is the maximum shear rate (sec-1) exerted in the extruder; and Z is an extrusion rate (kg/h).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automobile interior skin material made of an olefin-based thermoplastic elastomer, and more particularly to an automobile interior skin material excellent in vacuum moldability.

[0002]

2. Description of the Related Art Instrumental panels for automobiles,
Conventionally, soft vinyl chloride resin has been mainly used for interior skin materials such as door trims, but in recent years, olefin-based thermoplastic elastomers have begun to be used from the viewpoint of lightening of materials. Vacuum molding is generally used to shape interior skin sheets into the shape of instrument panels and door trims, but olefin-based thermoplastic elastomers tend to be inferior in vacuum moldability to conventional soft vinyl chloride resins. There was a strong demand for improvements.

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, have found that using a specific ethylene / α-olefin / non-conjugated polyene copolymer rubber polymerized using a metallocene catalyst. The present inventors have found that an automobile interior skin material excellent in vacuum formability can be obtained, and completed the present invention.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and an object of the present invention is to provide an automobile interior skin material excellent in vacuum formability.

[0005]

The present invention includes the following inventions. (I) Ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprising 10 to 60 parts by weight of crystalline polyolefin resin (A), ethylene, α-olefin having 3 to 20 carbon atoms and non-conjugated polyene 90 to 40 parts by weight [total of (A) and (B) is 100 parts by weight. Wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is crosslinked to form a thermoplastic elastomer composition,
The non-conjugated polyene copolymer rubber (B) is obtained by randomly copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene in the presence of a metallocene catalyst, and (1) (a ) A unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms in a molar ratio of 40/60 to 95/5 [(a) / (b)]; 2) an iodine value of 1 to 50,
(3) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.0 to 10 dl / g, and the thermoplastic elastomer composition has the following formula:

[0006]

5.5 <2.2 log X + log Y-log Z + (T-18
0) ÷ 100 <6.5 (where T is the resin temperature at the die exit of the extruder (° C)
X is the screw diameter (mm) of the extruder,
Y is the maximum shear rate (sec ^-1 ) experienced in the extruder, and Z is the throughput (kg / h). A car interior skin material comprising an olefin-based thermoplastic elastomer composition, which is produced by dynamically heat-treating according to the conditions described in (1).

(Ii) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is (4) the (3)
The intrinsic viscosity [η] measured by the above and the ethylene content having the same weight average molecular weight (by the light scattering method) as that of the ethylene / α-olefin / non-conjugated polyene copolymer rubber having the intrinsic viscosity [η] are 70 mol. % Linear ethylene / propylene copolymer in intrinsic viscosity [η] measured in decalin at 135 ° C. Ratio to _blank [gη ^* (= [η] / [η]
_blank ))] is 0.2 to 0.95.

(Iii) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is (5) ¹³ C-NM
Intensity ratio D of Tαβ to Tαα in R spectrum
(Tαβ / Tαα) is 0.5 or less, and (6) ¹³ C-
NMR spectrum and the following formula:

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is (a) in the random copolymer rubber
The molar fraction of units derived from ethylene, [P
_O ] is the mole fraction of the unit derived from (b) α-olefin in the random copolymer rubber, and [P _OE ] is α- to the total number of dyad chains in the random copolymer rubber. It is the ratio of the number of olefin / ethylene chains. ) Is from 1.00 to 1.50, and (7) the glass transition temperature (Tg) determined by DSC
The automotive interior skin material according to the above (ii), which has a temperature of -50 ° C or lower.

(Iv) Crystalline polyolefin resin (A) 1
An ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising 0 to 60 parts by weight and ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, wherein ethylene and ethylene are present in the presence of a metallocene catalyst. Α having 3 to 20 carbon atoms
-Obtained by random copolymerization of an olefin and a non-conjugated polyene, wherein (1) a unit derived from (a) ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms are 40 / 60 to 95/5 [(a) /
(B)], and (2) an iodine value of 1 to 50.
(3) ethylene · α having an intrinsic viscosity [η] of 1.0 to 10 dl / g measured in decalin at 135 ° C.
-Olefin / non-conjugated polyene copolymer rubber (B) 90
４０40 parts by weight [total of (A) and (B) is 100 parts by weight. And the following equation:

[0010]

5.5 <2.2 log X + log Y-log Z + (T-18
0) ÷ 100 <6.5 (where T is the resin temperature at the die exit of the extruder (° C)
X is the screw diameter (mm) of the extruder,
Y is the maximum shear rate (sec ^-1 ) experienced in the extruder, and Z is the throughput (kg / h). A) dynamically producing an olefin-based thermoplastic elastomer composition by subjecting it to a heat treatment in the presence of a crosslinking agent in accordance with the conditions described in (1), and molding it into a desired shape; Method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an automotive interior skin material of the present invention will be specifically described. The automotive interior skin material of the present invention comprises a crystalline polyolefin resin (A) and ethylene / α.
-An olefin-based thermoplastic elastomer composition composed of an olefin / non-conjugated polyene copolymer rubber (B) and crosslinked with the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).

The thermoplastic elastomer composition used in the present invention is based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). It may contain 2 to 100 parts by weight of a softener (C) and / or 2 to 100 parts by weight of an inorganic filler (D).

Further, the thermoplastic elastomer composition used in the present invention comprises at least a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) in the presence of a crosslinking agent. It is manufactured by a method of dynamically heat-treating below, and the cross-linking agent is preferably an organic peroxide. (Olefin-based thermoplastic elastomer composition) Crystalline polyolefin resin (A)

The crystalline polyolefin resin (A) used in the present invention comprises a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either a high-pressure method or a low-pressure method. . Such resins include, for example, isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

Suitable starting olefins for the crystalline polyolefin resin (A) include, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl -1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like. These olefins are used alone or in combination of two or more.

The polymerization mode may be random or block, and any polymerization mode may be adopted as long as a resinous material is obtained. These crystalline polyolefin resins may be used alone or in combination of two or more. In particular, in the present invention, ethylene content 8
It is preferable to use 5 mol% or more of the crystalline ethylene / α-olefin copolymer in combination.

The crystalline polyolefin resin (A) used in the present invention is an MFR (ASTM D1238-65T, 2
30 ° C.) is usually 0.01 to 100 g / 10 min, particularly 0.1 g.
It is preferably in the range of 0.5 to 50 g / 10 minutes. The crystalline polyolefin resin (A) has a role of improving the fluidity and heat resistance of the composition.

In the present invention, the crystalline polyolefin resin (A) is used based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). , 10 to 60 parts by weight, preferably 15 to 55 parts by weight.

When the crystalline polyolefin resin (A) is used in the above ratio, an olefin-based thermoplastic elastomer composition having excellent rubber elasticity and excellent moldability can be obtained. Ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) Ethylene / α used in the present invention
-The olefin / non-conjugated polyene copolymer rubber (B)
It can be obtained by random copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of a metallocene catalyst as described below.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) preferably has a long-chain branched molecular structure. Α having 3 to 20 carbon atoms
Examples of the olefin include propylene, 1-butene, 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, 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, 9-
Methyl-1-decene, 11-methyl-1-dodecene, 1
2-ethyl-1-tetradecene, and combinations thereof.

Of these, long-chain branched ethylene / α
As the α-olefin constituting the -olefin / non-conjugated polyene copolymer rubber, an α-olefin having 3 to 10 carbon atoms is preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used. .

Long-chain branched ethylene / α-olefins
The non-conjugated polyene constituting the non-conjugated polyene copolymer rubber is a non-conjugated polyene having only one carbon-carbon double bond per molecule which can be polymerized with a metallocene catalyst, among carbon-carbon double bonds. It is. Such non-conjugated polyenes do not include chain polyenes having vinyl groups at both ends. When one of the two or more vinyl groups is a terminal vinyl group, the other vinyl group preferably has an internal olefin structure instead of a terminal. Examples of such a non-conjugated polyene include an aliphatic polyene and an alicyclic polyene.

Specific examples of the aliphatic polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. , 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-
1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1,6-octadiene, 4-
Methyl-1,4-octadiene, 5-methyl-1,4-
Octadiene, 4-ethyl-1,4-octadiene, 5
-Ethyl-1,4-octadiene, 5-methyl-1,5
-Octadiene, 6-methyl-1,5-octadiene,
5-ethyl-1,5-octadiene, 6-ethyl-1,
5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-
1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl- 1,4-nonadiene, 5-ethyl-
1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-
1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-
1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-
1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-
1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-
1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-
1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-
1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-
1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-
Examples thereof include 1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, and 9-methyl-1,8-undecadiene.

The alicyclic polyene is preferably a polyene composed of an alicyclic portion having one unsaturated bond and a chain portion having an internal olefin bond. 2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylidene-2-norbornene and the like can be mentioned. Also, 2,3-diisopropylidene-5
And trienes such as -norbornene and 2-ethylidene-3-isopropylidene-5-norbornene. Among these non-conjugated polyenes, 5-ethylidene-2-norbornene, 1,4-hexadiene and the like are particularly preferred. These non-conjugated polyenes can be used alone or in combination of two or more.

The long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) (hereinafter referred to as “copolymer rubber (B)”) preferably used in the present invention is as follows.
It has the following characteristics. (1) Ethylene / α-olefin component ratio The copolymer rubber (B) is composed of (a) a unit derived from ethylene, and (b) an α-olefin having 3 to 20 carbon atoms (hereinafter, referred to as “α-olefin”).
It may be simply referred to as “α-olefin”. Is derived from 40/60 to 95/5, preferably 5
It is contained in a molar ratio of 5/45 to 90/10 [(a) / (b)]. Such an ethylene / α-olefin / non-conjugated polyene copolymer rubber having an ethylene component / α-olefin component ratio has excellent low-temperature flexibility and heat resistance.

(2) Iodine value The copolymer rubber (B) has an iodine value, which is an index of the amount of the non-conjugated polyene component, of 1 to 50, preferably 5 to 40. The ethylene / α-olefin / non-conjugated polyene copolymer rubber having the above-mentioned iodine value has a high vulcanization rate and can be vulcanized at high speed.

(3) Intrinsic Viscosity [η] The intrinsic viscosity [η] of the copolymer rubber (B) measured in decalin at 135 ° C. is 1.0 to 10 dl / g, preferably 1.2 to 6 dl. / G, more preferably 1.5-5 dl
/ G.

[0028] Jiita ^* value of (4) gη ^* value long-chain branched copolymer rubber (B) is 0.2
-0.95, preferably 0.4-0.9, more preferably 0.5-0.85. This gη ^* value is defined by the following equation.

[0029]

Gη ^* = [η] / [η] _blank (where [η] is the intrinsic viscosity measured in the above (3), and [η] _blank is the intrinsic viscosity [η] of the intrinsic viscosity [η]. It is the intrinsic viscosity of a linear ethylene / propylene copolymer having the same weight average molecular weight (by light scattering method) as the ethylene / α-olefin / non-conjugated polyene copolymer rubber and having an ethylene content of 70 mol%. )

When the gη ^* value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is 0.95 or less, it indicates that a long-chain branch is formed in the molecule. Note that g
The η ^* value can be measured by the method described in Japanese Patent Publication No. 3-14045. Further, the long-chain branched copolymer rubber (B) preferably satisfies the following properties (5) to (7).

(5) D value Intensity (area) ratio of Tαβ to Tαα in the ¹³ C-NMR spectrum of the copolymer rubber (B) D (Tαβ / T
αα) is desirably 0.5 or less, particularly 0.3 or less.

The strength ratio D of the random copolymer rubber differs depending on the type of α-olefin constituting the random copolymer rubber. Here, Tαβ and Tαα in the ¹³ C-NMR spectrum are the peak intensities of CH _{2 in} the unit derived from α-olefin, respectively.
As shown below, two types of CH ₂ having different positions with respect to the tertiary carbon are meant.

[0033]

Embedded image

The strength ratio D of the random copolymer rubber can be determined as follows. The ¹³ C-NMR spectrum of the random copolymer rubber was measured, for example, by JEOL Ltd.
Using manufactured JEOL-GX270 NMR measuring apparatus, a sample concentration of 5 wt% of hexachlorobutadiene / d ₆ - a mixed solution of benzene = 2/1 (volume ratio), 67.8MH
It is measured on the basis of d ₆ -benzene (128 ppm) at z and 25 ° C.

The analysis of the ¹³ C-NMR spectrum is basically based on the proposal of Lindemann Adams (Analysis Chemistry, 4
3, p.1245 (1971)), JCRandall (Review Macromolecu
lar Chemistry Physics, C29, 201 (1989)). Here, regarding the intensity ratio D, ethylene / 1
-Butene-7-methyl-1,6-octadiene copolymer rubber will be described more specifically by way of example.

This ethylene / 1-butene / 7-methyl-
In the ¹³ C-NMR spectrum of the 1,6-octadiene copolymer rubber, the peak appearing at 39 to 40 ppm is Tαα.
And the peak appearing at 31 to 32 ppm is assigned to Tαβ. The intensity ratio D is calculated from the integrated value (area) ratio of each peak portion.

The strength ratio D thus determined is generally the ratio of the occurrence of the 1,1 addition reaction of 1-butene followed by the 2,1 addition reaction or the ratio of the occurrence of the 2,1 addition reaction of 1-butene. It is considered a scale indicating the rate at which 1,2 addition reactions occur. Therefore, it is shown that the larger the intensity ratio D value is, the more irregular the bonding direction of α-olefin (1-butene) is. Conversely, a smaller D value indicates that the α-olefin bond direction is more regular. If the regularity is higher, the molecular chains are more likely to assemble, and the random copolymer rubber tends to have higher strength and the like. Preferred.

In the present invention, as described below, the strength ratio D is increased by copolymerizing ethylene, an α-olefin and a non-conjugated polyene using a specific Group 4 (titanium group) metallocene catalyst. A random copolymer rubber having a ratio of 0.5 or less is obtained, but ethylene, 1-butene and 7-methyl-1,6-octadiene are copolymerized in the presence of a Group 5 metallocene catalyst such as vanadium. Even if it is polymerized, an ethylene / 1-butene / 7-methyl-1,6-octadiene copolymer rubber having the strength ratio D of 0.5 or less cannot be obtained. The same applies to α-olefins other than 1-butene.

(6) B value The copolymer rubber (B) has a ¹³ C-NMR spectrum and the following formula:

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is (a) in the random copolymer rubber
The molar fraction of units derived from ethylene, [P
_O ] is the mole fraction of the unit derived from (b) α-olefin in the random copolymer rubber, and [P _OE ] is α- to the total number of dyad chains in the random copolymer rubber. It is the ratio of the number of olefin / ethylene chains. ) Is preferably 1.00 to 1.50.

This B value is an index indicating the distribution state of ethylene and α-olefin in the copolymer rubber.
It can be determined based on the report of J. Ray (Macromolecules, 10, 773 (1977)).

The larger the B value, the shorter the block chain of ethylene or α-olefin, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer rubber. I have. In addition, the composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00, and such a copolymer rubber is, for example, in the case of being crosslinked, as compared with a copolymer rubber having a narrow composition distribution. Physical properties such as strength may not be sufficiently exhibited.

In the present invention, as described below, ethylene, an α-olefin and a non-conjugated polyene are copolymerized using a specific Group 4 (titanium group) metallocene catalyst, so that the B value is 1 A random copolymer rubber having a molecular weight of 0.001 to 1.50 is obtained. For example, even if ethylene, an α-olefin and a non-conjugated polyene are copolymerized in the presence of a titanium-based nonmetallocene-based catalyst, Cannot obtain an ethylene / α-olefin / non-conjugated polyene copolymer rubber having a B value of

(7) Glass Transition Temperature The glass transition temperature (Tg) of the copolymer rubber (B) measured by DSC (differential scanning calorimeter) is desirably -50 ° C. or lower. From a random copolymer rubber having a glass transition temperature (Tg) of −50 ° C. or lower, a thermoplastic elastomer composition having excellent low-temperature flexibility can be obtained.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention, for example, a random copolymer rubber of ethylene, 1-butene and ethylidene norbornene (ENB) is used as the random copolymer rubber. The glass transition temperature (Tg) is lower by about 5 to 10 ° C. than the copolymer rubber of ethylene, propylene and ENB (EPDM) having the same composition ratio of ethylene, α-olefin and non-conjugated polyene, It has excellent characteristics.

The long-chain branched copolymer rubber (B) is prepared by random copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene in the presence of a specific metallocene catalyst. It is manufactured by having The metallocene catalyst used in the present invention is a metallocene compound [A]
Is not particularly limited except that it contains a metallocene compound [A] and a compound [C] which forms an ion pair by reacting with the organoaluminum oxy compound [B] and / or the metallocene compound [A]. May be done. Further, it may be formed from a metallocene compound [A], an organic aluminum compound [D] together with an organic aluminum oxy compound [B] and / or a compound [C] forming an ion pair. Hereinafter, components used when forming the metallocene-based catalyst will be described. As the metallocene compound [A], the following general formula (I):

[0046]

Embedded image

The compounds represented by In the above formula (I), M is a transition metal atom of Group 4 of the periodic table (titanium group), specifically, titanium, zirconium and hafnium, and particularly preferably zirconium.

R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group,
Alkyl groups such as isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl;
An alkenyl group such as a vinyl group and a propenyl group is exemplified. Of these, a primary alkyl group in which carbon bonded to the indenyl group is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group and an ethyl group are particularly preferred.

R ² , R ⁴ , R ⁵ and R ⁶ may be the same or different and are each a hydrogen atom, a halogen atom or R ¹
Is a hydrocarbon group having 1 to 6 carbon atoms. Here, the halogen atom is fluorine, chlorine, bromine, or iodine. R ³ is an aryl group having 6 to 16 carbon atoms. This aryl group is, for example, the halogen atom, the carbon number 1 to
It may be substituted with 20 hydrocarbon groups and / or organic silyl groups. As the aryl group, specifically, a phenyl group, an α-naphthyl group, a β-naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, an acenaphthyl group, a phenalenyl group, an aceanthrenyl group, a tetrahydronaphthyl group, an indanyl group, And a biphenylyl group. Among these, a phenyl group, a naphthyl group, an anthracenyl group and a phenanthryl group are preferred.

The hydrocarbon group having 1 to 20 carbon atoms which is a substituent of the aryl group includes, for example, a methyl group,
Alkenyl groups such as ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, dodecyl group, eicosyl group, norbornyl group, adamantyl group, vinyl group, propenyl group, cyclohexenyl group, etc. Benzyl group, phenylethyl group, arylalkyl group such as phenylpropyl group, the aryl group exemplified for R ³ , and tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, methylnaphthyl group, benzyl An aryl group having 6 to 20 carbon atoms such as a phenyl group is exemplified.

Examples of the organic silyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group. X ¹ and X ² may be the same or different from each other, and may have a hydrogen atom, the halogen atom, or may be substituted with the halogen atom.
0 hydrocarbon group, oxygen-containing group or sulfur-containing group.

Further, as the oxygen-containing group, specifically,
C1-C20 alkoxy groups such as hydroxyl, methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; phenylmethoxy and phenylethoxy And aryl-C _1-20 -alkoxy groups.

Examples of the sulfur-containing group include substituents in which oxygen in the oxygen-containing group is replaced by sulfur; methylsulfonyloxy, trifluoromethanesulfonyloxy, phenylsulfonyloxy, benzylsulfonyloxy, p-type -Sulfonyloxy groups such as toluenesulfonyloxy group, trimethylbenzenesulfonyloxy group, triisobutylbenzenesulfonyloxy group, p-chlorobenzenesulfonyloxy group, pentafluorobenzenesulfonyloxy group; methylsulfonyl group, phenylsulfonyl group, benzenesulfonyl group , A p-toluenesulfonyl group, a trimethylbenzenesulfonyl group, a sulfonyl group such as a pentafluorobenzenesulfonyl group, and the like.

Of these, X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-,- CO
-, - S -, - SO -, - SO 2 -, - NR 7 -, - P
^{(R 7) -, - P} (O) (R 7) -, - BR 7 - or -
AlR ⁷ - (wherein, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group, or one or more of the hydrocarbon group having 1 to 20 carbon atoms which is substituted with a halogen atom having 1 to 20 carbon atoms Represents a methylene group, a dimethylmethylene group, an ethylene group, a dimethylethylene group,
Alkylene groups such as trimethylene group, tetramethylene group, 1,2-cyclohexylene group and 1,4-cyclohexylene group; alkylidene groups such as cyclohexylidene group; arylalkylene groups such as diphenylmethylene group and diphenylethylene group; A divalent hydrocarbon group having 1 to 20 carbon atoms;
A halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms, for example, chloromethylene; methylsilylene group, dimethylsilylene group, diethylsilylene group, di (n-propyl) silylene group, di ( alkylsilylene groups such as i-propyl) silylene group, di (cyclohexyl) silylene group, methylphenylsilylene group, diphenylsilylene group, di (p-tolyl) silylene group, di (p-chlorophenyl) silylene group, and alkylarylsilylene group ,
A divalent silicon-containing group such as an alkylsilyl group such as an arylsilylene group, a tetramethyl-1,2-disilyl group, or a tetraphenyl-1,2-disilyl group; an alkylaryldisilyl group or an aryldisilyl group; Examples thereof include a divalent germanium-containing group in which silicon of the divalent silicon-containing group is substituted with germanium.

Of these, Y is preferably a divalent silicon-containing group or a divalent germanium-containing group,
It is more preferably a divalent silicon-containing group, particularly preferably an alkylsilylene group, an alkylarylsilylene group or an arylsilylene group.

Hereinafter, specific examples of the metallocene compound represented by the general formula (I) will be shown. rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Methyl-4- (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, rac-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, rac-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- (2,4-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- (2,6-
Dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-
4- (p-ethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4- (p-isopropylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-benzylphenyl)
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-biphenylyl) -1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2-methyl-4- (m-biphenylyl) -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-phenyl-4-phenyl-1)
-Indenyl) zirconium dichloride, rac-diethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di- (isopropyl) 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, rac-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-dimethylstannylene-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, ra
c-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride SO ₂ Me,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride OSO ₂ M
e, rac-dimethylsilylene-bis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2-ethyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-ethyl-4- (β-
Naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-
(2-methyl-1-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Ethyl-4- (5-acenaphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-ethyl-4- (9-anthracenyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-ethyl-4- (o-methylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-
(M-methylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (p-methylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2- Ethyl-4- (2,3-dimethylphenyl) -1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (2,4-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-
(2,5-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Ethyl-4- (2,4,6-trimethylphenyl)-
1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (o-chlorophenyl) -1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2-ethyl-4- (m-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-
(P-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (2,3-dichlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-ethyl-4- (2,6-dichlorophenyl)
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (3,5-dichlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-
(2-bromophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (3-bromophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2- Ethyl-4- (4-bromophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (4-biphenylyl) -1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4- (4-trimethylsilylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-propyl-
4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-propyl-4
-(Α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-propyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 −n-
Propyl-4- (2-methyl-1-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-propyl-4- (5-acenaphthyl) -1-indenyl) zirconium dichloride, rac -
Dimethylsilylene-bis (2-n-propyl-4- (9-
Anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-propyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Isopropyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Isopropyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-isopropyl-4- (β-naphthyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-isopropyl-4- (8-methyl-
9-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-isopropyl-4- (5-acenaphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Isopropyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-isopropyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-s-butyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-s-butyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-s-butyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride;
rac-dimethylsilylene-bis (2-s-butyl-4- (2
-Methyl-1-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-s-
Butyl-4- (5-acenaphthyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-s-butyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-s-butyl-4- (9-phenanthryl) ) -1-Indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-n-pentyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-pentyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-n-butyl-4-phenyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-n-butyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride;
rac-dimethylsilylene-bis (2-n-butyl-4- (β
-Naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-butyl-4-
(2-methyl-1-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-N-butyl-4- (5-acenaphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-n-butyl-4- (9-anthracenyl) -1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-butyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2-isobutyl-4-phenyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-isobutyl-4- (α-
Naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-isobutyl-4
-(Β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-isobutyl-4- (2-methyl-1-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-isobutyl-4- (5-acenaphthyl) -1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-isobutyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-isobutyl-4-
(9-phenanthryl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-neopentyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-neopentyl-4- (α -Naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-hexyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-hexyl-4- (Α-naphthyl) -1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-ethyl-4- (Α-naphthyl) -1
-Indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-ethyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-ethyl-
4- (9-phenanthryl) -1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2
-Ethyl-4-phenyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-ethyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2
-Ethyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-ethyl-4- (9-phenanthryl) -1
-Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-ethyl-4- (4-biphenylyl) -1-indenyl) zirconium dichloride, rac-
Methylene-bis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylene-bis (2-ethyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-ethylene-bis ( 2
-Ethyl-4-phenyl-1-indenyl) zirconium dichloride, rac-ethylene-bis (2-ethyl-4-
(Α-naphthyl) -1-indenyl) zirconium dichloride, rac-ethylene-bis (2-n-propyl-4-
(Α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylgermyl-bis (2-ethyl-4)
-Phenyl-1-indenyl) zirconium dichloride, rac-dimethylgermyl-bis (2-ethyl-4-
(Α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylgermyl-bis (2-n-propyl-4-phenyl-1-indenyl) zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. In the present invention, a racemic form of the metallocene compound is generally used as a catalyst component, but an R-type or S-type may also be used. In the present invention, two or more metallocene compounds as described above can be used in combination.

The metallocene compound can be obtained from the Journal of Org
anometallic Chem. 288 (1985), pp. 63-67, EP-A-0,320,762. As the metallocene compound [A], in addition to the metallocene compound represented by the general formula (I), the following general formula (II) described in JP-A-3-16388 or the like:

[0059]

## STR3 ## L ^a MX ₂ (II) (wherein, M is Group 4 of the periodic table (a metal of the titanium group) or lanthanide series, L ^a is a moiety comprising a delocalized π bond The metal M active site has a constrained geometry, and X is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a silicon atom or a germanium atom. , A silyl group or a germyl group.). Among the compounds represented by the formula (II), specifically, the following formula (III):

[0060]

Embedded image

(Wherein M is titanium, zirconium or hafnium, X is the same as described above, and Cp is
A substituted cyclopentadienyl group having a π bond to M and having a substituent Z or a derivative thereof, wherein Z is oxygen,
A moiety containing sulfur, boron or an element of group 14 (carbon group) of the periodic table, Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and forms a condensed ring with Z and Y You may. Are preferred.

Specific examples of the compound represented by the formula (III) include (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t- butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl)
Titanium dichloride, (dibenzyl (t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, (dimethyl (t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane) dibenzyltitanium, (dimethyl (t-butylamide)
(Tetramethyl- eta ⁵ - cyclopentadienyl) silane) dimethyl titanium, ((t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl) dibenzyl titanium, ((methylamide) (Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) dineopentyl titanium, ((phenyl phosphide)
(Tetramethyl-η ⁵ -cyclopentadienyl) methylene) diphenyltitanium, (dibenzyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dibenzyltitanium, (dimethyl (benzylamide) (η ⁵ - cyclopentadienyl) silane) di (trimethylsilyl) titanium, (dimethyl (phenyl phosphide) - (tetramethyl-eta ⁵ - cyclopentadienyl)
Silane) dibenzyltitanium, ((tetramethyl-η ⁵ −
(Cyclopentadienyl) -1,2-ethanediyl) dibenzyltitanium, (2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dibenzyltitanium, (2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dimethyltitanium,
(2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl)
Cyclohexanolate (2-)) dimethyltitanium, (2-((4
a, 4b, 8a, 9,9a- [eta])-9H-fluoren-9-yl) cyclohexanolate (2-)) dibenzylzirtitanium.

In the present invention, two or more metallocene compounds represented by the above formula (II) can be used in combination. In the above description, a titanium compound is exemplified as a metallocene compound, but a compound in which titanium is replaced with zirconium or hafnium can also be exemplified.

These compounds may be used alone or in combination of two or more. In preparing the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), among the above-mentioned metallocene compounds, the metallocene compound represented by the general formula (I) is preferably used.

The organoaluminum oxy compound [B] used for the preparation of the metallocene catalyst may be a conventionally known aluminoxane.
Or a benzene-insoluble organic aluminum oxy compound as exemplified in Japanese Patent Application Laid-Open No. H10-260,000. A conventionally known aluminoxane can be produced, for example, by the following method.

(1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate,
An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate and the like to react. A method of recovering as a hydrocarbon solution.

(2) A method in which an organic aluminum compound such as a trialkylaluminum is directly reacted with water, ice or steam in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover a hydrocarbon solution. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent. As the organoaluminum compound used in the production of aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Tricycloalkylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dimethylaluminum methoxide, diethylaluminum ethoxide and the like Dialkylur Mini um alkoxide; dialkylaluminum arylene Loki Sid such as diethylaluminum phenoxide and the like. Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.

The organoaluminum compound used in the production of aluminoxane is represented by the formula (i-C ₄ H)
₉₎ in _{x Al y (C 5 H 10} ) z ( wherein, x, y, z are each a positive number, may be used isoprenyl aluminum represented by a z ≧ 2x.). The above-mentioned organoaluminum compounds may be used in combination of two or more.

Solvents used in the production of aluminoxane include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene and light oil; and the above-mentioned aromatic hydrocarbons and fats Group hydrocarbons, alicyclic hydrocarbon halides,
Particularly, halogenated hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

Examples of the compound [C] which forms an ion pair by reacting with the metallocene compound [A] include:
No. 01950, Japanese Unexamined Patent Publication No. Hei.
JP, JP-A-3-207703, JP-A-3-2703
No. 07704, U.S. Pat. No. 5,321,106, and the like, Lewis acids, ionic compounds, borane compounds, and carborane compounds.

Examples of the Lewis acid include a magnesium-containing Lewis acid, an aluminum-containing Lewis acid, and a boron-containing Lewis acid. Of these, a boron-containing Lewis acid is preferable. As the boron-containing Lewis acid, specifically,
The following general formula: BR ⁸ R ⁹ R ¹⁰ (wherein, R ⁸ , R ⁹ and R ¹⁰ may each independently have a substituent such as a fluorine atom, a methyl group, a trifluoromethyl group, etc. A phenyl group or a fluorine atom).

Specific examples of the boron-containing Lewis acid represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound [A] by reacting with the metallocene compound [A], thereby stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and an anion that is relatively bulky and stabilizes a transition metal cation species is preferable. Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation,
Examples thereof include a sulfonium cation, a phosphonium cation, and an ammonium cation. Specific examples include triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, ferrocenium cation, and the like.

The ionic compound is preferably an ionic compound having an organic boron compound anion. Specifically, triethylammonium tetra (phenyl)
Boron, tripropylammonium tetra (phenyl)
Boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammoniumtetra ( 2,4-dimethylphenyl) boron, tributylammoniumtetra (3,5-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (o-tolyl) boron, Trialkyl-substituted ammonium salts such as tri (n-butyl) ammonium tetra (4-fluorophenyl) boron; N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N , N-2,4,6-pentame N, N-dialkylanilinium salts such as luanilinium tetra (phenyl) boron; dialkylammonium salts such as di (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron; triphenylphosphonium Examples include triarylphosphonium salts such as tetra (phenyl) boron, tri (methylphenyl) phosphoniumtetra (phenyl) boron, and tri (dimethylphenyl) phosphoniumtetra (phenyl) boron.

Examples of ionic compounds containing a boron atom include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate. Can also be mentioned. In addition, the following ionic compounds containing a boron atom can also be exemplified. (The counter ion in the ionic compounds listed below is, but not limited to, tri (n-butyl) ammonium.)

Salts of anions such as bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri ( n-
Butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate,
Bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carboundecaborate, tri (n-butyl) Ammonium
-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate and the like, and furthermore, the following borane compounds: And carborane compounds. These compounds are
Lewis acids are used as ionic compounds.

Examples of the borane compound, the carborane complex compound and the salt of the carborane anion include decaborane (14), 7,8-dicarboundecaborane (13), and 2,7-
Dicarboundecaborane (13), Undecahydride-
7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl) ammonium 6-carbadecaborate (1
4), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-dicarboundecabate Borate (12), bird (n-
Butyl) ammonium 2,9-dicarboundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarboundecaborate, tri (n-
Butyl) ammonium undecahydride 8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate And the like.

Examples of the carborane compound and the salt of the carborane include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), and 6,9-dicarbadecaborane (1).
4), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydrid-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-di Carbanonaborane and the like. Furthermore, the following compounds can also be exemplified. (The counter ion in the ionic compounds listed below is, but not limited to, tri (n-butyl) ammonium.)

Salts of metal carboranes and metal borane anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-dicarboundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarboundecaborate) cubate (cuprate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n- Butyl) ammonium bis (nonahydride-7,8-
Dimethyl-7,8-dicarboundecaborate) ferrate
(III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)
Chromate (chromate) (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-
Butyl) ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl)
Ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (IV), bis [Tri (n-butyl) ammonium] bis (undecahydride-7
-Carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV)
And the like.

The above compound [C] can be used in combination of two or more kinds. The organoaluminum compound [D] used in the present invention is, for example, a compound represented by the following general formula (a): R ¹¹ _n AlX _3-n ... (A) (where R ¹¹ is a hydrocarbon group having 1 to 12 carbon atoms) And X
Is a halogen atom or a hydrogen atom, and n is 1 to 3. ).

In the above formula (a), R ¹¹ has 1 to 1 carbon atoms.
2 hydrocarbon groups, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl Group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; isoprenylaluminum and the like. Alkenylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethyl aluminum Alkylaluminum sesquihalide such as Sukiburomido; methyl aluminum dichloride,
Examples thereof include alkylaluminum dihalides such as ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

[0084] Further, as the organoaluminum compound [D], the following formula _{^{(b): R 11 n AlY}} 3-n ··· (b) ( wherein, R ¹¹ is a R ¹¹ in the formula (a) the same, Y is, -OR ¹² group, -OSi R ¹³ ₃ group, -OAlR
¹⁴ ₂ group, -NR ¹⁵ ₂ group, -Si R ¹⁶ ₃ group or -N
(R ¹⁷ ) ₂ groups of AlR ¹⁸ , n is 1-2,
R ¹² , R ¹³ , R ¹⁴ and R ¹⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, A phenyl group, a trimethylsilyl group or the like, and R ¹⁶ and R ¹⁷ are a methyl group, an ethyl group, or the like. ) Can also be used.

Specific examples of such an organoaluminum compound include the following compounds. _{^{(i) R 11 n Al (}} OR 12) a compound represented by the _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and the like.

(Ii) R¹¹ _nAl (OSi R¹³ _Three)_3-nIndicated by
Compounds such as (C_TwoH_Five)_TwoAl (OSi (C
H_Three)_Three), (Iso-C_FourH₉)_TwoAl (OSi (C
H_Three)_Three), (Iso-C_FourH₉)_TwoAl (OSi (C_TwoH
_Five)_Three)etc. (iii) R¹¹ _nAl (OALR)¹⁴ _Two)_3-nCompound indicated by
Object, for example (C_TwoH_Five) _TwoAl (OAl (C
_TwoH_Five)_Two), (Iso-C_FourH₉)_TwoAl (OAl (iso-
C_FourH₉)_Two)etc.

(Iv) R¹¹ _nAl (NR^Fifteen _Two)_3-nIndicated by
Compound such as (CH_Three)_TwoAl (N (C
_TwoH_Five)_Two), (C_TwoH_Five)_TwoAl (NH (C
H_Three)), (CH_Three)_TwoAl (NH (C_TwoH_Five)),
(C_TwoH_Five)_TwoAl [N (Si (CH_Three)_Three)_Two],
(Iso-C_FourH₉)_TwoAl [N (Si (CH_Three)_Three)_Two]
etc. (v) R¹¹ _nAl (Si R¹⁶ _Three)_3-nA compound represented by
For example (iso-C_FourH₉) _TwoAl (Si (CH_Three)_Three)
etc.

Of these, R ¹¹ ₃ Al and R ¹¹ _n Al
(OR ¹²⁾ _3-n, can be mentioned organoaluminum compounds represented by _{^{R 11 n Al (OAlR 14 2}} ) 3-n Suitable examples, R ¹¹ is an isoalkyl group, compounds which are n = 2 Is particularly preferred. These organoaluminum compounds may be used in combination of two or more. The metallocene-based catalyst used in the present invention contains the metallocene compound [A] as described above. For example, it can be formed from the metallocene compound [A] and the organic aluminum oxy compound [B] as described above. it can. Further, it may be formed from a metallocene compound [A] and a compound (E) which forms an ion pair by reacting with the metallocene compound [A]. Further, together with the metallocene compound [A], an organic aluminum oxy compound [B] And a compound [C] which reacts with the metallocene compound [A] to form an ion pair. Also, in these embodiments,
It is particularly preferable to use an organic aluminum compound [D] in combination.

In the present invention, the metallocene compound [A] is
It is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of transition metal atoms, per liter of polymerization volume. The organoaluminum oxy compound [B] has an aluminum atom of usually about 1 to 1 mol of the transition metal atom.
It can be used in an amount such that it becomes 10 to 10,000 mol, preferably 10 to 5,000 mol.

The compound [C] which forms an ion pair by reacting with the metallocene compound [A] has a boron atom of usually about 0.5 to 20 mol, preferably 1 to 1 mol per mol of the transition metal atom. It is used in an amount to give 10 moles. Further, the organoaluminum compound [D] is usually used in an amount of about 0 to 1,000 mol per 1 mol of the aluminum atom in the organoaluminum oxy compound [B] or 1 mol of the boron atom in the compound [C] forming an ion pair. , Preferably about 0-5
It is used as needed in such an amount that it becomes 00 mol.

Using the metallocene catalyst as described above,
When ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene are copolymerized, a long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber having excellent polymerization activity (B) Can be obtained. Even when ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene are copolymerized using a Group 5 transition metal compound-based catalyst such as a vanadium-based catalyst, the copolymerization is performed with sufficient polymerization activity. Unable to get united rubber.

Further, when a Group 5 transition metal compound-based catalyst is used to produce, for example, ethylene / 1-butene / non-conjugated polyene copolymer rubber, ethylene / propylene / diene copolymer rubber (EPDM), etc. In many cases, the type of non-conjugated polyene is also limited to norbornene ring-containing polyenes such as 5-ethylidene-2-norbornene (ENB).

On the other hand, when a metallocene catalyst is used as in the present invention, the non-conjugated polyene is not limited to the norbornene ring-containing polyenes, but may be any of the various polyenes described above, for example, 7-methyl-1,6- Chain non-conjugated polyenes such as methyloctadiene (MOD) such as octadiene can also be copolymerized.

In the present invention, ethylene and C 3-20
When the α-olefin is copolymerized with a non-conjugated polyene, the metallocene compound [A], the organoaluminum oxy compound [B], the compound [C] forming an ion pair, which constitutes a metallocene-based catalyst, and The organoaluminum compound [D] may be separately supplied to the polymerization reactor, or a metallocene catalyst containing the metallocene compound [A] may be prepared in advance and then subjected to the copolymerization reaction.

In preparing the metallocene catalyst, a solvent which is inactive with the catalyst component can be used.
Specific examples of such an inert solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic rings such as cyclopentane, cyclohexane and methylcyclopentane. Aromatic hydrocarbons, benzene, toluene, aromatic hydrocarbons such as xylene, ethylene chloride, chlorobenzene,
Halogenated hydrocarbons such as dichloromethane can be used. These solvents can be used alone or in combination.

The metallocene compound [A], the organoaluminum oxy compound [B], the compound [C] forming an ion pair and the organoaluminum compound [D] are usually -1.
The mixed contact can be carried out at a temperature of from 00 to 200C, preferably from -70 to 100C. Copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene is usually performed at 40 to 200 ° C, preferably 50 to 150 ° C, particularly preferably 60 to 120 ° C, and at atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably be carried out under conditions of atmospheric pressure 30 kg / cm ^2.

This copolymerization reaction can be carried out by various polymerization methods, but is preferably carried out by solution polymerization. At this time, the above-mentioned solvent can be used as the polymerization solvent. The copolymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system, but is preferably performed by a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Further, the ethylene / α-
The olefin / non-conjugated polyene copolymer rubber (B) is obtained by the method described above, and the molecular weight of the copolymer rubber (B) is adjusted by changing polymerization conditions such as a polymerization temperature. It can also be controlled by controlling the amount of hydrogen (molecular weight regulator) used.

In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprises a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) 90 to 40 parts by weight, preferably 80 to 4 parts by weight, based on 100 parts by weight of
Used in a proportion of 5 parts by weight.

Other Components In addition to the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), the olefinic thermoplastic elastomer composition used in the present invention contains And / or an inorganic filler (D).

As the softener (C), a softener usually used for rubber can be used. Specifically, petroleum softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt and petrolatum; coal tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, and rapeseed oil , Oils such as soybean oil and coconut oil; tall oil; sub (factice);
Waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate and zinc laurate; naphthenic acid; pine oil, rosin or derivatives thereof; , Petroleum resin, atactic polypropylene, coumarone indene resin and other synthetic high molecular substances; dioctyl phthalate, dioctyl adipate,
Ester softeners such as dioctyl sebacate; and microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiochol, and hydrocarbon-based synthetic lubricating oils.

The softening agent (C) is used in an amount of usually 2 to 100 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). Parts, preferably 5 to 80 parts by weight. When the softening agent (C) is used in the above ratio, the obtained thermoplastic elastomer composition has excellent fluidity at the time of molding, does not lower the mechanical properties of the molded product, and has heat resistance and heat aging. The properties are also good.

Examples of the inorganic filler (D) include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, and sulfuric acid. Examples include calcium, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, and aluminum borate whisker.

These inorganic fillers (D) are composed of crystalline polyolefin resin (A) and ethylene / α-olefin /
Usually 2 to 100 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the total amount of the non-conjugated polyene copolymer rubber (B).
It is used in a proportion of 0 parts by weight. When the amount of the inorganic filler (D) is set as described above, the obtained thermoplastic elastomer composition has good rubber elasticity and moldability.

The olefin-based thermoplastic elastomer composition used in the present invention includes a crystalline polyolefin resin (A), an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), a softener (C) and an inorganic Filler (D)
Besides, polyisobutylene, butyl rubber, propylene
Other rubbers such as ethylene copolymer rubber, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber can be included. Specific examples of ethylene / propylene / non-conjugated diene copolymer rubber include:
Examples include an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber and an ethylene / propylene / dicyclopentadiene copolymer rubber. Among these other rubbers, polyisobutylene, butyl rubber, and propylene / ethylene copolymer rubber having a propylene content of 50 mol% or more are particularly preferable. These rubbers can be used alone or in combination of two or more.

In the present invention, when the above-mentioned other rubber is used, the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is 100%. It is used in a proportion of usually 2 to 200 parts by weight, preferably 5 to 150 parts by weight with respect to parts by weight.

Further, in the olefin-based thermoplastic elastomer composition used in the present invention, conventionally known heat-resistant stabilizers, anti-aging agents, weather-resistant stabilizers, antistatic agents, metal soaps, waxes and other lubricants are added. It can be added in a range that does not impair the object of the invention.

The olefin-based thermoplastic elastomer composition used in the present invention comprises the above-mentioned crystalline polyolefin resin (A), ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), if necessary. It is obtained by dynamically heat-treating and crosslinking the mixture with the softener (C) and / or the inorganic filler (D) to be blended in the presence of the following organic peroxide. Here, "dynamically heat-treating" means kneading in a molten state.

As the organic peroxide used in the present invention, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane , 2,5-dimethyl-2,5-di- (te
rt-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-chloro Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-
Butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like.

Among them, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di- ( (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene is preferred, and
2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane is most preferred.

[0111] Such an organic peroxide is used for the whole object to be treated, ie, the crystalline polyolefin resin (A),
α-olefin / non-conjugated polyene copolymer rubber (B) and, optionally, polyisobutylene, butyl rubber, a propylene / ethylene copolymer having a propylene content of 50 mol% or more, preferably 65 mol% or more Normally, 0.0
It is used in an amount of 2-3 parts by weight, preferably 0.05-1 part by weight. By setting the amount of the organic peroxide in the above range, an appropriate degree of crosslinking can be obtained, and sufficient heat resistance, tensile properties, elastic recovery, rebound resilience, and moldability can be obtained.

Further, a phenol resin can be used as the crosslinking agent. In this case, the amount of the phenol resin used is the whole of the object to be treated, that is, the crystalline polyolefin resin (A), the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), and if necessary, Usually 1 to 20 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of other rubbers such as polyisobutylene, butyl rubber, propylene content of 50 mol% or more, preferably 65 mol% or more of propylene / ethylene copolymer rubber. Is 2 to 15 parts by weight, more preferably 3 to 12 parts by weight.

In the present invention, sulfur, p-quinonedioxime, p, p '
-Peroxy crosslinking aids such as dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene , Triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
Polyfunctional methacrylate monomers such as trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using a compound as described above,
A uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, and is composed of a crystalline polyolefin resin (A) and ethylene.
It has good compatibility with the α-olefin / non-conjugated polyene copolymer rubber (B), has the effect of solubilizing the organic peroxide, and acts as a dispersant for the organic peroxide.
A thermoplastic elastomer composition having a uniform crosslinking effect by heat treatment and a good balance between fluidity and physical properties can be obtained.

The compound such as the above-mentioned crosslinking aid or polyfunctional vinyl monomer is used in an amount of usually not more than 2 parts by weight, preferably from 0.3 to 100 parts by weight, based on 100 parts by weight of the whole object to be treated.
It is used in an amount of 1 part by weight. In order to promote the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, Decomposition accelerators such as naphthenates such as manganese, magnesium, lead and mercury may be used.

The dynamic heat treatment in the present invention is preferably performed using a twin-screw extruder, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature of the heat treatment is 3 degrees from the melting point of the crystalline polyolefin resin (A).
It is in the range of 00 ° C, usually 150 to 280 ° C, preferably 170 to 270 ° C. The kneading time is usually 1 to 20
Minutes, preferably 1 to 10 minutes. The applied shearing force is 10 to 1 at the maximum shear rate received in the extruder.
00,000 sec ^-1 , usually 100 to 50,000 sec
c ^-1 , preferably 1,000 to 10,000 sec ^-1 ,
More preferably, it is in the range of 2,000 to 7,000 sec ^-1 . Further, the dynamic heat treatment in the present invention is represented by the following formula:

[0117]

5.5 <2.2 log X + log Y-log Z + (T-1
80) ÷ 100 <6.5 (where T is the resin temperature at the die exit of the extruder (° C)
X is the screw diameter (mm) of the extruder,
Y is the maximum shear rate (sec ^-1 ) experienced in the extruder, and Z is the throughput (kg / h). ). Here, the maximum shear rate (Y) received in the extruder is represented by the following equation:

[0118]

Y (sec ⁻¹ ) = [(screw diameter of extruder; X (mm)) × π × (number of screw rotations per second (rps))] / (barrel inner wall and kneading segment of screw) (Distance (mm) of the narrowest part of the clearance (gap) between the (kneading segments)).

According to the present invention, the crystalline polyolefin resin (A) and ethylene
A crosslinked olefin-based thermoplastic elastomer composition comprising an α-olefin / non-conjugated polyene copolymer rubber (B) is obtained. In the present invention, the term "crosslinked thermoplastic elastomer composition" means that the gel content measured by the following method is preferably 20% by weight or more, particularly preferably 45% by weight or more.

Method for measuring gel content: A 100 mg sample of the thermoplastic elastomer composition was sampled and 0.5 mm ×
A sample cut into 0.5 mm × 0.5 mm strips is immersed in 30 ml of cyclohexane at 23 ° C. for 48 hours in a closed container, and then the sample is taken out on a filter paper and kept at room temperature for 72 hours or more. Dry until dry. The value obtained by subtracting the weight of all the cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component and the weight of the crystalline polyolefin resin (A) in the sample before immersion in cyclohexane from the weight of the dried residue. As “corrected final weight (Y)”. On the other hand, the weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) in the sample is
This is referred to as “corrected initial weight (X)”. Here, the gel content is determined by the following equation.

[0121]

## EQU11 ## Gel content [% by weight] = [corrected final weight (Y) / corrected initial weight (X)] × 100 (automobile interior skin material) The automobile interior skin material of the present invention is as described above. The olefin-based thermoplastic elastomer composition obtained in the above manner is supplied to a plastic processing machine such as an extruder equipped with a T-die and a calendering machine and molded into a desired shape such as a sheet according to a conventional method. It is.

The automobile interior skin material thus obtained is made of the olefinic thermoplastic elastomer composition 10 described above.
0 parts by weight of the crystalline polyolefin resin 20 to 2
00 parts by weight. Examples of the crystalline polyolefin resin used here include the crystalline polyolefin resin used in the production of the olefin-based thermoplastic elastomer composition. In particular, low density polyethylene, linear low density polyethylene, polypropylene,
Polybutene-1, a crystalline ethylene / α-olefin copolymer (for example, ethylene / 4-methyl-1-pentene random copolymer) and the like are preferable.

The surface layer of the automotive interior skin material of the present invention may comprise a surface layer made of at least one compound selected from polyurethane, saturated polyester, acrylate resin, polyvinyl chloride and isocyanate resin. it can. As the saturated polyester used for forming such a surface layer, polyethylene terephthalate, polybutylene terephthalate and derivatives thereof are used. In addition, as the acrylate resin, polymethyl (meth) acrylate, polyisobutyl (meth) acrylate, poly-2-ethylhexyl (meth) acrylate, or the like is used. Further, as the isocyanate resin, polyhexamethylene diisocyanate, polyisophorone diisocyanate and the like are used.

It is preferable that such a surface layer has a thickness of 300 μm or less. A primer layer can be interposed between the skin layer and such a surface layer. Further, the automobile interior skin material of the present invention constitutes a laminate with a polyolefin foam. As the polyolefin used here,
The crystalline polyolefin resin used in the production of the olefin-based thermoplastic elastomer is exemplified. Particularly, polyethylene, polypropylene and the like are preferable.

Such a laminate is formed, for example, by extruding an olefin-based thermoplastic elastomer composition with an extruder equipped with a T-die, and extruding the extruded molten thermoplastic elastomer composition into a polyolefin foam sheet. It is manufactured by passing between a pair of rolls in a laminated state. The car interior skin material of the present invention is a door trim,
It is used as a skin layer of instrumental panels, ceilings, handles, console boxes, seats and the like.

[0126]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Production Example 1) Ethylene / 1-butene / 5-ethylidene-
Production of 2-norbornene copolymer rubber (B-1)

(1) Pre-contact of zirconium compound with methylalumoxane and preparation of catalyst solution A predetermined amount of zirconium compound (rac-dimethylsilylene-
Bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride) and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom) were allowed to stand in a dark place at room temperature for 30 minutes. The mixture was mixed by stirring to prepare a toluene solution in which the zirconium compound and methylalumoxane were dissolved.
The Zr concentration of this toluene solution is 0.004 mmol / m
1 and the concentration of methylalumoxane is 1.2 milligram atoms / ml in terms of aluminum atoms.

Next, hexane having a volume 5 times the volume of toluene was added to this toluene solution with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, and this was polymerized. Used as a reaction catalyst. Zr concentration: 0.00067 mmol / ml (= 0.67
(Mmol / liter) Methylalumoxane concentration (in terms of Al atom): 0.
20 mmol / ml (= 200 mmol / liter)

(2) Polymerization Using a 15-liter stainless steel polymerization vessel equipped with a stirring blade, ethylene, 1-butene and 5-ethylidene-2-norbornene (hereinafter also referred to as “ENB”) are continuously used. ) Was carried out in the presence of the polymerization reaction catalyst (1). First, 3.185 liters / hour of dehydrated and purified hexane, 0.67 liters / hour of the above-mentioned catalyst solution, and a hexane solution of triisobutylaluminum (concentration: 17 mmol / liter) at a rate of 0 hour / hour were introduced into the polymerization reactor from the top of the polymerization reactor. 0.3 liter and a 1.5 liter / hour ENB hexane solution (concentration 0.02 liter / liter) were continuously supplied.

Further, 200 liters / hour of ethylene and 155 liters / hour of 1-butene were continuously supplied from the upper part of the polymerization vessel into the polymerization vessel. This copolymerization reaction is
The reaction was performed at 80 ° C. and the average residence time was 1 hour (that is, 5 liters of polymerization scale). Next, a small amount of methanol was added to the polymerization solution taken out from the lower part of the polymerization vessel to stop the polymerization reaction, and the copolymer was separated from the solvent by steam stripping, and then subjected to the conditions of 100 ° C. and reduced pressure (100 mmHg). For 24 hours.

As described above, an ethylene / 1-butene / ENB copolymer rubber [copolymer rubber (B-1)] was obtained in an amount of 250 g / h. The obtained copolymer rubber (B
Physical properties of -1) are shown below.

(I) Molar ratio of units derived from ethylene to units derived from 1-butene (ethylene / 1-butene) 79/21 (ii) Iodine value based on ENB 13 (iii) In decalin at 135 ° C. Intrinsic viscosity [η] measured by
2.6 dl / g (iv) Intensity ratio of Tαβ to Tαα in D ¹³ C-NMR spectrum less than D0.01 (v) B value 1.1 (vi) Glass transition temperature (Tg) -5 determined by DSC
6 ° C (vii) gη ^* value 0.67

Example 1 Ethylene-1-butene-5-
Ethylidene-2-norbornene copolymer rubber (B-1)
65 parts by weight and propylene homopolymer (A-1) (M
35 parts by weight of FR10 (g / 10 minutes); the same applies hereinafter) into a Banbury mixer, and kneaded at 180 ° C. for 7 minutes.
The sheet was formed into a sheet through an open roll and cut with a sheet cutter to obtain square pellets. Then, an organic peroxide [2,5-dimethyl-2,5-di- (te
rt-butylperoxy) hexane] and 0.4 parts by weight of divinylbenzene (DVB) were mixed well in a Henschel mixer, and then fed to a twin-screw extruder to perform dynamic heat treatment. A plastic elastomer composition pellet was obtained.

Next, 80 parts by weight of the thermoplastic elastomer composition pellets and an ethylene-4-methyl-1-pentene random copolymer (ethylene content: 97 mol%, density: 0.920 g / cm ³ , MFR (190 ° C.) = 20g /
10 minutes) A mixture of 20 parts by weight of pellets is 65 mmφT
-Extruder with die (full flight screw, L / D =
26, using a coat hanger die) and extruding at 210 ° C., and a mixture of the extruded sheet-shaped thermoplastic elastomer composition and the ethylene / 4-methyl-1-pentene random copolymer in a molten state and crosslinked foaming of polyethylene. Body sheet [Sekisui Chemical Co., Ltd., trade name: Softlon,
The sheet was passed between a pair of rolls in a state of being laminated with an expansion ratio of 30 times and a thickness of 3 mm]. At this time, the thermoplastic elastomer sheet is brought into contact with the embossing roll side at a roll temperature of 90 ° C., and the crosslinked foam sheet is brought into contact with the mirror roll side at 30 ° C., and the skin layer has a thickness of 0.5 mm. Was manufactured.

Next, a coating liquid for forming a first primer layer comprising 10 parts by weight of chlorinated polypropylene, 2 parts by weight of silicic anhydride and 88 parts by weight of toluene was coated on the surface of the skin layer of the laminate sheet with a 120 mesh gravure roll. And dried at 70 ° C. for 20 seconds. A coating liquid for forming a second primer layer, comprising 8 parts by weight of polyvinyl chloride, 2 parts by weight of pigment and 90 parts by weight of methyl ethyl ketone, was subjected to cloud printing using a gravure roll, and dried again at 70 ° C. for 20 seconds.

Subsequently, 5 parts by weight of polyvinyl chloride, 5 parts by weight of an acrylate resin (polymethyl acrylate),
A coating liquid for forming a top coat layer composed of 3 parts by weight of silicic anhydride and 87 parts by weight of methyl ethyl ketone was applied once with a 100 mesh gravure roll, and dried again at 70 ° C. for 20 seconds. The thickness of the surface layer thus obtained is 8
μm.

Then, the sheet was subjected to a vacuum pressure forming machine CUPF-1115 manufactured by Fuse Vacuum Co., Ltd.
% Of the sheet surface temperature, 14 ° C, 14%
Vacuum forming was performed at 0 ° C. and 150 ° C. The molded article was evaluated for residual grain retention on a scale of 5 out of 5.

(Score) 5 points: The grain pattern hardly changed from that before molding. 4 points: The grain pattern is slightly thinner than before molding. 3 points: The grain pattern is slightly thinner than before molding. 2 points: The grain pattern is considerably thinner than before molding. 1 point: The grain pattern is very thin as compared to before molding, and is disappearing. The results are shown in Table 1.

(Example 2) Ethylene 1-butene-5-
Ethylidene-2-norbornene copolymer rubber (B-1)
55 parts by weight, 26 parts by weight of propylene homopolymer (A-1), an ethylene / 4-methyl-1-pentene random copolymer (ethylene content: 97 mol%, density: 0.920 g /
cm ³ , MFR (190 ° C.) = 20 g / 10 min) (C-
1) 19 parts by weight, mineral oil-based softener [paraffin-based process oil manufactured by Idemitsu Kosan Co., Ltd .: Diana Process P
W-380] (D-1) 28 parts by weight, organic peroxide [2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane] 0.27 parts by weight and divinylbenzene (DVB) 0 A sheet having a surface treated in the same manner as in Example 1 was prepared from 0.4 parts by weight, and vacuum-formed. Table 1 shows the results. (Comparative Examples 1 and 2) Sheets which had been subjected to surface treatment in the same manner as in Example 1 were produced using the raw materials and the compounding ratios shown in Table 1, and the vacuum moldability was measured. Table 1 shows the results.

[0140]

[Table 1]

Extruder A: Twin screw extruder, ZSK-5 from Werner & Freidel
3, screw diameter 53mm B: twin screw extruder, KTX-73 manufactured by Kobe Steel, screw diameter 73mm extruder set temperature A: C1 / C2 / C3 / C4 / C5 / D = 140/160/180 / 220/220/210 (° C) B: C1 / C2 / C3 / C4 / C5 / D = 150/170/190/230/230/210 (° C) Equation (1) in Table 1 is as follows: .

[0142]

5.5 <2.2 log X + log Y-log Z + (T-
180) ÷ 100 <6.5 (where T is the resin temperature (° C) at the die exit of the twin-screw extruder, and X is the screw diameter (m
m), Y is the maximum shear rate (sec ^-1 ) experienced in the twin screw extruder, and Z is the throughput (kg / h). )

[0143]

According to the present invention, it is possible to provide an automobile interior skin material excellent in vacuum formability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B29L 31:58 (72) Inventor Akira Uchiyama 3rd Chigusa Coast, Ichihara City, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72 ) Inventor Masaaki Kawasaki 3 Chigusa Kaigan, Ichihara-shi, Chiba F-term in Mitsui Chemicals, Inc. MB01 MG11 MG22 MH06 4J002 BB00W BB03W BB05W BB12W BB14W BB15X BB17W EK016 EK036 EK046 EK056 EK066 EK086 FD010 FD020 FD146 GN00

Claims (4)

[Claims] 1. A crystalline polyolefin resin (A)
60 to 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene (B) [(A) and (B) ) Is 100 parts by weight. And the ethylene / α-olefin /
A thermoplastic elastomer composition in which a non-conjugated polyene copolymer rubber (B) is cross-linked, wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is ethylene And α- having 3 to 20 carbon atoms
(1) (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms obtained by subjecting an olefin and a non-conjugated polyene to random copolymerization, in a ratio of 40/60. ~ 95/5 [(a) /
(B)], and (2) an iodine value of 1 to 50.
(3) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.0 to 10 dl / g, and the thermoplastic elastomer composition has the following formula: 5.5 < 2.2 log X + log Y-log Z + (T-18
0) ÷ 100 <6.5 (where T is the resin temperature at the die exit of the extruder (° C)
X is the screw diameter (mm) of the extruder,
Y is the maximum shear rate (sec ^-1 ) experienced in the extruder, and Z is the throughput (kg / h). A car interior skin material comprising an olefin-based thermoplastic elastomer composition, which is produced by dynamically heat-treating according to the conditions described in (1). 2. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) has (4) the intrinsic viscosity [η] measured in (3) and the intrinsic viscosity [η]. A linear ethylene / propylene copolymer having the same weight average molecular weight (by light scattering method) as the ethylene / α-olefin / non-conjugated polyene copolymer rubber and having an ethylene content of 70 mol% is measured in decalin at 135 ° C. that the intrinsic viscosity [η] ratio of the ^{_{bl ank [gη * (= [}} η] /
2. The automotive interior skin material according to claim 1, wherein [η] _blank )] is 0.2 to 0.95. 3. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) has an intensity ratio D (T (α) of Tαβ to Tαα in (5) ¹³ C-NMR spectrum.
αβ / Tαα) is 0.5 or less, and (6) ¹³ C-NM
R spectrum and the following formula: ## EQU2 ## B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is (a) in the random copolymer rubber. )
The molar fraction of units derived from ethylene, [P
_O ] is the mole fraction of the unit derived from (b) α-olefin in the random copolymer rubber, and [P _OE ] is α- to the total number of dyad chains in the random copolymer rubber. It is the ratio of the number of olefin / ethylene chains. ) Is from 1.00 to 1.50, and (7) the glass transition temperature (Tg) determined by DSC
The automotive interior skin material according to claim 2, wherein the temperature is -50C or less. 4. A crystalline polyolefin resin (A)
An ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising 60 parts by weight, ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, wherein ethylene and carbon number are present in the presence of a metallocene catalyst. (1) (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms, which is obtained by random copolymerization of an α-olefin having 3 to 20 and a non-conjugated polyene. And 40/60 to 95/5 [(a) / (b)]
(2) the iodine value is from 1 to 50,
(3) Ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having an intrinsic viscosity [η] of 1.0 to 10 dl / g measured in decalin at 135 ° C.
0 parts by weight [total of (A) and (B) is 100 parts by weight. And 5.5 <2.2 log X + log Y-log Z + (T-18)
0) ÷ 100 <6.5 (where T is the resin temperature at the die exit of the extruder (° C)
X is the screw diameter (mm) of the extruder,
Y is the maximum shear rate (sec ^-1 ) experienced in the extruder, and Z is the throughput (kg / h). A) dynamically producing an olefin-based thermoplastic elastomer composition by subjecting it to a heat treatment in the presence of a crosslinking agent in accordance with the conditions described in (1), and molding it into a desired shape; Method.