JP2001011120A - Production of olefinic thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefinic thermoplastic elastomer composition which has an excellent tensile strength, an excellent breaking elongation and excellent compression permanent set. SOLUTION: This method for producing an olefinic thermoplastic elastomer composition comprises dynamically thermally treating (A) 10 to 60 pts.wt. of a crystalline polyolefin resin and (B) 90 to 40 pts.wt. of an ethylene.α-olefin.non- conjugated polyethylene copolymer rubber comprising ethylene, a 3 to 20C α-olefin and a non-conjugated polyene [the total amount of (A) and (B) is 100 pts.wt.] in the presence of a crosslinking agent according to conditions expressed by the inequality: 5.5<2.2 log X+log Y-log Z+(T-180)÷100<6.5 [T is the temperature of the resin at the die exit of an extruder; X is the screw diameter (mm) of the extruder; Y is the maximum shear rate (see-1) received in the extruder; Z is an extruded amount (kg/h)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an olefin-based thermoplastic elastomer composition, and more particularly, to an olefin-based thermoplastic elastomer capable of providing a molded article excellent in tensile strength, elongation at break and compression set. The present invention relates to a method for producing an elastomer composition.

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are:
Since it is lightweight and easy to recycle, it is widely used as an energy-saving and resource-saving thermoplastic elastomer, particularly as a substitute for vulcanized rubber for automobile parts, industrial machine parts, electronic / electric equipment parts, building materials, and the like.

However, conventional olefin-based thermoplastic elastomers are inferior in vulcanized rubber in tensile strength, elongation at break, and compression set, and their improvement has been strongly demanded. As one of the olefinic thermoplastic elastomers having improved properties, a thermoplastic elastomer using an ethylene / α-olefin / non-conjugated polyene copolymer rubber polymerized with a metallocene catalyst has been proposed (Japanese Patent Application Laid-Open No. 9-1997). 012797).

[0004] However, such a thermoplastic elastomer has improved tensile strength, elongation at break and permanent compression set as compared with conventional thermoplastic elastomers,
It is still inferior to vulcanized rubber, and further improvement has been desired. The present inventors have studied to solve the above problems, and as a result, the crystalline polyolefin resin and the ethylene / α-olefin / non-conjugated polyene copolymer rubber have been dynamically adjusted in the presence of a crosslinking agent according to specific conditions. The present inventors have found that a thermoplastic elastomer composition having further excellent tensile strength, elongation at break and compression set can be obtained by heat treatment.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems associated with the prior art, and provides a thermoplastic elastomer composition having excellent tensile strength, elongation at break and compression set. The aim is to provide a way to do this.

[0006]

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. And the following equation:

[0007]

(Expression 2) 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). A method for producing an olefin-based thermoplastic elastomer composition, wherein the composition is dynamically heat-treated in the presence of a crosslinking agent according to the conditions described in (1).

(Ii) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is obtained by random copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. , (1) (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms by 40/60 to 95/5.
[(A) / (b)], (2) iodine value is 1 to 50, and (3) intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 0.1. The production method according to the above (i), which is 10 dl / g. (iii) The production method according to (i), wherein the crosslinking agent is an organic peroxide. (Iv) An olefin-based thermoplastic elastomer composition obtainable by the production method according to any one of (i) to (iii).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing an olefin-based thermoplastic elastomer composition according to the present invention comprises the steps of: preparing a polyolefin resin (A) in an amount of 10 to 60 parts by weight;
90 to 40 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) composed of 20 α-olefins and a non-conjugated polyene [the sum of (A) and (B) is 1
00 parts by weight. ] Is dynamically heat-treated in the presence of a crosslinking agent according to specific conditions.

Crystalline polyolefin resin (A) The crystalline polyolefin resin (A) used in the present invention is a crystalline polyolefin resin obtained by polymerizing one or more monoolefins by either a high-pressure method or a low-pressure method. Consists of a high molecular weight solid product. 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.

Regarding the polymerization mode, any type of polymerization mode can be adopted as long as a resinous material can be obtained, whether it is a random type or a block type. These crystalline polyolefin resins may be used alone or in combination of two or more. 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.

[0013] 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 a crystalline polyolefin resin (A) and ethylene α
-Used in an amount of 10 to 60 parts by weight, preferably 15 to 55 parts by weight, based on 100 parts by weight of the total amount of the olefin / non-conjugated polyene copolymer rubber (B). When the crystalline polyolefin resin (A) is used at the above ratio,
An olefin-based thermoplastic elastomer composition having excellent rubber elasticity and excellent moldability can be obtained.

Ethylene / α-olefin / non-conjugated polyether
Copolymer rubber (B) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention is obtained by the presence of a suitable catalyst such as a metallocene catalyst, a titanium nonmetallocene catalyst, and a vanadium catalyst. Below, it can be obtained by random copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) may have either a linear or long-chain branched molecular structure.

As the α-olefin having 3 to 20 carbon atoms, for example, 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, 12-ethyl-1-
And tetradecene, and combinations thereof.

Of these, α-α constituting the linear ethylene / α-olefin / non-conjugated polyene copolymer rubber
As the olefin, an α-olefin having 4 to 10 carbon atoms is preferable, and 1-butene, 1-hexene, 1-octene, 1-decene and the like are particularly preferably used. The α-olefin constituting the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber is preferably an α-olefin having 3 to 10 carbon atoms, particularly propylene, 1-butene, 1- Hexene, 1-octene and the like are preferably used. Linear ethylene, α-olefin,
Examples of the non-conjugated polyene constituting the non-conjugated polyene copolymer rubber include an aliphatic polyene, an alicyclic polyene, and an aromatic polyene.

Specific examples of the aliphatic polyene include 1,4-hexadiene, 1,5-hexadiene,
1,6-heptadiene, 1,6-octadiene, 1,7
-Octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 3-methyl-1,
4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-
1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,
4-dimethyl-1,5-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, 3-methyl- 1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6
Heptadiene, 4-methyl-1,6-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-1,8-decadiene, 8-ethyl-
Examples thereof include 1,8-decadiene, 6-methyl-1,6-undecadiene, and 9-methyl-1,8-undecadiene.

Examples of the alicyclic polyene include vinylcyclohexene, vinylnorbornene, ethylidene norbornene (for example, 5-ethylidene-2-norbornene), dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3
-Divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,
4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1
-Allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane and the like.

Further, specific examples of the aromatic polyene include divinylbenzene and vinylisopropenylbenzene. Among these, non-conjugated polyenes having 7 or more carbon atoms are preferred, for example, methyloctadiene such as 7-methyl-1,6-octadiene,
Ethylidene norbornene such as ethylidene-2-norbornene, dicyclopentadiene and the like are preferably used.
These non-conjugated polyenes can be used alone or in combination of two or more.

The non-conjugated polyene constituting the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber can be polymerized with a catalyst such as a metallocene catalyst among carbon-carbon double bonds. Non-conjugated polyene having only one carbon-carbon double bond in one molecule. 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 moiety having one unsaturated bond and a chain having an internal olefinic 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 linear ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) (hereinafter referred to as “copolymer rubber (B)”) preferably used in the present invention has the following properties. have. (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 4
0/60 to 90/10, more preferably 50/50 to 8
It is contained at a molar ratio of 5/15 [(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 1 to 30. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the copolymer rubber (B) measured in decalin at 135 ° C. is 0.1 to 10 dl / g, preferably 1.5 to 7 dl / g. is there. Jiita ^* value of (4) gη ^* value linear copolymer rubber (B) is greater than 0.95. This gη ^* value is defined by the following equation.

[0025]

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 exceeds 0.95, no long-chain branch is formed in the molecule, that is, it has a linear molecular structure. Indicates that Note that the value of gη ^* is
It can be measured by the method described in -14045. Furthermore, the linear 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 usually 0.8 or less, preferably 0.5 or less, particularly preferably 0.3 or less. The strength ratio D value 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
Is CH in the unit derived from each α-olefin.
₂ , which means two types of CH ₂ having different positions with respect to the tertiary carbon as shown below.

[0028]

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. The ¹³ C-NMR spectrum of this ethylene / 1-butene / 7-methyl-1,6-octadiene copolymer rubber is 39 to 40 pp.
The peak appearing at m is assigned to 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 rate of 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.

JP-A-9-12790, JP-A-9-1990
By copolymerizing ethylene, an α-olefin and a non-conjugated polyene by using a specific Group 4 (titanium group) metallocene catalyst described in 137001 or the like, the strength ratio D is 0.5 or less. A random copolymer rubber is obtained. (6) B value The copolymer rubber (B) has a ¹³ C-NMR spectrum and the following formula:

[0033]

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. The B value obtained from the above is usually 0.7 to 2.0, and particularly preferably 1.00 to 1.50.

The B value is an index indicating the distribution of ethylene and α-olefin in the copolymer rubber, and is indicated by JCRandall (Macromolecules, 15, 353 (1982)).
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. The composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00.

JP-A-9-12790, JP-A-9-1990
The B value is 1.00 to 1.50 by copolymerizing ethylene, an α-olefin, and a non-conjugated polyene using a specific Group 4 (titanium group) metallocene catalyst described in JP-A-137001. Is obtained.

(7) Glass Transition Temperature The glass transition temperature (Tg) of the copolymer rubber (B) measured by DSC (differential scanning calorimeter) is usually -40 ° C. or lower, particularly -50 ° C. or lower. Desirably. on the other hand,
The long-chain branched copolymer rubber (B) preferably used in the present invention has the following properties.

(1) Ethylene / α-Olefin Component Ratio The copolymer rubber (B) comprises (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)].

(2) Iodine value The copolymer rubber (B) has an iodine value 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.

[0040] 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 above equation. 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.
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 usually 0.8 or less, preferably 0.5 or less, particularly preferably 0.3 or less. (6) B value The above-mentioned B value of the copolymer rubber (B) is usually 0.7 to
2.0, particularly preferably 1.00 to 1.50. (7) Glass transition temperature The glass transition temperature (Tg) of the copolymer rubber (B) measured by DSC (differential scanning calorimeter) is usually -40 ° C or lower, particularly -50 ° C or lower. desirable.

The above-mentioned linear or long-chain branched copolymer rubber (B) can be prepared by reacting ethylene with ethylene in the presence of a suitable catalyst such as a metallocene catalyst, a titanium nonmetallocene catalyst, or a vanadium catalyst. It is produced by randomly copolymerizing an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. Examples of the metallocene-based catalyst include, for example, JP-A No. 9-1.
2790 and JP-A-9-137001.

The metallocene catalyst is not particularly limited except that it contains the metallocene compound [A]. For example, the metallocene compound [A] reacts with the organic aluminum oxy compound [B] and / or the metallocene compound [A]. To form an ion pair. 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. As the metallocene compound [A], the following general formula (I):

[0044]

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 usually an aryl group having 6 to 16 carbon atoms when the target copolymer rubber (B) is a long-chain branched type. The aryl group may be substituted with, for example, the halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and / or an organic silyl group. 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,
Examples include 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.

R ³ is usually a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a carbon number when the target copolymer rubber (B) is linear. 1
To 20 halogenated aliphatic hydrocarbon groups. Here, the halogen atom is fluorine, chlorine, bromine, iodine, and examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, Alkyl groups such as an octyl group, a nonyl group, a dodecyl group, an eicosyl group and the like, a vinyl group, a propenyl group and the like, and examples of the halogenated aliphatic hydrocarbon group having 1 to 20 carbon atoms include a chloromethyl group. And a halogenated alkyl group such as a trifluoromethyl group.

X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, the halogen atom, or a C 1-20 hydrocarbon group which may be substituted with the halogen atom, Or sulfur-containing groups. Examples of the oxygen-containing group include an alkoxy group having 1 to 20 carbon atoms such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthoxy group. And aryl-C _1-20 -alkoxy groups such as a phenylmethoxy group and a phenylethoxy group.

Specific examples of the sulfur-containing group include a substituent in which oxygen in the oxygen-containing group is replaced with sulfur; a methylsulfonyloxy group, a trifluoromethanesulfonyloxy group, a phenylsulfonyloxy group, a benzylsulfonyloxy group, a p-type group. -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.

Among 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. Among the metallocene compounds represented by the general formula (I), compounds in which R ³ is an aryl group having 6 to 16 carbon atoms include, for example,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride. Further, among the metallocene compounds represented by the general formula (I), compounds in which R ³ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms include, for example, rac-dimethylsilylene-
Bis (2-ethyl-4-isopropyl-7-methyl-1
-Indenyl) zirconium dichloride.

As the metallocene compound, a racemate is usually used as a catalyst component, but an R type or an S type can also be used. The organoaluminum oxy compound [B] used for the preparation of the metallocene catalyst may be a conventionally known aluminoxane.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-8687.

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.

The organoaluminum compound [D] may be, for example, a compound represented by the following general formula (a): R ¹¹ _n AlX _3-n (a) wherein R ¹¹ is a hydrocarbon group having 1 to 12 carbon atoms. Yes, X
Is a halogen atom or a hydrogen atom, and n is 1 to 3. ), Or the following general formula _{^{(b): R 11 n AlY}} 3-n ··· (b) ( wherein, R ¹¹ is the formula (a) is the same as R ¹¹ in, 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 be used.

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 linear or long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer having excellent polymerization activity is obtained. Rubber (B) can be obtained. The catalyst for producing the copolymer rubber (B) is not limited to the above-described metallocene-based catalyst, but may be other metallocene-based catalysts, group V transition metal compound-based catalysts such as vanadium catalysts, and titanium-based non-metallic catalysts. A metallocene catalyst or the like may be used.

As the vanadium catalyst, for example, JP-A-6
4-54010, specifically VOC
l ₂ (OC ₂ H ₅ ) and VOCl _3, which may be used in combination with an organoaluminum compound such as dialkylaluminum halide (eg, diethylaluminum chloride). Examples of the titanium-based nonmetallocene-based catalyst include a catalyst described in JP-A-2-84404.

The copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene is usually carried out in a range of 40 to 20.
0 ° C, preferably 50 to 150 ° C, particularly preferably 60 ° C.
At to 120 ° C., atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably atmospheric pressure 30 kg /
cm ² can be performed. This copolymerization reaction is
It 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 carried out in any of a batch system, a semi-continuous system and a continuous system, but is preferably carried out in a continuous system. Further, the polymerization was carried out by changing the reaction conditions.
It can also be performed in multiple stages. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention can be obtained by the method described above. The molecular weight of the copolymer rubber (B) is determined by the polymerization temperature or the like. Can be adjusted by changing the polymerization conditions, and can also be adjusted by controlling the amount of hydrogen (molecular weight modifier) 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 the present invention, in addition to the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), the olefin-based thermoplastic elastomer composition contains necessary components. Optionally, a softener (C) and / or an inorganic filler (D) can be included.

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 usually used in an amount of 2 to 100 parts by weight based on 100 parts by weight of the total of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). , Preferably 2
Used in a proportion of 50 parts by weight.

In the present invention, the olefin-based thermoplastic elastomer composition contains a crystalline polyolefin resin (A), an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), a softener (C), and an inorganic filler. Agent (D)
Besides, polyisobutylene, butyl rubber, propylene
Other rubbers, such as ethylene copolymer rubber, ethylene / propylene copolymer rubber, can be included. These rubbers can be used alone or in combination of two or more.

In the present invention, when the other rubber as described above 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, conventionally known heat stabilizers, anti-aging agents, weather stabilizers, antistatic agents, metal soaps, lubricants such as wax, etc., within a range that does not impair the object of the present invention. Can be added.

In the present invention, the olefin-based thermoplastic elastomer composition is blended with the above-mentioned crystalline polyolefin resin (A) and ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), if necessary. A mixture with the softener (C) and / or the inorganic filler (D) to be used,
It is obtained by dynamically heat-treating and crosslinking in the presence of a crosslinking agent, preferably an organic peroxide as described below. 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.

Such an organic peroxide is used for the whole object to be treated, ie, the crystalline polyolefin resin (A),
Based on 100 parts by weight of the total amount of the α-olefin / non-conjugated polyene copolymer rubber (B) and other rubbers such as polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber, etc. , Usually 0.02 to 3 parts by weight, preferably 0.05 to 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 phenolic 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, Polyisobutylene, butyl rubber, propylene · ethylene copolymer rubber and other rubber total amount of 100 parts by weight,
It is usually 1 to 20 parts by weight, preferably 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 the 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 above-mentioned compound such as a crosslinking aid or a polyfunctional vinyl monomer is used in an amount of usually not more than 2 parts by weight, preferably 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:

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:

[0078]

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

The crystalline polyolefin resin (A) and the ethylene / α-olefin /
A crosslinked olefin-based thermoplastic elastomer composition comprising the non-conjugated polyene copolymer rubber (B) is obtained. In the present invention, in particular, an olefin excellent in tensile strength, elongation at break, and compression set, which are important properties as a thermoplastic elastomer composition, is obtained by dynamically heat-treating according to the specific conditions represented by the above formula. A thermoplastic elastomer composition is obtained.

In the present invention, the fact that the thermoplastic elastomer composition is crosslinked means that the gel content measured by the following method is preferably 20% by weight or more, particularly preferably 4% by weight or more.
It means that it is in the range of 5% by weight or more. Measurement method of gel content: 100 mg of a sample of the thermoplastic elastomer composition was collected, and 0.5 mm × 0.5 mm ×
A sample cut into 0.5 mm strips was placed in a closed container in 3
After immersing in 0 ml of cyclohexane at 23 ° C. for 48 hours, the sample is taken out on a filter paper and dried at room temperature for at least 72 hours until a constant weight is obtained. 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 referred to as “corrected initial weight (X)”. Where the gel content is
It is obtained by the following equation.

## EQU7 ## Gel content [% by weight] = [corrected final weight (Y) / corrected initial weight (X)] × 100

[0082]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of the physical property performed about the olefin-type thermoplastic elastomer composition of an Example and a comparative example is as follows.

[Measurement Method of Physical Properties] (1) Tensile strength: 200 in accordance with JIS K6301
The tensile strength at break was measured at a tensile speed of mm / min (unit: kg / cm ² ). (2) Elongation at break: 200 in accordance with JIS K6301
The elongation at break was measured at a tensile speed of mm / min (unit:%). (3) Compression set: 25 in accordance with JIS K6301
% Compression, strain at 70 ° C. for 22 hours (unit:
%).

(Production Example 1) Ethylene / 1-butene / 5-
Ethylidene-2-norbornene copolymer rubber (B-1)
(1) Pre-contact of zirconium compound with methylalumoxane and preparation of catalyst solution 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.

Then, to this toluene solution, 5 times the volume of hexane with respect to toluene was added under 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”). ) 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) were introduced from the upper part of the reactor into the reactor. , And a hexane solution of ENB (concentration 0.02 L / L) was continuously supplied at a rate of 1.5 L / hour.

Further, 200 l / h of ethylene and 155 l / h of 1-butene were continuously supplied from the upper part of the polymerization reactor into the polymerization reactor. 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 withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction.
After the copolymer was separated from the solvent by steam stripping, the copolymer was treated under reduced pressure (100 mmHg) at 100 ° C.
Dried for 4 hours. As described above, ethylene / 1-butene / ENB copolymer rubber [copolymer rubber (B-1)]
Was obtained in an amount of 250 g per hour. The properties of the obtained copolymer rubber (B-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

(Production Example 2) Ethylene 1-butene-5-
Ethylidene-2-norbornene copolymer rubber (B-2)
The zirconium compound (rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-) used in Production Example 1 (1) was used.
Indenyl) zirconium dichloride) was converted to rac-dimethylsilylene-bis (2-ethyl-4-isopropyl-7-).
An ethylene / 1-butene / ENB copolymer rubber [copolymer rubber (B-2)] was obtained in the same manner as in Production Example 1 except that methyl-1-indenyl) zirconium dichloride was used instead. The physical properties of the copolymer rubber (B-2) obtained 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 10 (iii) In decalin at 135 ° C. Intrinsic viscosity [η] measured by
2.7 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 0.98

(Production Example 3) Ethylene / propylene / 5-
Production of vinyl-2-norbornene copolymer rubber (B-3) Ethylene and propylene were continuously produced using a 100-liter substantial internal volume stainless steel polymerization vessel (stirring rotation speed: 250 rpm) equipped with stirring blades. And 5-vinyl-2-norbornene.

That is, 60 liters / hour of dehydrated and purified hexane and 3.6 hours / hour of ethylene were added to the liquid phase from the side of the polymerization reactor.
kg, propylene 3.0 kg / h, 5-vinyl-2-
Norbornene at a rate of 320 g / h, hydrogen at 40 l / h, and (a) VOCl ₃ at a rate of 32
Mmol, (b) diethylaluminum chloride (Al
(Et) ₂ Cl) 160 mmol / h, Al (Et)
_1.5 Cl _1.5 was continuously fed at a rate of 32 mmol / h. The copolymerization reaction was performed at 40 ° C.

When the copolymerization reaction was carried out under the above conditions, an ethylene / propylene / 5-vinyl-2-norbornene copolymer was obtained in a uniform solution state. Next, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the copolymer was separated from the solvent by a steam stripping treatment. Dried for hours.

The physical properties of the copolymer rubber (B-3) obtained as described above are shown below. (I) Molar ratio between units derived from ethylene and units derived from propylene (ethylene / propylene) 75/2
5 (ii) Iodine value based on 5-vinyl-2-norbornene 8.5 (iii) Intrinsic viscosity [η] measured in decalin at 135 ° C
2.81 dl / g (iv) Intensity ratio of Tαβ to Tαα in D ¹³ C-NMR spectrum less than D0.01 (v) B value 1.0 (vi) Glass transition temperature (Tg) -5 determined by DSC
3 ° C (vii) gη ^* value 0.81

(Production Example 4) Ethylene propylene 5-
Ethylidene-2-norbornene copolymer rubber (B-4)
Using a known vanadium catalyst (VOCl ₂ (OC ₂ H ₅ )), ethylene, propylene and 5-ethylidene-
Copolymerization with 2-norbornene was performed. The physical properties of the obtained copolymer rubber (B-4) are shown below. (I) Molar ratio of units derived from ethylene to units derived from propylene (ethylene / propylene) 79/2
1 (ii) Iodine value based on ENB 13 (iii) Intrinsic viscosity [η] measured in decalin at 135 ° C
2.7 dl / g (iv) Intensity ratio of Tαβ to Tαα in D ¹³ C-NMR spectrum less than D0.01 (v) B value 1.0 (vi) Glass transition temperature (Tg) -5 determined by DSC
1 ° C (vii) gη ^* value 0.97

Example 1 Ethylene / 1-butene / 5-
Ethylidene-2-norbornene copolymer rubber (B-1)
45 parts by weight, propylene homopolymer (A-1) (MF
30 parts by weight of R10 (g / 10 minutes)) and 25 parts by weight of a mineral oil-based softener [paraffin-based process oil manufactured by Idemitsu Kosan Co., Ltd .: Diana Process PW-380] (C-1) are charged into a Banbury mixer. After kneading at 180 ° C. for 7 minutes, the mixture was formed into a sheet through an open roll and cut with a sheet cutter to obtain square pellets. Next, an organic peroxide [2,5-dimethyl-2,5-
0.27 parts by weight of di- (tert-butylperoxy) hexane] and 0.4 parts by weight of divinylbenzene (DVB) were added, mixed well in a Henschel mixer, and fed to a twin-screw extruder under the following conditions. A dynamic heat treatment was performed to obtain a thermoplastic elastomer composition pellet.

Dynamic heat treatment conditions Extruder: ZSK-53 manufactured by Werner & Freidel, screw diameter 53 mm Temperature setting: C1 / C2 / C3 / C4 / C5 / D = 140/160/180/220/220/200
(° C) Maximum shear rate: 2800 (sec ^-1 ) Extrusion amount: 50 (kg / h) Resin temperature at die exit: 238 (° C) Then, a predetermined test piece is prepared by injection molding using the pellet. And its physical properties were measured according to the above-mentioned measuring methods.

A single screw extruder (screw diameter: 50 mm; L / D = 30, CR = 3.2) manufactured by Toshiba Machine Co., Ltd. and AST
The appearance of the extruded product was evaluated using an M-Garbe die. (C1 / C2 / C3 / C4 / C5 / D = 160/180/200/210/210/200 (℃),
Screw rotation 30rpm)

Evaluation criteria for the appearance of the extruded product: 押出: The skin of the extruded product is smooth. Δ: The skin of the extruded product was slightly rough. ×: The skin of the extruded product is rough. Table 1 shows the results. (Examples 2 to 4, Comparative Examples 1 to 8) A thermoplastic elastomer composition was prepared in the same manner as in Example 1 using the raw materials and the compounding ratios shown in Table 1, the physical properties were measured, and the appearance of the extruded product was evaluated. . Table 1 shows the results.

[0102]

[Table 1]

The equation (1) in Table 1 is as follows.

5.5 <2.2 log X + log Y-log Z + (T-18
0) ÷ 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). )

[0104]

According to the present invention, it is possible to provide an olefin-based thermoplastic elastomer composition which is more excellent in tensile strength, elongation at break and compression set than conventional olefin-based thermoplastic elastomers.

Continuation of the front page F term (reference) 4F070 AA04 AA12 AA13 AA15 AA16 AA40 AC56 AE08 GA05 GA06 GB02 GB08 4J002 BB041 BB052 BB142 BB151 BB172 CC033 EK036 EK046 EK056 EK066 EK086 FD010 AFDAAQA FD020 FD143 A08A15A08 AB16R AR16R AR21R AR22R AS11R AS13R AS15R AS25R BB01R BC02R BC03R BC04R CA05 DA09 DA31

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 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). A method for producing an olefin-based thermoplastic elastomer composition, wherein the composition is dynamically heat-treated in the presence of a crosslinking agent according to the conditions described in (1). 2. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is composed of ethylene and C3 to C3.
(1) (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms, obtained by random copolymerization of an α-olefin and a non-conjugated polyene. , 40 / 60-95 / 5
[(A) / (b)], (2) iodine value is 1 to 50, and (3) intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 0.1. The production method according to claim 1, wherein the amount is 10 dl / g. 3. The method according to claim 1, wherein the crosslinking agent is an organic peroxide. 4. An olefin-based thermoplastic elastomer composition obtainable by the production method according to claim 1.