JPH08208903A - Crosslinked thermoplastic elastomer composition and its production - Google Patents

Abstract

PURPOSE: To inexpensively produce a crosslinked thermoplastic elastomer composition excellent in heat resistance and mechanical strength without using a crosslinking agent such as an organic peroxide. CONSTITUTION: This crosslinked thermoplastic elastomer composition comprises 65-95 pts.wt. polypropylene resin (A) having a molecular weight distribution Mw/Mn of 4.0 or below as determined by GPC and 35-5 pts.wt. partially crosslinked olefin copolymer elastomer (B) and satisfies the relationship: X>=0.1×WB (wherein X is the rate of o-xylene insolubles, and WB is the content of component B). This composition is produced by forming component A in the presence of a catalyst comprising a group IVA-VIA transition metal compound having at least one cyclopentadienyl skeleton and an aluminoxane or noncoordinated anion-containing compound and copolymerizing a nonconjugated polyene with an α-olefin without adding any fresh catalyst in the presence of component A to form component B.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a crosslinkable thermoplastic elastomer composition and a method for producing the same. More specifically, the present invention provides a crosslinkable thermoplastic elastomer composition comprising a specific polypropylene resin and a specific partially crosslinked olefin elastomer component, which is flexible and has excellent heat resistance and tensile strength, and an inexpensive method for producing the same.

[0002]

2. Description of the Related Art Olefinic thermoplastic elastomers are generally classified into a cross-linking type and a non-crosslinking type. The non-crosslinking type thermoplastic elastomer is easy to manufacture because it does not involve a crosslinking reaction and the manufacturing cost is low, but it is inferior to the crosslinking type thermoplastic elastomer in strength, heat resistance and permanent elongation. The crosslinkable thermoplastic elastomer is generally obtained by dynamically heat-treating a crystalline polyolefin such as polypropylene and an olefin elastomer component in the presence of an organic peroxide. Such a cross-linking type thermoplastic elastomer has advantages such as excellent mechanical strength, heat resistance and elastic recovery property as compared with the non-cross-linking type thermoplastic elastomer. However, on the other hand, since a crosslinking agent such as an organic peroxide is used for the production, the production cost is high and the production is complicated. Regarding the non-crosslinked and crosslinked olefinic thermoplastic elastomers, for example, Japanese Patent Publication No. 53-21.
021, JP-B-55-18448, JP-B-58-461
38, Japanese Patent Publication No. 62-938, Japanese Patent Publication No. 62-59139 and the like.

[0003]

Under such circumstances, a crosslinkable thermoplastic elastomer having excellent strength, heat resistance and the like can be obtained without performing a crosslinking step with a crosslinking agent like a non-crosslinkable thermoplastic elastomer. Is desired. An object of the present invention is to provide a crosslinkable thermoplastic elastomer having good tensile strength and heat resistance, which can be easily produced without a crosslinking step with a crosslinking agent.

[0004]

SUMMARY OF THE INVENTION The present invention comprises a component A) having a molecular weight distribution Mw / Mn by gel permeation chromatography of 4.0 or less and 20% by weight or less of ethylene and / or α-olefin copolymerized. A composition comprising 20 or more and less than 65 parts by weight of a polypropylene resin which may be added, and component B) more than 35 parts by weight and not more than 80 parts by weight of a partially cross-linked olefin copolymer elastomer, wherein: The ratio X of the component insoluble in boiling o-xylene and the content ratio W _B of the component B) satisfy the following formula (X and W _B are both weight%): X ≧ 0.1 × W _B It is a crosslinkable thermoplastic elastomer composition.

Further, in the composition comprising the components A) and B), the component soluble in room temperature o-xylene has a) a CSD value defined by the following formula of 3.0 or less, and CSD = [(0.5 Aδδ + 0.25 Aγδ + 0.5Aβδ) × Aα
α] / [0.5 (Aαγ + Aαδ)] ² where Aδδ, Aγδ, Aβδ, Aαδ, Aαα, A
αγ is the following peak derived from a methylene group in ¹³ C-NMR: Sδδ, Sγδ, Sβδ, Sαδ,
These are the integrated intensities of Sαα and Sαγ. b) two adjacent 3's in the ¹³ C-NMR spectrum
Signal S derived from two methylene groups between primary carbon atoms
The polypropylene resin composition is characterized in that the strength ratio Aαβ / Aαα of αβ and Sαα satisfies the condition of 0.5 or less.

Further, the present invention is the above composition, wherein the melting point Tm of the above component A) measured by a differential scanning calorimeter is 115 ° C. or higher, which is a crosslinkable thermoplastic elastomer composition. . Further, 1 part of the softener is added to 100 parts by weight of the above components A) and B).
It is a crosslinked thermoplastic elastomer composition characterized in that it is compounded in a range of 50 parts by weight or less and has a Shore hardness D value of 70 or less.

Further, in producing the above-mentioned crosslinkable thermoplastic elastomer composition, (a) a transition metal compound of Group 4A to 6A of the periodic table having at least one cyclopentadienyl skeleton and (b) an aluminoxane. Alternatively, after the component A) is produced by a catalyst comprising a non-coordinating anion-containing compound, the non-conjugated polyene and the α-olefin are copolymerized in the presence of the component A) without newly adding a catalyst. The method for producing a crosslinked thermoplastic elastomer composition is characterized by comprising the step of producing component B) according to

The present invention will be described in detail below. The component A) polypropylene resin in the crosslinked thermoplastic elastomer composition of the present invention may be a homopolymer of propylene or a copolymer of propylene and other α-olefin. The α-olefin is ethylene and one having 4 to 20 carbon atoms, and specifically, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl. Examples include -1-pentene and 4-methyl-1-pentene. Among these, ethylene, 1-butene and 1-hexene are preferable. The content of these α-olefins is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less. When the content of α-olefin exceeds 20% by weight, heat resistance is lowered, which is not preferable.

In the crosslinkable thermoplastic elastomer composition of the present invention, the value of the molecular weight distribution M _w / M _n of the component A) by gel permeation chromatography is 4.0.
It is desirable that it is below, more preferably 3.2 or below, and most preferably 2.7 or below. When the value of the molecular weight distribution M _w / M _n exceeds 4.0, heat resistance is lowered due to the presence of the low molecular weight component, and problems such as stickiness occur. When the value of the molecular weight distribution M _w / M _n is 2.7 or less, the heat resistance becomes the best. Conventionally, in order to produce a polypropylene resin having such a molecular weight distribution, a method of heat treating the polypropylene resin together with an organic peroxide has been performed. However, such a method often causes problems such as a decrease in impact resistance due to molecular cleavage of polypropylene resin, coloring due to a decomposed product of an organic peroxide, and generation of odor. On the other hand, with the polypropylene-based resin component A) of the present invention, a value of molecular weight distribution M _w / M _{n of} 4.0 or less can be achieved without the above-mentioned problems, as described later.

In the crosslinkable thermoplastic elastomer composition of the present invention, from the viewpoint of heat resistance, the melting point Tm of the component A) is
Is preferably 115 ° C. or higher. Preferred melting point T
m is more preferably 120 ° C. or higher, and most preferably 130 ° C. or higher. When Tm is 130 ° C. or higher, the heat resistance is the best.

Component A) having a melting point suitable for the purpose can be achieved by adjusting the content of ethylene and / or α-olefin in the component. It is also possible by selecting the production conditions of the component A), for example, selecting an appropriate polymerization temperature.

The partially crosslinked olefinic copolymer elastomer component B) in the present invention contains an α-olefin and a non-conjugated polyene as constituent components. Here, the non-conjugated polyene is an essential component for forming the crosslinking component in component B).

As the α-olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-
Octene, 3-methyl-1-pentene, 4-methyl-1
-Pentene, 1-decene and the like, and two or more of these may be used in combination. Among these, those selected from ethylene, propylene, 1-butene, 1-hexene and 1-octene are preferable. From the viewpoint of flexibility, it is particularly preferable to use ethylene in combination with at least one selected from propylene, 1-butene, 1-hexene and 1-octene. In this case, the ethylene content is more than 20 parts by weight and 85 parts by weight or less, preferably 30 parts by weight or more and 80 parts by weight or less, further preferably 40 parts by weight.
It is from 70 parts by weight to 70 parts by weight. Ethylene content is 2
If it is 0 parts by weight or less and exceeds 85 parts by weight, the flexibility as an elastomer will be impaired. Component B)
The sum of the content of the non-conjugated polyene and the content of the α-olefin containing ethylene is 100 parts by weight.

The non-conjugated polyene is represented by the following formula,

Embedded image In the above formula, R ^a , R ^b , R ^c , and R ^d are a hydrogen atom or an alkyl group or aryl group having a carbon number of 1 to 20, which may be linear or branched. Further, these may be different from each other or may be the same. R ^e is a hydrocarbon group having 1 or more carbon atoms and may be linear or branched.

Specific examples of these non-conjugated polyenes include 1,4-pentadiene, 1,4-hexadiene and 1,5
-Hexadiene, 1,4-heptadiene, 2,5-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 1,4-octadiene, 2,5-octadiene,
1,5-octadiene, 2,6-octadiene, 1,6
-Octadiene, 1,7-octadiene, 1,4-nonadiene, 1,5-nonadiene, 2,5-nonadiene,
1,6-nonadiene, 1,7-nonadiene, 1,8-nonadiene, 2,6-nonadiene, 2,7-nonadiene,
1,9-decadiene, 1,13-tetradecadiene, 3
-Methyl-1,4-pentadiene, 4-methyl-1,5
-Hexadiene, 3-methyl 1,5-hexadiene and the like. Among these, for improving heat resistance and tensile strength,
Those in which R ^a is hydrogen are preferred, and R is particularly preferred.
^{This is the case where a} , R ^b , R ^c , and R ^d are all hydrogen atoms.
Specific examples of such compounds include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,
1,7-octadiene, 1,8-nonadiene, 1,9-
Decadiene, 1,13-tetradecadiene, 3-methyl-1,4-pentadiene, 4-methyl-1,5-hexadiene, 3-methyl-1,5-hexadiene and the like are mentioned, and particularly preferred is 1,4. -Pentadiene, 1,5
-Hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene.

The content of these non-conjugated polyenes in component B) is in the range of 0.01-40 parts by weight, preferably 0.1-20 parts by weight, more preferably 0.5-.
10 parts by weight. Content of non-conjugated polyene is 0.01
If it is less than part by weight, the cross-linking component is not effectively formed and heat resistance and tensile strength are lowered. Even if it exceeds 40 parts by weight, there is no further effect on the formation of the cross-linking component, and the manufacturing cost becomes high.

In the crosslinked thermoplastic elastomer composition of the present invention, the content ratio X of the component insoluble in boiling o-xylene is X.
And the content ratio W _B of the component B) satisfy the following relationship (X,
W _B is expressed in% by weight). X ≧ 0.1 × W _{B If} X and W _B do not satisfy this relationship, the heat resistance and tensile strength of the crosslinked thermoplastic elastomer composition will be reduced. From this point of view, X and W _B preferably satisfy the relationship of X ≧ 0.2 × W _B , and more preferably X ≧ 0.3 × W _B. X ≧ 0.3
Most heat resistance and tensile strength is improved in the case of satisfying the relationship × W _B.

In the present invention, the constituent ratio of the component A) and the component B) is such that the component B) is more than 35 parts by weight and 80 parts by weight or less in 100 parts by weight in total of the components A) and B). is there.
If the amount of component B) is 35 parts by weight or less, the flexibility becomes insufficient.
If the amount of component B) exceeds 80 parts by weight, the heat resistance will decrease. From this point of view, the preferred range of component B) is 45 parts by weight or more and 75 parts by weight or less, more preferably 50 parts by weight or more and 70 parts by weight or less, and in this range, the balance between heat resistance and flexibility is the best. Becomes

The room temperature o-xylene soluble component in the polypropylene resin composition of the present invention preferably has a CSD value defined by the following formula of 3.0 or less. CSD = [(0.5 Aδδ + 0.25 Aγδ + 0.5Aβδ) × Aα
α] / [0.5 (Aαγ + Aαδ)] ² where Aδδ, Aγδ, Aβδ, Aαδ, Aαα, A
αγ is the following peak derived from a methylene group in the ¹³ C-NMR spectrum: Sδδ, Sγδ, Sβ
δ, Sαδ, Sαα, Sαγ, and the respective integrated intensities. As an example of the ¹³ C-NMR spectrum showing such a peak, FIG. 1 shows the ¹³ C-NMR spectrum of an ethylene-propylene copolymer elastomer produced by a catalyst containing titanium as a main component (FIG. 1 shows the present invention. However, the present invention is not limited by this figure). Each peak: Sδδ, Sγδ, S
βδ, Sαδ, Sαα, and Sαγ correspond to the peaks (7), (6), (9), (3), (2), and (1) in FIG. 1, respectively.

CSD is a value indicating the distribution of chain of constituent monomers in the copolymer, and the larger this value, the closer the copolymer is to the block copolymer. This definition is edited by Baifukan (1975), "Copolymerization 1 Reaction Analysis", edited by Japan Society of Polymer Science.
Pages 13 to 13 were followed. The calculation method is Suga, K
Park, J .; R Shiono, T Polymer
communication, Vol. 32, No. 10, 310
Page (1991). It is considered that the smaller this value is, the more the crystal component in the component B) is reduced, and as a result, the flexibility is improved. When this value is 2.5 or less, the flexibility of the composition is good, more preferably 2.2 or less, and most preferably 1.8 or less.

The room temperature o-xylene soluble component in the polypropylene resin composition of the present invention is the signal Sαβ and Sαα derived from two methylene groups between two adjacent tertiary carbon atoms in the ¹³ C-NMR spectrum. The intensity ratio Aαβ / Aαα has a value of 0.5 or less. Sαβ is 32 to 3 in the ¹³ C-NMR spectrum.
Appears at a position around 3 ppm. On the other hand, Sαα appears at a position around 45 ppm as shown in FIG. Aαβ /
When Aαα is 0.5 or less, it is preferable from the viewpoint of heat resistance and strength. The intensity ratio Aαβ / Aαα is more preferably 0.3 or less, and most preferably 0.2 or less.

This intensity ratio Aαβ / Aαα indicates the regularity of the bonding direction of the monomer in the component B), and is the ratio of the 1,2-addition reaction of propylene followed by the 2,1-addition reaction, or It is a measure showing the ratio of 1,2-addition reaction of 2,1-addition reaction of propylene. That is, the smaller the strength ratio Aαβ / Aαα, the more regular the bonding direction, and it is considered that the heat resistance and the tensile strength are improved by the increase of the cohesive force between molecules.

In another embodiment of the present invention, a softening agent is added in an amount of 150 parts by weight or less based on a total of 100 parts by weight of the components A) and B), and the Shore hardness D is 70.
It is a crosslinked thermoplastic elastomer composition characterized by the following.

Examples of the softening agent used here include process oil, liquid paraffin, paraffin, lubricating oil,
Vaseline, petroleum asphalt, coal tar, castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil, carnauba wax, castor wax, microcrystalline wax, beeswax, lanolin, petroleum resin, atactic polypropylene, liquid polybutadiene, etc. It is a plasticizer such as rubber or dioctyl phthalate. These are added for the purpose of promoting plasticization and improving the fluidity of the resulting composition. Among these, the process oil is most preferable, and it may be any of paraffin type, naphthene type and aromatic type, but paraffin type is particularly preferable since it has good color tone and weather resistance. The blending amount of these softeners is 150 parts by weight or less, preferably 100 parts by weight, based on 100 parts by weight of the components A) and B).
It is not more than 50 parts by weight, more preferably not more than 50 parts by weight.
If the addition amount of the softening agent exceeds 150 parts by weight, the softening agent bleeds out and the heat resistance decreases.

The crosslinked thermoplastic elastomer composition according to this embodiment has a Shore hardness D of 70 or less. If the Shore hardness D exceeds this value, the flexibility of the present embodiment decreases,
It becomes difficult to use it as a thermoplastic elastomer. The value of Shore hardness D is preferably 65 or less, more preferably 60 or less.

Next, a method for producing the crosslinked thermoplastic elastomer composition of the present invention will be described. The production method of the present invention comprises (a) a transition metal compound having at least one cyclopentadienyl skeleton, a group 4A to 6A transition metal compound and (b) a catalyst containing aluminoxane or a non-coordinating anion-containing compound. After producing A), the component B) is produced by copolymerizing the non-conjugated polyene and the α-olefin in the presence of the component A) without newly adding a catalyst.

Generally, in the production of polypropylene resin, a catalyst containing an organoaluminum compound and titanium as essential components is used. However, when it is attempted to produce the crosslinkable thermoplastic elastomer composition of the present invention using such a catalyst, it is difficult to form sufficient crosslinks in the component B) because the non-conjugated polyene has low polymerizability. Further, as a result, the dispersion of the component B) becomes poor, and problems such as deterioration of heat resistance and tensile strength and deterioration of molding appearance occur. Furthermore, when such a catalyst is used, the _Mw / _Mn of component A) is 4.0 or less, and the CSD
It is difficult to satisfy the value of 2.8 or less. Further, a catalyst composed of a vanadium compound is known as a catalyst for olefin polymerization. However, it is difficult to produce polypropylene having practical performance with this catalyst, and it is mainly used for producing elastomers. Such an elastomer cannot satisfy the above-mentioned Aαβ / Aαα value of 0.5 or less, and that a product obtained by dispersing a cross-linked product of the elastomer in polypropylene is not always sufficient in heat resistance and tensile strength. I can not say.

The catalysts used in the present invention shown below are:
A crosslinkable thermoplastic elastomer composition having desired properties can be obtained at low cost without causing the above-mentioned problems relating to the component B).

Constituting the catalyst used in the present invention (a)
A group 4A to 6A transition metal compound component of the periodic table having at least one cyclopentadienyl skeleton is represented by the following formula (the periodic table here is a long periodic table, and its group number is shown). Is based on the IUPAC nomenclature of 1970. Such a long-period type periodic table is described in Michinori Oki et al., 1989, Tokyo Kagaku Dojin, "Chemical Encyclopedia," 1st edition, page 1079. Hereinafter, the periodic table used in this specification refers to this).

General formula (1) (C ₅ R ¹ R ² R ³ R ⁴ R ⁵ ) _p (C ₅ R ⁶ R ⁷ R ⁸ R
⁹ R ¹⁰ ) MQ _{3-p In the} formula, p is an integer of 0 to 2, M is a Group 4A, Group 5A, or Group 6A metal. (C ₅ R ¹ R ² R ³ R ⁴ R ⁵ ) and (C ₅ R ⁶ R ⁷ R ⁸ R ⁹ R ¹⁰ ) are a cyclopentadienyl skeleton or a substituted cyclopentadienyl skeleton, and R ¹ to R ¹⁰ may be the same or different from each other.
R ^{1 to} R ¹⁰ are hydrogen, or an alkyl, cycloalkyl, alkenyl, aryl, alkylaryl, or arylalkyl group, alkylsilyl group, or silylalkyl group having 1 to 20 carbon atoms. Further, R ^{1 to} R ¹⁰ may be an alkylene group, a silicon-containing group such as a dialkylgermylene group or a silylene group, an alkylphosphine group or an imino group, and in such a case, a plurality of cyclopentadiene groups may be interposed therebetween. It is a structure in which an enyl skeleton or a substituted cyclopentadienyl skeleton is bonded, or a structure in which one or more Qs are bonded to a cyclopentadienyl skeleton or a substituted cyclopentadienyl skeleton. Further, instead of each R, a substance having a structure in which an aromatic ring or an alicyclic hydrocarbon is condensed may be used.

Q is a hydrocarbon group having 1 to 20 carbon atoms, a halogen or an atomic group containing a hetero atom. The hydrocarbon group is an aryl group, an alkyl group, an alkenyl group, an alkylaryl group, an arylalkyl group, an alkylsilyl or the like, and the halogen may be chlorine, bromine, iodine or fluorine. The atomic group containing a hetero atom includes amide, alkoxide, sulfide and the like. These Q may be the same as or different from each other.

Specific examples of the compound (a) in which M is zirconium are shown below. As those having one cyclopentadienyl skeleton, for example, dimethylsilylene (cyclopentadienyl) (t-butylamino) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (t-butylamino) zirconium dichloride, etc. And the cyclopentadienyl skeleton is 2
The following are examples of the individual components.

1) Those having C2 symmetry Bis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (2-methylindenyl) zirconium dimethyl, ethylenebis (2 -Methyl 4,5,6,7 tetrahydroindenyl) zirconium dichloride, ethylene bis (2
-Methyl-4-isopropylindenyl) zirconium dimethyl, ethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, ethylenebis (2
-Methyl-4-naphthylindenyl) zirconium dichloride, ethylenebis (4,5,6,7 tetrahydroindenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibenzyl, ethylenebis (t
-Butyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methylbenzoindenyl) zirconium dichloride, dimethylsilylenebis (3-t-
Butylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dibromide,
Dimethylsilylenebis (4-methylindenyl) zirconium dimethyl, dimethylsilylenebis (2,3,5,5)
2 ', 4', 5'-hexamethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2-methylindenyl) zirconium dimethyl, dimethylsilylene bis (2-methyl4,5,6,7 tetrahydroindenyl) Zirconium dichloride, diphenyl silylene bis (2-methyl-4-isopropylindenyl) zirconium dimethyl, dimethyl silylene bis (2
-Methyl-4-phenylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2,4,3 ', 5'-tetra-t-butylcyclopentadiene (Enyl) zirconium dimethyl, isopropylidene bis (indenyl) zirconium dichloride

2) Those having Cs symmetry Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,4,5 tetramethylcyclopentadienyl) zirconium dimethyl , Isopropylidene (cyclopentadienyl) (3,4 dimethylfluorenyl) zirconium dimethyl isopropylidene (cyclopentadienyl) (7,8 dimethylfluorenyl) zirconium dimethyl

3) Those having C1 symmetry Isopropylidene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-t-butylcyclopentadienyl) Zirconium dichloride,
Dimethylsilylene (tetramethylcyclopentadienyl) (3-t-butylcyclopentadienylzirconium) dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-neomenthylcyclopentadienylzirconium) dichloride, dimethylsilylene ( Tetramethylcyclopentadienyl) (3-menthylcyclopentadienylzirconium) dichloride, dimethylsilylene (cyclopentadienyl) (indenyl)
Zirconium dimethyl, isopropylidene (cyclopentadienyl) (tetrahydroindenyl) zirconium dibromide, methylmethylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride ethylene (3-methyl-cyclopentadienyl) (3-
Methyl-indenyl) zirconium dichloride, ethylene (3-tbutyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, ethylene (3-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium Dichloride, ethylene (3-methyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, ethylene (3
-Methyl-cyclopentadienyl) (3-trimethylsilyl-indenyl) zirconium dichloride, isopropylidene (3-methyl-cyclopentadienyl) (3-
Methyl-indenyl) zirconium dichloride, isopropylidene (3-tbutyl-cyclopentadienyl)
(3-methyl-indenyl) zirconium dichloride,
Isopropylidene (3-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, dimethylsilylene (3-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, dimethylsilylene (3 -T-Butyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, dimethylsilylene (3-t-butyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, isopropylidene (3-methyl- Cyclopentadienyl) (1,2,3-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (3-tbutylcyclopentadienyl) (1,
2,3-Trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (3-tbutylcyclopentadienyl) (1,2,3-tritbutylcyclopentadienyl) zirconium dichloride, isopropylidene (3-methyl- Cyclopentadienyl) (3-methyl-indenyl) zirconium dimethyl, isopropylidene (3-tbutyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dimethyl, isopropylidene (3-tbutyl-cyclopentadienyl) ) (3-
t-Butyl-indenyl) zirconium dimethyl, ethylene (3-methyl-cyclopentadienyl) (3-methyl-indenyl) hafnium dichloride, dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3
-T-butylcyclopentadienyl) (fluorenyl)
Hafnium dichloride, dimethyl silylene (3-cyclohexylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethyl silylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethyl silylene (3-((1,1-
Diethyl) butyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3
-Phenylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-mesitylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3- (o-tolyl)
Cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3- (2,6-xylyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-benzylcyclopentadienyl) (fluorenyl) zirconium dichloride Dimethylsilylene (3-tritylcyclopentadienyl) (fluorenyl) zirconium dichloride,
Dimethylsilylene (3-trimethylsilylcyclopentadienyl) (fluorenyl) zirconium dichloride,
Methylphenylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride,
Methylphenylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, methylphenylsilylene (3-cyclohexylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-isopropylcyclopentadienyl) (Fluorenyl) zirconium dichloride, methylphenylsilylene (3-((1,1-diethyl) butyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-phenylcyclopentadienyl) (fluorenyl) zirconium dichloride , Methylphenylsilylene (3-mesitylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3- (o-tolyl) cycl Pentadienyl) (fluorenyl) zirconium dichloride and the like can be exemplified.

It is also possible to use a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, vanadium metal or the like in the zirconium compound as described above.

Of these, those having two cyclopentadienyl skeletons are preferable, and those having 2 cyclopentadienyl skeletons are more preferable.
Having one cyclopentadienyl skeleton bound thereto, such as ethylenebis (indenyl) zirconium dichloride,
Ethylenebis (indenyl) zirconium dimethyl, ethylenebis (2-methylindenyl) zirconium dimethyl, ethylenebis (2-methyl4,5,6,7 tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methyl-4-isopropyl) Indenyl) zirconium dimethyl, ethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, ethylenebis (4,5,6,7 tetrahydroindene Nyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibenzyl, ethylene bis (t-butyl-indenyl) zirconium dichloride, ethylene (3-methyl-cyclopentadienyl)
(3-methyl-indenyl) zirconium dichloride,
Ethylene (3-t-butyl-cyclopentadienyl) (3
-Methyl-indenyl) zirconium dichloride, ethylene (3-t butyl-cyclopentadienyl) (3-t
Butyl-indenyl) zirconium dichloride, ethylene (3-methyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, ethylene (3-methyl-cyclopentadienyl) (3-trimethylsilyl-indenyl) zirconium dichloride, And transition metal compounds in which these zirconium metals are replaced with titanium metal, hafnium metal, vanadium metal, etc., in which case not only the heat resistance is particularly high but also the tensile strength is further improved.

From this point of view, most preferably, two cyclopentadienyl skeletons are bonded via one carbon atom or one silicon atom, and specifically, dimethylsilylenebis (2-methyl). Indenyl) zirconium dichloride, dimethylsilylene bis (3-t
-Butylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dibromide, dimethylsilylenebis (4-methyl-indenyl)
Zirconium dimethyl, dimethyl silylene bis (2,
3,5,2 ′, 4 ′, 5′-hexamethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dimethyl,
Dimethyl silylene bis (2-methyl-4,5,6,7 tetrahydroindenyl) zirconium dichloride, diphenyl silylene bis (2-methyl-4-isopropylindenyl) zirconium dimethyl, dimethyl silylene bis (2-methyl-4-phenyl) Indenyl) zirconium dichloride, isopropylidene (3-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, isopropylidene (3-tbutyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride , Isopropylidene (3-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, dimethylsilylene (3-
Methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, dimethylsilylene (3
-T-Butyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, dimethylsilylene (3-t-butyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, isopropylidene (3-methyl- Cyclopentadienyl) (1,
2,3-Trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (3-tbutylcyclopentadienyl) (1,2,3-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (3-tbutylcyclopenta) Dienyl) (1,2,3
-Tri-t-butylcyclopentadienyl) zirconium dichloride, isopropylidene (3-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dimethyl, isopropylidene (3-t-butyl-cyclopentadienyl) (3- Methyl-indenyl) zirconium dimethyl, isopropylidene (3-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dimethyl, and transitions in which these zirconium metals are replaced with titanium metal, hafnium metal, vanadium metal, etc. Metal compounds and the like.

Aluminoxanes and non-coordinating anion-containing compounds can be used as the cocatalyst component (b).

The aluminoxane used as the cocatalyst component (b) is an organoaluminum compound represented by the general formula (2) or the general formula (3). General formula (2)

Embedded image General formula (3)

Embedded image R ¹² is a methyl group, an ethyl group, a propyl group, a butyl group,
A hydrocarbon group such as an isobutyl group, preferably a methyl group or an isobutyl group. m is an integer of 4 to 100, preferably 6 or more and particularly 10 or more.
A method for producing this type of compound is known, and for example, a method in which a salt having crystallization water is added to a hydrocarbon solvent suspension of (copper sulfate hydrate, aluminum sulfate hydrate) and trialkylaluminum is exemplified. You can do it.

Further, aluminoxanes represented by the general formulas (4) and (5) may be used. General formula (4)

[Chemical 4] General formula (5)

Embedded image R ¹³ is a methyl group, an ethyl group, a propyl group, a butyl group,
A hydrocarbon group such as an isobutyl group, preferably a methyl group or an isobutyl group. R ¹⁴ is a methyl group,
It is a hydrocarbon group such as an ethyl group, a propyl group, a butyl group and an isobutyl group, or a halogen or hydrogen atom such as chlorine and bromine, and a hydroxyl group, and is different from R ¹³ .
R ¹⁴ may be the same or different. m is usually 1
To an integer of 100, preferably 3 or more, m
+ N is 4 to 100, preferably 6 or more. In the general formulas (4) and (5),

[Chemical 6] It may be a block-shaped combination or a regular or irregularly connected one. The method for producing such an aluminoxane is the same as that for the aluminoxane represented by the general formula described above. Instead of one kind of trialkylaluminum, two or more kinds of trialkylaluminum are used, or one or more kinds of trialkylaluminum and one kind are used. The above dialkylaluminum monohalides may be used. Further, it is not limited by the difference in solubility of the aluminoxane in the organic solvent.

Examples of the non-coordinating anion-containing compound used as the cocatalyst component (b) include those having a structure represented by the general formula (6). Formula ^{(6) (M 2 X 1} X 2 X 3 X 4) (nm) - · C (nm) + ( wherein, M ² is a Group 5A - Group 8 of the periodic table, Group 1B - Elements selected from Group 5B, X ¹ , X ² , X ³ , X ⁴
Are hydrogen atom, dialkylamino group, alkoxy group, aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, substituted alkyl group, halogen-substituted aryl, respectively. Represents a group, an organic metalloid group or a halogen atom. C represents a counter cation such as carbonium or ammonium. m is a valence of M ^{2 and} is an integer of 1 to 7, and n is an integer of 2 to 8. ) Specific examples of these compounds include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butylammonium tetraphenylborate), trimethylammonium tetra (p-tolyl) borate, tributyl. Ammonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (3,5-trifluoromethylphenyl) borate, tributylammonium Examples include tetra (o-tolyl) borate, triphenylcarbenium tris (pentafluorophenyl) methylborate, and the like. It is preferably dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylcarbenium tetrakis (pentafluorophenyl) borate.

The catalyst used in the production method of the present invention is obtained by contacting the above-mentioned catalyst components (a) and (b) with or without a monomer to be polymerized outside or inside the polymerization tank. Can be obtained by The contact method is arbitrary, and they may be introduced separately and contacted during the polymerization, or those contacted in advance may be used.
The amounts of the component (a) and the component (b) used are arbitrary,
When an aluminoxane is used as the component (b), the atomic ratio of aluminum in the component (b) to the transition metal in the component (a) is 0.01 to 100,000, preferably 0.1 to 30. 1,000. When a non-coordinating anion-containing compound is used as the component (b), a metal selected from the groups 5A to 8 and 1B to 5B in the periodic table in the component (b) and the component (a). The atomic ratio of the transition metal in) is 0.00
1 to 1,000 is common, preferably 0.01 to
A range of 100 is preferred.

The above catalyst used in the present invention includes
Other catalyst constituents such as a carrier may be included. The powder property of the crosslinked thermoplastic elastomer composition obtained by supporting the catalyst on such a carrier is improved, and the granulation process can be omitted. Further, the powder thus obtained can be directly used as a product after being mixed with additives, which is preferable.

There is no limitation on the kind of such a carrier, and it may be an inorganic carrier such as an inorganic oxide carrier or an organic carrier such as a porous polyolefin, and these may be used in combination. As the inorganic oxide carrier, silica, alumina, magnesium oxide, zirconium oxide, titanium oxide, iron oxide,
Examples thereof include calcium oxide and zinc oxide. Examples of other inorganic carriers include magnesium halides such as magnesium chloride and magnesium bromide, and magnesium alkoxides such as magnesium ethoxide.

Other inorganic carriers include ion-exchangeable layered compounds. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the contained ions are exchangeable. Specific examples of these include kaolin, bentonite, talc, kaolinite, vermiculite, montmorillonite group, mica group,
α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO
₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ
-Ti _{(NH 4} PO 4), such as ₂ · H ₂ O and the like.

As the organic carrier, polyethylene, polypropylene, polystyrene, ethylene-butene copolymer, ethylene-propylene copolymer, polymethacrylic acid ester, polyacrylic acid ester, polyacrylonitrile,
Polyamide, polycarbonate, polyester such as polyethylene terephthalate, polyvinyl chloride and the like, which may be crosslinked such as styrene-divinylbenzene copolymer. Further, those in which a catalyst is chemically bound to these organic carriers can also be used.

The particle size of these carriers is generally from 0.1 to 300.
μm, preferably 1 to 200 μm, and more preferably 10 to 100 μm. If the particle size is small, it becomes a fine powdery polymer, and if it is too large, coarse particles are generated, and handling of the powder becomes easy.

The pore volume of these carriers is usually 0.1 to 5 c.
m ² / g, preferably 0.3 to ³ cm ² / g. The pore volume can be measured by, for example, the BET method or the mercury penetration method. In the production method of the present invention, using the above catalyst, any known polymerization method, such as solution polymerization, solventless polymerization in a liquid phase monomer, gas phase polymerization, and melt polymerization, can be adopted. As a solvent for solution polymerization, saturated aliphatic hydrocarbons and aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene and toluene can be used alone or as a mixture. Polymerization temperature is -78 to 200
The temperature is preferably -20 to 100 ° C. The pressure of the reaction system is not particularly limited, but is usually in the range of atmospheric pressure to 1000 psi in the polymerization in the liquid phase and atmospheric pressure to 600 psi in the gas phase. In the polymerization, known means,
For example, the molecular weight of each component can be controlled by selecting the temperature and pressure or introducing hydrogen.

The crosslinkable thermoplastic elastomer composition obtained by the production method of the present invention comprises other resins, rubbers and fillers in addition to the polypropylene resin component A) and the partially crosslinked olefin copolymer elastomer component B). ,
It also includes those containing other components such as additives.

Examples of such fillers include talc, calcium carbonate, mica, glass fiber and silica.
Examples of additives include heat resistance stabilizers, weather resistance stabilizers, colorants, antistatic agents, flame retardants, nucleating agents, lubricants, slip agents, antiblocking agents, and the like. Phenol-based as heat resistance stabilizer,
Known materials such as phosphorus and sulfur can be used. Colorants include carbon black, titanium white, zinc white,
Benga, azo compounds, nitroso compounds, phthalocyanine compounds and the like. Antistatic agent, flame retardant, nucleating agent,
Known lubricants, slip agents, antiblocking agents and the like can all be used.

As described above, the crosslinkable thermoplastic elastomer composition of the present invention is excellent in heat resistance and tensile strength, and can be manufactured inexpensively without using a crosslinking agent such as an organic peroxide. . Further, the crosslinkable thermoplastic elastomer obtained in the present invention can be used in a wide range of fields similar to those of conventional crosslinkable thermoplastic elastomers, for example, automobile exteriors, automobile interiors, home appliances, civil engineering, and construction.

[0053]

The present invention is not limited to the following examples. The measuring methods and the resins used in the examples are as follows. Molecular weight distribution M _W / M _N 1,2,4-trichlorobenzene as a solvent,
Gel permeation chromatography device 150C manufactured by rs (column Shodex AT-806MS)
At 130 ° C. Measurement of melting point Tm Differential scanning calorimeter DSC manufactured by PERKIN-ELMER
The measurement was carried out according to -7 at a temperature rising rate of 20 ° C./min. ¹³ C-NMR JNM-GSX400 manufactured by JEOL Ltd. Measurement temperature 120
° C., 1,2,4-trichlorobenzene / benzene -d ₆
It was measured with a (3/1) solvent. Both ends of a 100 mm × 15 mm × 0.5 mm test piece were fixed with jigs and heated in a constant temperature bath at 120 ° C. for 3 minutes. After that, the test piece was taken out from the constant temperature bath, and how much the central portion of the test piece drooped from both ends was measured. The smaller the amount of droop, the better the heat resistance. Shore hardness D 1 mm thick 6 test pieces are stacked, ASTM 676-49
Was measured according to. Ethylene content measured by ¹³ C-NMR

Component of catalyst Component (a-1) rac-Ethylenebis (indenyl) zirconium dichloride Component (a-2) Dimethylsilylenebis (2-methyl-benzoindenyl) zirconium dichloride Component (a-3) Isopropylidene ( 3-t-butylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride component (b-1) triphenylcarbenium tetrakis (pentafluorophenyl) borate component (b-2) methylaluminoxane

Example 1 Component A) and component B) were prepared by multistage polymerization according to the following. Into a 1.5 L stainless steel autoclave, 1.5 mmol of triethylaluminum and 8 mol of propylene were introduced and well stirred. Triethylaluminum (0.5 M) toluene solution (1.5 ml) and the above component (a-
1) and component (b-1) in toluene respectively 0.001
After pre-contact mixing with 5 mmol and 0.002 mmol,
This mixture was pressed into the autoclave and the polymerization temperature was adjusted to 1
Polymerization was carried out for 20 minutes while maintaining the temperature at 0 ° C. to prepare Component A). Then, 6 ml of 1,9-decadiene was press-fitted, and ethylene was introduced into the autoclave until the partial pressure thereof became 10 kg / cm ² . 25 while maintaining the polymerization temperature at 10 ℃
Polymerization for minutes produced component B). Thereafter, methanol was pressed into the autoclave to stop the polymerization, and propylene gas was purged to obtain the desired crosslinked thermoplastic elastomer composition. The crosslinked thermoplastic elastomer composition thus obtained was dissolved in boiling o-xylene, and this solution was poured into a large amount of room temperature hexane to obtain Component A) as a precipitate. The proportion of component A) in the composition was 37.0% by weight, calculated from the weight of the precipitate obtained. The boiling o-xylene insoluble content was 41.0%.

Example 2 Component A) and component B) were prepared by multistage polymerization according to the following. In a 1.5 L stainless steel autoclave, 400 ml of toluene and 1.5 mmo of triethylaluminum.
1 and 4 mol of propylene were introduced into the autoclave. Further, ethylene was introduced until the partial pressure thereof became 0.5 kg / cm ^2, and well stirred. Next, 1.5 ml of a triethylaluminum (0.5 M) toluene solution and the above component (a-
1) and component (b-1) in toluene respectively 0.001
After pre-contact mixing with 5 mmol and 0.002 mmol,
This mixture was pressed into the autoclave and the polymerization temperature was adjusted to 2
Polymerization was carried out for 20 minutes while maintaining the temperature at 0 ° C. to prepare Component A). Then, 6 ml of 1,5-hexadiene was press-fitted, and ethylene was introduced into the autoclave until the partial pressure thereof became 10 kg / cm ² . 2 more while keeping the polymerization temperature at 20 ℃
Polymerization was carried out for 5 minutes to produce component B). Thereafter, methanol was pressed into the autoclave to stop the polymerization, propylene gas was purged, and the obtained liquid was put into acetone to obtain a desired thermoplastic elastomer composition. The content of component A) in the composition obtained in the same manner as in Example 1 was measured and found to be 40.9% by weight. The ethylene content in component A) was 3.5% by weight. The boiling o-xylene insoluble content was 38.4% by weight.

Example 3 Instead of the component (a-1) in Example 1, the component (a-
The same procedure was performed except that 2) was used.

Example 4 Instead of the component (a-1) in Example 1, the component (a-
The same procedure was carried out except that 3) was used and the polymerization time in the production of component B) was 15 minutes.

Examples 5 to 8 The same operations as in Examples 1 to 4 were carried out except that the component (b-2) was used instead of the component (b-1).

Example 9 Catalyst Preparation 2.0 g of porous polypropylene and the above component (a-1)
1.0 mmol and 1.5 mmol of component (b-1) were contacted in toluene for 1 hour under a nitrogen stream. Toluene was distilled off with nitrogen and dried under reduced pressure to obtain a catalyst component. Preparation of Composition 1.5 mmol of triethylaluminum and 8 mol of propylene were introduced into a 1.5 L stainless steel autoclave and well stirred. 0.3 g of the catalyst prepared above was pressed into this autoclave to keep the polymerization temperature at 30 ° C.
Polymerization for 0 minutes produced component A). Then 1,9-
Decadiene 6 ml is press-fitted, and the partial pressure of ethylene is 10
It was introduced into the autoclave until it reached kg / cm ² .
Component B) was produced by polymerizing for 40 minutes while maintaining the polymerization temperature at 30 ° C. Thereafter, methanol was pressed into the autoclave to stop the polymerization, and propylene gas was purged to obtain the desired thermoplastic elastomer composition.

Examples 10 to 16 The same procedure as in Examples 2 to 8 was carried out except that the following catalyst was used as the catalyst component. Porous polypropylene 2.0g
And the above component (a-1) 1.0 mmol, the component (b-1)
1.5 mmol was contacted for 1 hour in toluene under a nitrogen stream. Toluene was distilled off with nitrogen and dried under reduced pressure to obtain a catalyst component.

Comparative Example 1 1) Polymerization catalyst Preparation of solid titanium catalyst component A 200 ml three-necked flask equipped with a thermometer and a stirrer was thoroughly replaced with nitrogen, and then diethoxymagnesium 1.1 was added.
1 g (9.47 mmol), toluene 10 ml and di-n-butyl phthalate 0.46 ml (1.73 mmo)
1) is charged and stirred at 70 ° C. for 2 hours. Then, the mixture is cooled to room temperature and 50 ml of TiCl _{4 is} added dropwise from the dropping funnel over 1 hour. After the dropping is completed, the temperature is raised to 110 ° C. and the reaction is performed for 2 hours while stirring. After completion of the reaction, the mixture was cooled to room temperature, washed with 200 ml of n-hexane several times, and dried under reduced pressure at 60 ° C. for 30 minutes to obtain a solid titanium catalyst component. Preparation of Polymerization Catalyst To 10 mg of the solid titanium catalyst component prepared above, 1.5 mmol of triethylaluminum and 0.3 mmol of cyclohexylmethyldimethoxysilane were added to prepare a catalyst. 8 mol of propylene and 730 ml of hydrogen (volume at normal pressure) were introduced into an autoclave having an internal volume of 1.5 L. After the internal temperature of the autoclave reached 70 ° C., a catalyst was added to start polymerization. After polymerizing for 20 minutes, it was quickly cooled to 50 ° C and the ethylene partial pressure was 7k.
Ethylene was continuously supplied so as to maintain g / cm ^2, and polymerization was carried out for 30 minutes. Then, methanol was pressed into the autoclave to stop the polymerization. Propylene and ethylene were purged to obtain a thermoplastic elastomer composition.

Comparative Example 2 Example 1 was repeated except that 1,9-decadiene was not used.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the polymerization times of the components A) and B) were 45 minutes and 10 minutes, respectively.

Comparative Example 4 The same procedure as in Example 1 was repeated except that the polymerization times of the components A) and B) were 5 minutes and 30 minutes, respectively.

Example 17 Into a 1.5 L stainless steel autoclave, 1.5 mmol of triethylaluminum and 8 mol of propylene were introduced and well stirred. Triethylaluminum (0.5
M) Toluene solution (1.5 ml) and the above-mentioned component (a-1) and component (b-1) each in 0.0015 mmo in toluene.
After preliminarily mixing with 0.001 mmol and 1, 0.002 mmol of the mixture, the mixed solution was injected into the autoclave under pressure to keep the polymerization temperature at 20 ° C. and polymerized for 30 minutes. 40 parts by weight of the composition obtained above and an ethylene-propylene-diene copolymer elastomer (Mooney viscosity ML
_{1 + 4} (100 ° C.) = 65 Iodine value 24) 60 parts by weight, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane 0.5 part by weight and diallyl terephthalate 1.2 parts by weight Was added and kneaded for 10 minutes at 210 ° C. with a Labo Plastomill manufactured by Toyo Seiki to obtain a composition.

Example 18 100 parts by weight of the composition obtained in Example 1, 10 parts by weight of process oil (trade name PW-380, manufactured by Idemitsu Kosan Co., Ltd.) and an antioxidant were added, and then Labo Plastomill manufactured by Toyo Seiki Co., Ltd. Was kneaded at 210 ° C. for 10 minutes to obtain the desired composition. This composition has a Shore hardness of 31 and a tensile breaking strength of 1.
13 kg / cm ² , the tensile elongation at break was 320%, and the hot sag was 0 mm.

The physical properties of the thermoplastic elastomer compositions obtained in Examples and Comparative Examples are shown in Tables 1 and 2.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

The crosslinkable thermoplastic elastomer composition of the present invention can be manufactured at low cost without using a crosslinking agent such as an organic peroxide, and has excellent heat resistance and mechanical properties equal to or higher than those of the crosslinkable thermoplastic elastomer. It shows the dynamic strength.

[Brief description of drawings]

FIG. 1 ¹³ C- for explaining CSD in the present invention
It is an example of an NMR spectrum diagram.

Claims (5)

[Claims] 1. A component A) having a molecular weight distribution Mw / Mn by gel permeation chromatography of 4.0 or less and 20% by weight or less of ethylene and / or α-.
A composition comprising 20 parts by weight or more and less than 65 parts by weight of a polypropylene-based resin in which an olefin may be copolymerized, and component B) a partially cross-linked olefin-based copolymer elastomer of more than 35 parts by weight and 80 parts by weight or less, in the composition, the content W _B the following formula (X ratio X and the component B) of the component insoluble in boiling o- xylene, W both _B weight%) X ≧ 0.1 × W _B A crosslinkable thermoplastic elastomer composition, which is satisfied. 2. A composition comprising the components A) and B) according to claim 1, wherein the component soluble in room temperature o-xylene is a) having a CSD value of 3.0 or less as defined by the following formula: CSD = [(0.5 Aδδ + 0.25 Aγδ + 0.5Aβδ) × Aα
α] / [0.5 (Aαγ + Aαδ)] ² where Aδδ, Aγδ, Aβδ, Aαδ, Aαα, A
αγ is the following peak derived from a methylene group in ¹³ C-NMR: Sδδ, Sγδ, Sβδ, Sαδ,
These are the integrated intensities of Sαα and Sαγ. b) two adjacent 3's in the ¹³ C-NMR spectrum
Signal S derived from two methylene groups between primary carbon atoms
The polypropylene resin composition according to claim 1, wherein the strength ratio Aαβ / Aαα of αβ and Sαα satisfies the condition of 0.5 or less. 3. The crosslinked type according to claim 1, wherein the melting point Tm of the component A) according to claim 1 measured by a differential scanning calorimeter is 115 ° C. or higher. Thermoplastic elastomer composition. 4. A softening agent is added in an amount of 150 parts by weight or less based on a total of 100 parts by weight of the components A) and B) of claim 1, and the Shore hardness D is 70 or less. The crosslinkable thermoplastic elastomer composition according to any one of claims 1 to 3, which is characterized in that. 5. In producing the crosslinked thermoplastic elastomer composition according to claim 1, at least one cyclopentadienyl skeleton (a) is used.
After the component A) is produced by a catalyst comprising a group 4A to group 6A transition metal compound and (b) an aluminoxane or a compound having a non-coordinating anion, the component A) is newly added in the presence of the component A). A method for producing a crosslinkable thermoplastic elastomer composition, which comprises a step of producing component B) by copolymerizing a non-conjugated polyene and an α-olefin without adding a catalyst.