JP3313151B2 - Olefin-based thermoplastic elastomer composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based thermoplastic elastomer composition and a method for producing the same, and more particularly, to a tensile strength and breaking elongation comprising a crystalline polyolefin resin and a higher α-olefin-based copolymer rubber. The present invention relates to an olefin-based thermoplastic elastomer composition having excellent degree and rubber elasticity, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are widely used as energy-saving and resource-saving elastomers, especially as substitutes for vulcanized rubber for automobile parts, industrial machine parts, electronic / electric equipment parts, building materials, and the like. I have.

[0003] Olefin-based thermoplastic elastomers can be classified into crosslinked and non-crosslinked types. Non-crosslinked thermoplastic elastomers have less variation in quality because they do not involve a crosslinking reaction and are inexpensive to manufacture. On the other hand, when compared with each other in terms of performance, tensile strength, elongation at break, or rubber-like properties (for example, permanent In terms of elongation and compression set) and heat resistance, the crosslinked olefin-based thermoplastic elastomer is superior to the non-crosslinked olefin-based thermoplastic elastomer. This is described by AYCoran et al. (Rubber Chemistry and Technology, vol. 53 (1980),
It is widely known as described in detail on page 141).

Non-crosslinked or partially crosslinked olefinic thermoplastic elastomers are described, for example, in JP-B-53-21021, JP-B-55-18448, JP-B-56-155741, and JP-B-56-15.
742, JP-B-58-46138, JP-B-58-56575, JP-B-59-30376, JP-B-62-938, and JP-B-62-5913.
No. 9 and other publications.

As described above, the olefin-based thermoplastic elastomer includes a non-crosslinked thermoplastic elastomer and a crosslinked thermoplastic elastomer. In the case of the noncrosslinked thermoplastic elastomer, a conventionally known noncrosslinked thermoplastic elastomer is used. Compared with thermoplastic elastomers, the emergence of an olefin-based thermoplastic elastomer composition having excellent tensile strength, elongation at break, rubber-like properties (permanent elongation, compression set, etc.), heat resistance, etc. is desired, and crosslinking is desired. In the case of type thermoplastic elastomer,
There has been a demand for an olefin-based thermoplastic elastomer composition having better tensile strength, elongation at break and rubber properties than conventionally known vulcanized rubbers.

[0006]

It is an object of the present invention to provide a non-crosslinked type having excellent tensile strength, elongation at break, rubbery properties and heat resistance. An object of the present invention is to provide an olefin-based thermoplastic elastomer composition which is more excellent in tensile strength, elongation at break and rubber properties than rubber.

It is another object of the present invention to provide a partially crosslinked olefin-based thermoplastic elastomer composition having excellent properties as described above.

[0008]

SUMMARY OF THE INVENTION An olefinic thermoplastic elastomer composition according to the present invention comprises a crystalline polyolefin resin (A) 1.
Olefin-based heat composed of 0 to 60 parts by weight and 90 to 40 parts by weight of a higher α-olefin-based copolymer rubber (B) [the total amount of (A) and (B) is 100 parts by weight] A higher α-olefin-based copolymer rubber (B), which comprises a higher α-olefin having 6 to 20 carbon atoms, ethylene, propylene and
-Composed of at least one or more monomers selected from the group consisting of butenes and a non-conjugated diene represented by the following general formula [I], having an iodine value in the range of 0.1 to 50, and It is characterized in that the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 1.0 to 10.0 dl / g.

[0009]

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In the general formula [I], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 4 carbon atoms,
² and R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, no R ² and R ³ are both hydrogen atoms.

The olefin-based thermoplastic elastomer composition according to the present invention is based on 100 parts by weight of the total amount of the above-mentioned crystalline polyolefin resin (A) and the above-mentioned higher α-olefin-based copolymer rubber (B). , 2 to 100 parts by weight of a softener (C) and / or 2 to 50 parts by weight of an inorganic filler (D).

The olefin-based thermoplastic elastomer composition according to the present invention has a tensile strength,
Excellent elongation at break, rubbery properties and heat resistance. Further, the olefin-based thermoplastic elastomer composition according to the present invention, particularly when partially crosslinked, is superior to conventional vulcanized rubber in tensile strength, elongation at break and rubber-like properties.

Further, the method for producing the partially crosslinked olefin-based thermoplastic elastomer composition described above comprises the steps of: 10 to 60 parts by weight of the crystalline polyolefin resin (A);
-90 to 40 parts by weight of the olefin copolymer rubber (B) [the total amount of (A) and (B) is 100 parts by weight]
Is dynamically heat-treated in the presence of an organic peroxide to partially crosslink the mixture.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the olefin-based thermoplastic elastomer composition according to the present invention and a method for producing the same will be described in detail.

The olefin-based thermoplastic elastomer composition according to the present invention is a non-crosslinked thermoplastic elastomer composition or a partially crosslinked thermoplastic elastomer composition, and comprises a specific crystalline polyolefin resin (A); And a specific higher α-olefin copolymer rubber (B).

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

Examples of suitable raw material olefins for the crystalline polyolefin resin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 2-hexene.
Examples thereof include methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-octene, 1-decene, and a mixed olefin obtained by mixing two or more of these olefins.

The polymerization mode may be random or block type, and any polymerization mode may be adopted as long as a resinous material is obtained. The crystalline polyolefin resin used in the present invention is an MFR (ASTM D 1238-65T,
(230 ° C.) is usually in the range of 0.01 to 100 g / 10 min, particularly preferably 0.05 to 50 g / 10 min.

The above-mentioned crystalline polyolefin resin (A) comprises:
It has a role in improving the fluidity and heat resistance of the composition. In the present invention, the crystalline polyolefin resin (A) is preferably 10 to 60 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B). Is 20-55
Used in parts by weight.

When the crystalline polyolefin resin (A) is used in the above proportion, an olefin-based thermoplastic elastomer composition having excellent rubber elasticity and excellent molding can be obtained.

Higher α-Olefin Copolymer Rubber (B) The higher α-olefin copolymer rubber (B) used in the present invention has 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. A rubber obtained by copolymerizing a higher α-olefin, a specific monomer, and a specific non-conjugated diene.

Specific examples of the higher α-olefin include 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-hexene.
Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-
Heptadecene, 1-nonadecene, 1-eicosene, 9-
Methyl-1-decene, 11-methyl-1-dodecene, 12-
Ethyl-1-tetradecene and the like.

In the present invention, the higher α-
The olefin may be used alone or as a mixture of two or more. Among the above higher α-olefins, 1-hexene, 1-octene and 1-decene are particularly preferably used.

The above non-conjugated diene is represented by the following general formula [I].

[0025]

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In the general formula [I], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are a hydrogen atom or a 1 to 5 carbon atom.
And R ² and R ³ are not both hydrogen atoms.

Specific examples of the non-conjugated diene represented by the above general formula [I] include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 4-ethyl-1,4 -Hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4
-Heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene,
4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-
1,5-octadiene, 5-ethyl-1,5-octadiene, 6-
Ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 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, 7-methyl-1,6-
Decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6
-Decadiene, 7-methyl-1,7-decadiene, 8-methyl-
1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl- 1,8-decadiene, 9-
Methyl-1,8-undecadiene and the like. Among these, 7-methyl-1,6-octadiene is particularly preferably used.

In the present invention, the above non-conjugated dienes may be used alone or as a mixture of two or more. The above monomers include ethylene, propylene and 1-butene. These monomers may be used alone or as a mixture of two or more. The molar ratio of higher α-olefin to monomer (higher α-olefin / monomer) is from 10/90 to 9
It is preferably within the range of 5/5.

The higher α-olefin copolymer rubber (B) used in the present invention has an iodine value of 0.1 to 50, preferably 1 to 30. The intrinsic viscosity [η] of the higher α-olefin copolymer rubber (B) measured in a decalin solvent at 135 ° C. is 1.0 to 10.0 dl /
g, preferably in the range of 1.5 to 7 dl / g.

In the present invention, the higher α-olefin copolymer rubber (B) comprises the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B).
Is used in an amount of 90 to 40 parts by weight, preferably 80 to 45 parts by weight, based on 100 parts by weight of the total amount.

The above-mentioned higher α-olefin copolymer rubber (B) can be produced by the following method.
The higher α-olefin-based copolymer rubber (B) used in the present invention is prepared by preparing a higher α-olefin having 6 to 20 carbon atoms, the above monomer, and the above general formula in the presence of an olefin polymerization catalyst. It is obtained by copolymerizing with the non-conjugated diene represented by [I].

The olefin polymerization catalyst used in the present invention comprises a solid titanium catalyst component (a), an organoaluminum compound catalyst component (b), and an electron donor catalyst component (c).

FIG. 1 shows an example of a flowchart of a method for preparing a catalyst component for olefin polymerization used in producing the higher α-olefin copolymer rubber used in the present invention. The solid titanium catalyst component (a) used in the present invention comprises:
It is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

The solid titanium catalyst component (a) is
It is prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below. In the present invention, the titanium compound used for preparing the solid titanium catalyst component (a) includes, for example, Ti (OR) _g X
_4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be exemplified.

More specifically, TiCl ₄ , TiBr
₄ , titanium tetrahalide such as TiI ₄ ; Ti (OC
H ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄
H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C
₄ H ₉ ) Trihalogenated alkoxytitanium such as Br ₃ ; T
i (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti
_{(O-n-C 4 H} 9) 2 Cl 2, Ti (OC 2 H 5) dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3
Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃
Monohalogenated trialkoxy titanium such as Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC
_{2 H 5) 4, Ti (} O-n-C 4 H 9) 4, Ti (O-iso-C 4 H
₉ ) ₄ , and tetraalkoxy titanium such as Ti (O-2-ethylhexyl) ₄ .

Of these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred. Among them,
Titanium tetrachloride is particularly preferably used. These titanium compounds may be used alone or in combination of two or more. In addition, these titanium compounds
It may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a reducing magnesium compound and a non-reducing magnesium compound.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of the magnesium compound having such a reducing property include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesiumchloride, butyl Magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium,
Butyl magnesium halide and the like can be mentioned. These magnesium compounds may be used alone, or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of the magnesium compound having no reducibility include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, and isopropoxy magnesium chloride. ,
Alkoxy magnesium halides such as butoxy magnesium chloride and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium and the like Alkoxy magnesium; allyoxy magnesium such as phenoxy magnesium and dimethyl phenoxy magnesium; and magnesium carboxylate such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

In the present invention, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property, the magnesium compound may be a complex compound, a double compound or another compound of the above-mentioned magnesium compound and another metal. It may be a mixture with a metal compound. Further, a mixture of two or more of the above compounds may be used.

In the present invention, among these, magnesium compounds having no reducing property are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferably used. Can be

In the present invention, examples of the electron donor used for preparing the solid titanium catalyst component (a) include an organic carboxylic acid ester and a polyvalent carboxylic acid ester described below. Compounds having the following skeleton.

[0044]

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[0045]

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[0046]

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[0047]

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In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
Preferably, at least one of R ³ and R ⁴ is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a cyclic structure. Examples of the substituted hydrocarbon group include a substituted hydrocarbon group containing a different atom such as N, O, and S. For example, -C-O-C
-, - COOR, -COOH, -OH , -SO 3 H, -
Substituted hydrocarbon groups having a structure such as C—N—C— and —NH ₂ are mentioned.

Among these, a diester derived from a dicarboxylic acid in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms is preferable. Specific examples of the polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, α-
Diisobutyl methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate,
Diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyldiisobutylmalonate, diethyldinormalbutylmalonate, dimethylmaleate, monooctylmaleate, diisooctylmaleate, diisobutylmaleate, diisobutylbutylmaleate, butylmaleate Fatty acid polycarboxylic acid esters such as diethyl acrylate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citrate, and dimethyl citrate; 1,2-cyclohexanecarboxylate Diethyl acid,
Aliphatic polycarboxylic acid esters such as diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadicate; monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, phthalate Ethyl isobutyl phthalate, mono-n-butyl phthalate, ethyl-n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as di-2-ethylhexyl, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; 3 And esters derived from heterocyclic polycarboxylic acids such as 1,4-furandicarboxylic acid.

Other examples of polycarboxylic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, di-2-ethylhexyl sebacate and the like. And esters derived from long-chain dicarboxylic acids.

Among these polycarboxylic acid esters,
Compounds having a skeleton represented by the aforementioned general formula are preferable, and more preferably esters derived from phthalic acid, maleic acid, substituted malonic acid and the like and alcohols having 2 or more carbon atoms, and phthalic acid and carbon atoms Number 2
Diesters obtained by the above reaction with alcohols are particularly preferred.

As these polycarboxylic acid esters, it is not always necessary to use the above-mentioned polycarboxylic acid esters as starting materials, and these polycarboxylic acid esters may be used during the preparation of the solid titanium catalyst component (a). A polycarboxylic acid ester may be formed in the step of preparing the solid titanium catalyst component (a) using a compound capable of deriving an ester.

In the present invention, examples of the electron donor other than the polyvalent carboxylic acid which can be used in preparing the solid titanium catalyst component (a) include alcohols, amines, amides, and the like as described below. Ethers, ketones, nitriles, phosphines, stippins, arsines, phosphoramides, esters, thioethers,
Organosilicon compounds such as thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, and amides of metals belonging to Groups I to IV of the Periodic Table And salts.

In the present invention, the solid titanium catalyst component (a) can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium) into contact with an electron donor and a titanium compound. In order to produce the solid titanium catalyst component (a), a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum.

The method for producing the solid titanium catalyst component (a) will be briefly described below with several examples. (1) A method in which a magnesium compound or a complex compound comprising a magnesium compound and an electron donor is reacted with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and / or a reaction assistant such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once. (2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium composite agent. (3) A method in which a titanium compound is further reacted with the reaction product obtained in (2). (4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted. (5) A solid obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. In this method, an electron donor is used at least once. (6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon. (7) A method of contacting a reaction product of a metal acid compound, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

Among the methods for preparing the solid titanium catalyst component (a) described in the above (1) to (8), a method using a liquid titanium halide at the time of preparing the catalyst, a method using a titanium compound, or a method using When using a compound, a method using a halogenated hydrocarbon is preferred.

The amount of each of the above components used in preparing the solid titanium catalyst component (a) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is about 0.01-5
Moles, preferably 0.05 to 2 moles, and about 0.01 to 500 moles, preferably 0.05 to 3 moles, of the titanium compound.
It is used in an amount of 00 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is about 4-200, preferably about 5-100,
The electron donor / titanium (molar ratio) is about 0.1 to 10,
Preferably, it is about 0.2 to about 6, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50.

The solid titanium catalyst component (a) contains a magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 1, 000m
² / g, more preferably about 100 to 800 m ² / g. Since the solid titanium catalyst component (a) forms a catalyst component by integrating the above components, the composition is not substantially changed by hexane washing.

Such a solid titanium catalyst component (a) is
Although it can be used alone, it can also be used after being diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity.

A method for preparing such a highly active titanium catalyst component is described in, for example, JP-A-50-108385.
No. 50-126590, No. 51-20297, No. 51-28189, No. 51-64586, No. 51-92885, No. 51-1366
No. 25, No. 52-87489, No. 52-100596,
No. 52-147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-430
No. 94, No. 55-135102, No. 55-135103,
No. 55-152710, No. 56-811, No. 56-11908, No. 56-18606, No. 58-83006, No. 58-1387
No. 05, No. 58-138706, No. 58-138707,
No. 58-138708, No. 58-138709, No. 58-1387
No. 10, No. 58-138715, No. 60-23404, No.
These are disclosed in JP-A-61-21109, JP-A-61-37802, and JP-A-61-37803.

As the organoaluminum compound catalyst component (b) used in the present invention, a compound having at least one Al-carbon bond in the molecule can be used. Examples of such a compound include: (i) a compound represented by the general formula (R ¹ ) _m Al (O (R ² )) _n H _p X _q (wherein R ¹ and R ² each usually have 1 to 15 carbon atoms) ,
Preferred are hydrocarbon groups containing 1 to 4 hydrocarbon groups, which may be the same or different. X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, and p is 0 ≦ p <
3, q is a number satisfying 0 ≦ q <3, and m +
(ii) an organoaluminum compound represented by the formula (M ¹ ) Al (R ¹ ) ₄ (wherein M ¹ is Li, Na, K, and R ¹ is the above-mentioned (i) And the same as R ¹ in formula ( ¹ ), and a complex alkylated product of a Group I metal and aluminum.

As the organoaluminum compound belonging to the above (i), the following compounds can be exemplified. Formula _{^{(R 1) n Al (O}} (R 2)) in _3-m (wherein, R ¹ R ¹ and R ² in the (i), R
Same as ² . m is a number preferably satisfying 1.5 ≦ m ≦ 3), the general formula ^{_{(R 1) m AlX 3-}} m ( wherein, R ¹ is the (i) the same .X is halogen and R ¹ in, m is a number preferably satisfying 0 <m <3), the general formula ^{_{(R 1) m AlH 3-}} m ( wherein, R ¹ is (i) above same .m preferably 2 ≦ a R ¹ in m <is a number satisfying 3), the general formula _{^{(R 1) m Al (oR}} 2) n X q ( wherein, R ¹ and R ² are the (i) R ¹ in, R
Same as ² . X is halogen, m is 0 <m ≦ 3, n is 0 ≦ n
<3, q is a number satisfying 0 ≦ q <3, and m + n + q
= 3).

As the aluminum compound belonging to the above (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; diethylaluminum ethoxide, dibutylaluminum butoxide and the like Dialkylaluminum alkoxides; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; (R ¹ ) _2.5 A
l (O (R ²⁾⁾ partially alkoxylated alkyl aluminum having an average composition represented by like _0.5;
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Alkyl aluminum dihalides such as alkylaluminum dihalide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Partially hydrogenated Kill aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, can be mentioned partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide.

Examples of the compound similar to the aluminum compound belonging to the above (i) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ A
_{lOAl (C 4 H 9) 2} , (C 2 H 5) 2 AlN (C 2 H 5) A
l (C ₂ H ₅ ) ₂ and methylaminooxane.

Compounds belonging to the above (ii) include L
iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. Among these, it is particularly preferable to use a trialkyl aluminum or an alkyl aluminum to which two or more of the above-mentioned aluminum compounds are bonded.

Examples of the electron donor catalyst component (c) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and oxygen-containing compounds such as alkoxysilanes. An electron donor, a nitrogen-containing electron donor such as ammonia, amine, nitrile, and isocyanate, or the above-mentioned polyvalent carboxylic acid ester can be used.

More specifically, carbon such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol, etc. Alcohols having 1 to 18 atoms; phenol, cresol, xylenol, ethylphenol, propylphenol,
Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol; and 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone. Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate , Ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, benzoic acid Tyl, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, maleate- n-butyl, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di2 phthalate Organic acid esters having 2 to 30 carbon atoms such as -ethylhexyl, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; 2 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride ~ 5 acid halides; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acids such as acetic acid amide, benzoic acid amide and toluic acid amide Amides; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, tolunitrile; acetic anhydride, phthalic anhydride And acid anhydrides such as benzoic anhydride.

As the electron donor (c), an organosilicon compound represented by the following general formula [1] can be used. R _n Si (OR ′) _4-n ... [1] (wherein R and R ′ are hydrocarbon groups, and n is 0 <n
<4. As the organosilicon compound represented by the general formula [1], specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis -m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-
Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltri Ethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane,
2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy (allyloxy) silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane, etc. Can be

Of these, ethyltriethoxysilane, n
-Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxy Preferred are silane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyldiethoxysilane.

Further, as the electron donor catalyst component (c),
An organosilicon compound represented by the following general formula [2] can also be used. SiR ¹ R ² _m (OR ³ ) _3-m [2] (wherein R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² has an alkyl group, a cyclopentyl group and an alkyl group A group selected from the group consisting of a cyclopentyl group, R ³ is a hydrocarbon group, and m is a number satisfying 0 ≦ m ≦ 2.) In the above formula [2], R ¹ is a cyclopentyl group or an alkyl group. a cyclopentyl group having, as the R ^1, other than cyclopentyl group, 2-methylcyclopentyl group, 3-methylstyrene cyclopentyl group, 2-ethyl-cyclopentyl group, a cyclopentyl group having an alkyl group such as 2,3-dimethyl-cyclopentyl group Can be mentioned.

In the above formula [2], R ² is any one of an alkyl group, a cyclopentyl group and a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, An allyl group such as an isopropyl group, a butyl group, and a hexyl group, or a cyclopentyl group having a cyclopentyl group and an alkyl group exemplified as R ¹ can be similarly mentioned.

In the above formula [2], R ³ is a hydrocarbon group, and examples of R ³ include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.

Among these, it is preferable to use an organosilicon compound in which R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, particularly a methyl group or an ethyl group.

Specific examples of the organosilicon compound include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane and dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane,
Monoallocoxysilanes such as dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane can be mentioned. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferable, and organic silicon compounds are particularly preferable.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component (a), the organoaluminum compound catalyst component (b), and the electron donor catalyst component (c) as described above. In the present invention, using the olefin polymerization catalyst, a higher α-olefin, at least one or more monomers selected from the group consisting of ethylene, propylene and 1-butene, and a non-conjugated diene are polymerized. However, using this olefin polymerization catalyst, α-
After prepolymerizing the olefin or higher α-olefin, the catalyst can be used to polymerize (main polymerization) the higher α-olefin, the above monomer, and a non-conjugated diene. At the time of prepolymerization, per 1 g of olefin polymerization catalyst,
The α-olefin or higher α-olefin is prepolymerized in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g.

In the prepolymerization, a catalyst having a considerably higher concentration than the catalyst concentration in the system in the main polymerization can be used.
The concentration of the solid titanium catalyst component (a) in the prepolymerization is as follows:
Usually, about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, and particularly preferably 1 to 50 mmol, per liter of the inert hydrocarbon medium described below, in terms of titanium atoms.
Desirably, it is in the mmol range.

The amount of the organoaluminum catalyst component (b) is
0.1 to 500 g per 1 g of the solid titanium catalyst component (a),
The amount is preferably such that a polymer of 0.3 to 300 g is produced, and usually about 0.1 to 100 mol, preferably about 0.1 to 100 mol per mol of titanium atom in the solid titanium catalyst component (a). It is desirable that the amount is 5 to 50 mol, particularly preferably 1 to 20 mol.

The electron donor catalyst component (c) is used in an amount of 0.1 to 5 per mole of titanium atom in the solid titanium catalyst component (a).
It is preferably used in an amount of 0 mol, preferably 0.5 to 30 mol, particularly preferably 1 to 10 mol.

The prepolymerization is preferably carried out under mild conditions by adding an olefin or a higher α-olefin and the above-mentioned catalyst component to an inert hydrocarbon medium. Specific examples of the inert hydrogen medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use an aliphatic hydrocarbon.
The olefin or higher α-olefin itself can be pre-polymerized in a solvent, or can be pre-polymerized in a substantially solvent-free state.

The higher α-olefin used in the prepolymerization may be the same as or different from the higher α-olefin used in the main polymerization described later. The reaction temperature during the prepolymerization is usually about -20 to + 100 ° C, preferably about -2.
It is desirable to be in the range of 0 to + 80 ° C, more preferably 0 to + 40 ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen may be used. Such a molecular weight modifier has an intrinsic viscosity [η] of about 0.1 of a polymer obtained by prepolymerization, measured in a decalin solvent at 135 ° C.
It is desirable to use an amount of 2 dl / g or more, preferably about 0.5 to 10 dl / g.

As described above, the prepolymerization is carried out so that about 0.1 to 500 g, preferably about 0.3 to 300 g, and particularly preferably 1 to 100 g of polymer is produced per 1 g of the solid titanium catalyst component (a). It is desirable to carry out. If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

The prepolymerization can be carried out batchwise or continuously. The solid titanium catalyst component (a) or the solid titanium catalyst component (a) obtained by prepolymerizing the olefin polymerization catalyst as described above, the organoaluminum catalyst component (b), and the electron donor catalyst component ( c) in the presence of an olefin polymerization catalyst formed from
-Copolymerization (main polymerization) of an olefin, the above monomer, and a non-conjugated diene.

In the copolymerization (main polymerization) of a higher α-olefin, the above monomer, and a non-conjugated diene, in addition to the above olefin polymerization catalyst, an organoaluminum compound catalyst component is used as an olefin polymerization catalyst. The same component as the organoaluminum compound catalyst component (b) used in producing the catalyst can be used. Copolymerization (main polymerization) of higher α-olefin, the above monomer, and non-conjugated diene
In this case, as the electron donor catalyst component, the same component as the electron donor catalyst component (c) used in producing the olefin polymerization catalyst can be used. The organoaluminum compound and the electron donor used in the copolymer (main polymerization) of the higher α-olefin, the above-mentioned monomer, and the non-conjugated diene are not necessarily prepared by preparing the above-mentioned olefin polymerization catalyst. It does not need to be the same as the organoaluminum compound and electron donor used.

The copolymerization (main polymerization) of a higher α-olefin, the above monomer, and a non-conjugated diene is usually performed in a liquid phase. As the reaction medium for the main polymerization, the above-mentioned inert hydrocarbon medium can be used, or an olefin liquid at the reaction temperature can be used.

In the copolymerization (main polymerization) of a higher α-olefin, the above-mentioned monomer, and a non-conjugated diene, the solid titanium catalyst component (a) is usually converted to titanium atoms per liter of polymerization volume. Is about 0.001 to about 1.0 mmol,
Preferably it is used in an amount of about 0.005 to 0.5 mmol. Further, the organoaluminum compound catalyst component (b)
Means that the metal atom in the organoaluminum compound catalyst component (b) is usually about 1 to 2,000 moles, preferably about 5 to 5 moles per mole of titanium atom in the solid titanium catalyst component (a).
It is used in an amount of 500 moles. Further, the electron donor catalyst component (c) is usually added in an amount of about 0.00 per mole of metal atom in the organoaluminum compound catalyst component (b).
It is used in an amount of 1 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.05 to 1 mol.

When hydrogen is used at the time of the main polymerization, the molecular weight of the obtained polymer can be adjusted. In the present invention, the polymerization temperature of the higher α-olefin, the above monomer, and the non-conjugated diene is usually about 20 to 200 ° C, preferably about 40 to 100 ° C, and the pressure is usually normal pressure to 100 kg.
/ Cm ² , preferably from normal pressure to 50 kg / cm ² . In the copolymerization (main polymerization) of the higher α-olefin, the above monomer, and a non-conjugated diene, the polymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin-based thermoplastic elastomer composition according to the present invention contains, in addition to the crystalline polyolefin resin (A) and the higher α-olefin-based copolymer rubber (B),
A softener (C) and / or an inorganic filler (D) can be included.

As the softener (C) used in the present invention, a softener usually used for rubber can be used.
Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tars such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, soybean oil, Fatty oils such as coconut oil; waxes such as tall oil, beeswax, carnauba wax, and lanolin; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, and calcium stearate or metal salts thereof; petroleum resins, cumarone indene Synthetic polymer substances such as resins and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene,
And liquid thiochol.

In the present invention, the softener (C) is used in an amount of 2 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B).
It is used in a proportion of not more than 00 parts by weight, preferably 2 to 100 parts by weight. In the present invention, when the amount of the softening agent (C) exceeds 200 parts by weight, the heat resistance and heat aging resistance of the obtained thermoplastic elastomer composition tend to decrease.

As the inorganic filler (D) used in the present invention, specifically, calcium carbonate, calcium silicate, clay, carion, talc, silica, diatomaceous earth,
Examples include mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, and shirasu balloon.

In the present invention, the inorganic filler (D) is
It is used in an amount of 100 parts by weight or less, preferably 2 to 50 parts by weight, based on 100 parts by weight of the total of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B). In the present invention, when the amount of the inorganic filler (D) exceeds 100 parts by weight, the rubber elasticity and the moldability of the obtained thermoplastic elastomer composition tend to decrease.

The olefin-based thermoplastic elastomer composition according to the present invention contains a crystalline polyolefin resin (A), a higher α-olefin-based copolymer rubber (B), a softener (C), and an inorganic filler ( In addition to D), ethylene / α-olefin copolymer rubbers in which the α-olefin has 3 to 5 carbon atoms, ethylene / α-olefin / non-conjugated diene in which the α-olefin has 3 to 5 carbon atoms A polymer rubber can be included.

Specific examples of the ethylene / α-olefin copolymer rubber include ethylene / propylene copolymer rubber and ethylene / 1-butene copolymer rubber. Specific examples of ethylene / α-olefin / non-conjugated diene copolymer rubber include ethylene / propylene /
5-ethylidene-2-norbornene copolymer rubber, ethylene / propylene / dicyclopentadiene copolymer rubber, and the like.

In the present invention, the above-mentioned copolymer rubber is composed of a crystalline polyolefin resin (A) and a higher α
-It is preferable to use 10 to 200 parts by weight with respect to 100 parts by weight of the total amount of the olefin copolymer rubber (B).

Further, in the present invention, known heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, anti-aging agents, weather-resistant stabilizers, antistatic agents, metal soaps Lubricants such as wax and the like can be used as long as the object of the present invention is not impaired.

The non-crosslinked olefinic thermoplastic elastomer composition according to the present invention is blended with the above-mentioned crystalline polyolefin resin (A) and a higher α-olefin copolymer rubber (B) as required. Softener (C) and / or inorganic filler (D);
-Obtained by mixing with an olefin copolymer rubber, an ethylene / α-olefin / non-conjugated diene copolymer rubber, etc., and then dynamically performing a heat treatment.

The partially crosslinked olefinic thermoplastic elastomer composition according to the present invention comprises the above-mentioned crystalline polyolefin resin (A), higher α-olefin copolymer rubber (B), Softener (C) and / or inorganic filler (D) blended in accordance with the above, and further the above-mentioned ethylene / α-olefin copolymer rubber,
It can be obtained by dynamically heat-treating a mixture with an α-olefin / non-conjugated diene copolymer rubber or the like in the presence of the following organic peroxide to partially crosslink.

Here, "dynamically heat-treating" means kneading in a molten state. As the organic peroxide, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-
Butylperoxy) hexane, 2,5-dimethyl-2,
5-di- (tert-butylperoxy) hexyne-3,
1,3-bis (tert-butylperoxyisopropyl)
Benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate,
Benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, etc. Is mentioned.

Such an organic peroxide is used in a total amount of 100 parts, that is, the total amount of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B).
0.02 to 3 parts by weight, preferably 0.05 to 3 parts by weight
It is used in such an amount that it becomes １1 part by weight. If the amount is less than the above range, the resulting thermoplastic elastomer composition has a low degree of cross-linking, so that heat resistance, tensile properties, elastic recovery, rebound resilience and the like are not sufficient. If the amount is more than the above range, the resulting thermoplastic elastomer composition may have an excessively high degree of cross-linking, resulting in a decrease in moldability.

In the present invention, sulfur, p-quinonedioxime,
p, p'-Dibenzoylquinone dioxime, N-methyl-
Peroxy crosslinking aids such as N, N'-m-phenylenedimaleimide; or polyfunctional methacrylates such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and acrylic methacrylate. Monofunctional, multifunctional vinyl monomers such as vinyl butyrate or vinyl stearate may be incorporated.

By using a compound such as the above-mentioned crosslinking aid, a uniform and mild crosslinking reaction can be expected.
Such a compound such as a crosslinking aid or a polyfunctional vinyl monomer is used in an amount of 100 parts by weight based on the whole object to be treated.
It is usually used in an amount of 2 parts by weight or less, more preferably 0.3 to 1 part by weight.

In order to accelerate the decomposition of the organic peroxide, triethylamine, tributylamine, 2,4,6
-Decomposition accelerators such as tertiary amines such as tri (dimethylamino) phenol and naphthenates such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead and mercury may be used.

The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature is 3 degrees from the melting point of the crystalline polyolefin resin (A).
It is in the range of 00 ° C, usually 150 to 250 ° C, preferably 170 ° C to 225 ° C. The kneading time is usually 1-2.
0 minutes, preferably 1 to 10 minutes. The applied shearing force is a shear rate of 10 to 100,000 sec.
c ^-1 , preferably 100 to 50,000 sec ^-1 .

As a kneading apparatus, a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder can be used, but a non-open type apparatus is preferable.

According to the present invention, the non-crosslinked or partially crosslinked non-crosslinked or partially crosslinked polyolefin resin (A) and the higher α-olefin copolymer rubber (B) are subjected to the above-mentioned dynamic heat treatment. The obtained olefin-based thermoplastic elastomer composition is obtained.

In the present invention, the phrase that the thermoplastic elastomer composition is partially crosslinked means that the gel content measured by the following method is 20% or more, preferably 20 to 99.
5%, particularly preferably in the range of 45 to 98%. Measurement of Gel Content A 100 mg sample of the thermoplastic elastomer composition was weighed, cut into 0.5 mm × 0.5 mm × 0.5 mm strips, and placed in 30 ml of cyclohexane in a closed container. After soaking at 48 ° 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.

From the weight of the dried residue, the weight of all cyclohexane-insoluble components (fibrous fillers, fillers, pigments, etc.) other than the polymer component and the weight of the crystalline polyolefin resin (A) in the sample before immersion in cyclohexane were determined. The reduced value is referred to as “corrected final weight (Y)”.

On the other hand, the higher α-olefin copolymer (B) in the sample is referred to as “corrected initial weight (X)”.
Here, the gel content is determined by the following equation.

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

[0112]

The olefin-based thermoplastic elastomer composition according to the present invention contains a specific crystalline polyolefin resin (A) and a specific higher α-olefin-based copolymer rubber (B) in a specific ratio. Therefore, even in the case of non-crosslinked, it is excellent in tensile strength, elongation at break, rubbery properties and heat resistance as compared with conventionally known non-crosslinked thermoplastic elastomers.

The olefin thermoplastic elastomer composition according to the present invention contains a specific crystalline polyolefin resin (A) and a specific higher α-olefin copolymer rubber (B) at a specific ratio. In particular, when partially crosslinked, it is superior to conventional vulcanized rubber in tensile strength, elongation at break and rubber-like properties.

Further, according to the method for producing an olefinic thermoplastic elastomer composition of the present invention, a partially crosslinked olefinic thermoplastic elastomer composition having the above-mentioned effects can be provided.

Hereinafter, the present invention will be described with reference to Examples.
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. (2) Elongation at break: 200 in accordance with JIS K 6301
The breaking elongation at break was measured at a tensile speed of mm / min. (3) Heat Sag: A test piece (size 128 mm × 25 mm × 3 mm, length 128 m) is attached to a cantilever fixture.
The fixed part of m is 28 mm, and the measuring part is 100 mm)
Was held horizontally and left at 90 ° C. or 120 ° C. for 1 hour, and the amount of deformation of the free end hanging down was measured with a caliper. (4) Permanent elongation: Measured according to JIS K6301. However, the retained length was a length corresponding to 100% elongation.

[Examples of non-crosslinked thermoplastic elastomer composition]

[0118]

Reference Examples 1-3 Preparation of Solid Titanium Catalyst Component (a) 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a homogeneous solution. Thereafter, 21.3 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of titanium tetrachloride 2 was kept at -20 ° C.
The entire amount was dropped into 00 ml over 1 hour. After completion of the charging, the temperature of the mixed solution was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 5.22 g of diisobutyl phthalate was added, and the mixture was kept under stirring at the same temperature for 2 hours. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After the completion of the reaction, the solid portion was collected by hot filtration again,
The plate was washed sufficiently with decane and hexane at 10 ° C. until no free titanium compound was detected in the washing solution. The titanium catalyst component (a) prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (a) thus obtained was 2.2% by weight of titanium, 58.1% by weight of chlorine, 19.2% by weight of magnesium, and 10.7% by weight of diisobutyl phthalate. [Preliminary polymerization] In a 400 ml glass polymerization vessel equipped with a stirring blade, 60 ml of decane, 2 ml of a 1 mmol / ml decane solution of triisobutylaluminum, and 18.6 ml of a decane slurry of the solid titanium catalyst component (a) were used.
(1 mmol in terms of titanium atoms) and 30 ℃
The temperature rose. The solution was then added to 1-octene 8.4.
ml was added dropwise over 1 hour, and the reaction was continued for another 1 hour. After completion of the reaction, the reaction solution was directly used for main polymerization. [Main polymerization] Using a 4 liter glass polymerization vessel equipped with a stirring blade, 1-octene, propylene,
-A copolymerization reaction with methyl-1,6-octadiene was carried out.

That is, a decane solution of 1-octene and 7-methyl-1,6-octadiene was added from the top of the polymerization vessel to
1-octene concentration in the polymerization vessel is 200ml / l, 7-octene
A decane slurry solution of the solid titanium catalyst component (a), which was preliminarily polymerized as a catalyst, was used as a catalyst at a rate of 1.4 liters per hour so that the methyl-1,6-octadiene concentration was 6 ml / l. 0.4 liter / h of decane solution of triisobutylaluminum at a rate of 0.03 mmol / l and 1.2 liter / h of trimethyl at a concentration of 3 mmol / l in a polymerization vessel. A decane solution of methoxysilane was added at an hourly rate such that the silane concentration in the polymerization vessel was 1 mmol / l.
Each was continuously fed into the polymerization vessel at a rate of 1 liter. On the other hand, the polymerization solution in the polymerization vessel from the lower part of the polymerization vessel is always 2
It was continuously withdrawn to liters. From the top of the polymerization vessel, propylene was supplied at 20 liters / hour, hydrogen was supplied at 1 liter / hour, and nitrogen was supplied at 50 liters / hour. The copolymerization reaction was carried out at 50 ° C. by circulating warm water through a jacket attached outside the polymerization vessel.

Next, a small amount of isobutyl alcohol was added to the polymerization solution withdrawn from the lower part of the polymerization vessel to terminate the polymerization, and then the polymerization solution was poured into a large amount of methanol to precipitate a copolymer. After the copolymer is sufficiently washed with methanol, it is dried under reduced pressure at 120 ° C. for 1 day and 1-octene.
Propylene-7-methyl-1,6-octadiene copolymer rubber (A-1) was obtained at a rate of 195 g / h.

The obtained 1-octene / propylene / 7-
Methyl-1,6-octadiene copolymer rubber (A-1)
Has a molar ratio of 1-octene to propylene (1-octene / propylene) of 70/30 and an iodine value of 5.
6, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 3.7 dl / g.

Table 1 shows the preparation conditions and the like in this polymerization. Table 1 also shows the intrinsic viscosity [η] and iodine value of these copolymer rubbers.

[0123]

[Table 1]

[0124]

Example 1 50 parts by weight of the 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) obtained in Reference Example 1 and MFR (ASTM D12
38-65T, 230 ° C.) of 11 g / 10 min and a density of 0.91 g / cm ³ of 50 parts by weight of polypropylene.
After kneading at 180 ° C. for 10 minutes using a Banbury mixer, the kneaded material was passed through an open roll and cut with a sheet cutter to obtain square pellets.

Next, a predetermined test piece was prepared by injection molding using the square pellet, and its physical properties were measured in accordance with the above-mentioned measuring methods. Table 2 shows the results.

[0126]

Comparative Example 1 In Example 1, instead of the 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1), the ethylene content was 80 mol% and the iodine value was 10, and the intrinsic viscosity [η] is 4.6 dl.
/ G of an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber was prepared in the same manner as in Example 1 to prepare an olefin-based thermoplastic elastomer composition, and its physical properties were measured.

Table 2 shows the results.

[0128]

[Table 2]

[0129]

Example 2 In Example 1, the amounts of the 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) and polypropylene were changed to 7 respectively.
An olefin-based thermoplastic elastomer composition was prepared and the physical properties were measured in the same manner as in Example 1 except that the amount was changed to 5 parts by weight or 25 parts by weight.

Table 3 shows the results.

[0131]

COMPARATIVE EXAMPLE 2 In Example 2, 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) was replaced with ethylene-propylene / 5-ethylidene- An olefin-based thermoplastic elastomer composition was prepared and its physical properties were measured in the same manner as in Example 2 except that the 2-norbornene copolymer rubber was used.

Table 3 shows the results.

[0133]

[Table 3]

[0134]

Example 3 In Example 1, in addition to 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) and polypropylene, a mineral oil-based softening agent [manufactured by Idemitsu Kosan Co., Ltd.] , PW-380], and 20 parts by weight of talc [ET-5, manufactured by Matsumura Sangyo Co., Ltd.] were prepared in the same manner as in Example 1 to prepare an olefin-based thermoplastic elastomer composition. And its physical properties were measured.

Table 4 shows the results.

[0136]

Comparative Example 3 In Example 3, the ethylene / propylene / 5-ethylidene- of Comparative Example 1 was used instead of the 1-octene / propylene / 7-methyl-1,6-octadiene copolymer rubber (B-1). An olefin-based thermoplastic elastomer composition was prepared and the physical properties were measured in the same manner as in Example 3, except that the 2-norbornene copolymer rubber was used.

Table 4 shows the results.

[0138]

[Table 4]

[Examples Related to Partially Crosslinked Thermoplastic Elastomer Composition]

[0140]

Example 4 50 parts by weight of the 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) obtained in Reference Example 1 and 50 parts by weight of the polypropylene of Example 1 In addition, organic peroxide (2,5-dimethyl-2,
5-di- (tert-butylperoxy) hexyne-3)
After adding 0.2 parts by weight and 0.3 parts by weight of divinylbenzene and thoroughly mixing in a Henschel mixer, using a Banbury mixer, kneading at 180 ° C. for 10 minutes,
The kneaded material was passed through an open roll and cut with a sheet cutter to obtain square pellets.

Next, a predetermined test piece was prepared by injection molding using the square pellet, and its physical properties were measured according to the above-mentioned measuring methods. Table 5 shows the results.

[0142]

Comparative Example 4 In Example 4, the ethylene-propylene / 5-ethylidene-comparative compound of Comparative Example 1 was used in place of the 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1). An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 4 except that the 2-norbornene copolymer rubber was used, and the physical properties were measured.

Table 5 shows the results.

[0144]

[Table 5]

[0145]

Example 5 In Example 4, the compounding amounts of 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) and polypropylene were each 7
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 4 except that 5 parts by weight and 25 parts by weight were used, and the physical properties were measured.

The results are shown in Table 6.

[0147]

Comparative Example 5 In Example 5, instead of the 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1), ethylene-propylene-5-ethylidene-comparative of Comparative Example 1 was used. An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the 2-norbornene copolymer rubber was used, and the physical properties were measured.

Table 6 shows the results.

[0149]

[Table 6]

[0150]

Example 6 In Example 4, in addition to 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) and polypropylene, a mineral oil-based softening agent [manufactured by Idemitsu Kosan Co., Ltd.] , PW-380] and 20 parts by weight of talc [ET-5, manufactured by Matsumura Sangyo Co., Ltd.] were prepared in the same manner as in Example 4 to prepare an olefin-based thermoplastic elastomer composition. And its physical properties were measured.

Table 7 shows the results.

[0152]

Comparative Example 6 The procedure of Example 6 was repeated, except that the 1-octene-propylene-7-methyl-1,6-octadiene copolymer rubber (B-1) was replaced with ethylene-propylene / 5-ethylidene- An olefin-based thermoplastic elastomer composition was prepared and the physical properties were measured in the same manner as in Example 6, except that the 2-norbornene copolymer rubber was used.

Table 7 shows the results.

[0154]

[Table 7]

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for preparing an olefin polymerization catalyst component used in producing a higher α-olefin copolymer rubber used in the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 23/02 C08L 23/02 (72) Inventor Masaaki Kawasaki 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui (56) References JP-A-56-151741 (JP, A) JP-A-64-31845 (JP, A) JP-A-4-76026 (JP, A) JP-A-4-28706 (JP, A) JP-A-5-25301 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/02-23/24 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A crystalline polyolefin resin (A)
0 parts by weight, higher α-olefin copolymer rubber (B)
90 to 40 parts by weight [the total amount of (A) and (B) is 10
0 parts by weight], wherein the higher α-olefin-based copolymer rubber (B) comprises: a higher α-olefin having 6 to 20 carbon atoms; It comprises at least one or more monomers selected from the group consisting of ethylene, propylene and 1-butene, and a non-conjugated diene represented by the following general formula [I], and has an iodine value of 0.1 to 50. And the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 1.0 to 10.0 d.
an olefinic thermoplastic elastomer composition characterized by being in the range of 1 / g; [In the formula, n is an integer of 1 to 5, and R ¹ has ¹ carbon atom.
Represents to 4 alkyl groups, R ² and R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ²
And R ³ cannot both be hydrogen atoms]. 2. The total amount of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B) is 1
2. The olefin-based thermoplastic elastomer according to claim 1, comprising 2 to 100 parts by weight of a softening agent (C) and / or 2 to 50 parts by weight of an inorganic filler (D) based on 00 parts by weight. Composition. 3. The method according to claim 1, wherein the olefin-based thermoplastic elastomer composition is non-crosslinked.
3. The olefin-based thermoplastic elastomer composition according to 1.). 4. The olefinic thermoplastic elastomer composition according to claim 1, wherein the olefinic thermoplastic elastomer composition is partially crosslinked. 5. A crystalline polyolefin resin (A) 10-6.
0 parts by weight, a higher α-olefin having 6 to 20 carbon atoms, at least one kind of monomer selected from the group consisting of ethylene, propylene and 1-butene, and represented by the following general formula [I] A non-conjugated diene, an iodine value in the range of 0.1 to 50, and an intrinsic viscosity [η] of 1.0 to 10.0 d measured in a decalin solvent at 135 ° C.
A mixture of 90 to 40 parts by weight of a higher α-olefin copolymer rubber (B) having a total amount of (A) and (B) of 100 parts by weight in the range of 1 / g was prepared by using an organic peroxide. A method for producing an olefin-based thermoplastic elastomer composition, characterized in that the composition is subjected to dynamic heat treatment in the presence of a product to partially crosslink. [In the formula, n is an integer of 1 to 5, and R ¹ has ¹ carbon atom.
Represents to 4 alkyl groups, R ² and R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ²
And R ³ cannot both be hydrogen atoms].