JPH0770376A - Thermoplastic olefin elastomer composition - Google Patents

Abstract

PURPOSE:To provide the title composition which, when used in an uncrosslinked state or a partially crosslinked state, can give a molding improved in tensile strength, elongation at break and rubber elasticity by mixing a crystalline polyolefin resin with a specified higher alpha-olefin copolymer rubber. CONSTITUTION:10-60 pts.wt. crystalline polyolefin resin (A) having a melt index of 0.01-100g/10min at 230 deg.C is mixed with 90-40 pts.wt. higher alpha-olefin copolymer rubber (B) comprising a 6-20 C higher alpha-olefin (a), an aromatic-ring-containing vinyl monomer (b) of formula I wherein n is 0-5; R<1> to R<3> are each H or 1-8 C alkyl and a nonconjugated diene (c) of formula II wherein n is 1-5; R<4> is 1-4 C alkyl; and R<5> and R<6> are H or 1-8 C alkyl and having an (a)/(b) molar ratio of 95/3 to 30/70, a component (c) content of 0.01-30mol% and an intrinsic viscosity [eta] of 0.1-10.0dl/g as measured in decalin at 135 deg.C to obtain a thermoplastic olefin elastomer. This elastomer is optionally mixed with a softener and/or an inorganic filler.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin-based thermoplastic elastomer composition, more specifically, a tensile strength comprising a crystalline polyolefin resin (A) and a higher α-olefin-based copolymer rubber (B), The present invention relates to an olefin-based thermoplastic elastomer composition having excellent elongation at break and rubber elasticity.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are widely used as energy-saving and resource-saving type elastomers, especially as substitutes for vulcanized rubber for automobile parts, industrial machine parts, electronic / electric equipment parts, building materials, etc. There is.

The olefinic thermoplastic elastomer is used in a crosslinked state or a non-crosslinked state. The thermoplastic elastomer used in the non-crosslinked state (hereinafter referred to as the non-crosslinked thermoplastic elastomer) has little variation in quality because it does not involve a crosslinking reaction and the manufacturing cost is low, but the two are compared in terms of performance. Then, in terms of tensile strength, elongation at break, rubber-like properties (for example, permanent elongation, compression set) and heat resistance, the olefin-based thermoplastic elastomer (hereinafter , Crosslinked thermoplastic elastomer) is superior. This is AYCora
n et al. (Rubber Chemistry and Technology, 53 (1
980), p. 141) and is widely known.

Non-crosslinked or crosslinked olefinic thermoplastic elastomers are described in, for example, Japanese Patent Publication No. 53-2.
1021, JP-B-55-18448, JP-B-56-15741, JP-B-56-15742, JP-B-58-46138,
Japanese Patent Publication No. 58-56575, Japanese Patent Publication No. 59-30376, Japanese Patent Publication No.
62-938 and Japanese Patent Publication No. 62-59139.

As described above, the olefinic thermoplastic elastomer is used in a non-crosslinked state or a crosslinked state. In the case of the non-crosslinked type thermoplastic elastomer, as compared with the conventionally known non-crosslinked type thermoplastic elastomer, It has been desired to develop an olefin-based thermoplastic elastomer composition having excellent tensile strength, elongation at break, rubber-like properties (permanent elongation, compression set, etc.) and heat resistance.

Further, in the case of a cross-linkable thermoplastic elastomer, the appearance of an olefin-based thermoplastic elastomer composition which is superior in tensile strength, elongation at break and rubber-like properties as compared with conventionally known vulcanized rubber is desired. It was rare.

[0007]

The present invention is excellent in tensile strength, elongation at break, rubber property and heat resistance even when used in a non-crosslinked state, and when used in a crosslinked state,
An object of the present invention is to provide an olefin-based thermoplastic elastomer composition which is superior to conventional vulcanized rubbers in tensile strength, elongation at break and rubber-like properties.

[0008]

SUMMARY OF THE INVENTION The olefinic thermoplastic elastomer composition according to the present invention comprises a crystalline polyolefin resin (A) 1
Olefin heat composed of 0 to 60 parts by weight and higher α-olefin copolymer rubber (B) 90 to 40 parts by weight [the total amount of (A) and (B) is 100 parts by weight]. A plastic elastomer composition, wherein the higher α-olefin copolymer rubber (B) comprises a higher α-olefin having 6 to 20 carbon atoms and an aromatic ring-containing vinyl monomer represented by the following general formula [I]. And a non-conjugated diene represented by the following general formula [II], which is a higher α-olefin copolymer rubber, wherein (i) the molar ratio of the higher α-olefin and the aromatic ring-containing vinyl monomer [higher α -Olefin / aromatic ring-containing vinyl monomer] is 95/5 to 30/70,
(Ii) the content of the non-conjugated diene is 0.01 to 30 mol%,
(Iii) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C is in the range of 0.1 to 10.0 dl / g.

[0009]

[Chemical 3]

In the formula [I], n is an integer of 0 to 5 and R
¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0011]

[Chemical 4]

In the formula [II], n is an integer of 1 to 5 and R
⁴ represents an alkyl group having 1 to ⁴ carbon atoms, and R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However,
Neither R ⁵ nor R ⁶ is a hydrogen atom.

The olefinic thermoplastic elastomer composition according to the present invention contains 2 parts by weight per 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the higher α-olefinic copolymer (B). ˜100 parts by weight of softener (C) and / or 2 to 50 parts by weight of inorganic filler (D) may be included.

The olefinic thermoplastic elastomer composition according to the present invention is excellent in tensile strength, elongation at break, rubber property and heat resistance even when used in a non-crosslinked state.

The olefinic thermoplastic elastomer composition according to the present invention is more excellent in tensile strength, elongation at break and rubber-like properties than conventional vulcanized rubber, especially when used in a partially crosslinked state. .

[0016]

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

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

Crystalline Polyolefin Resin (A) Crystalline Polyolefin Resin (A) Used in the Present Invention
Comprises a crystalline, high molecular weight solid product obtained by polymerizing one or more monoolefins by either the high pressure or low pressure processes. Such resins include, for example, isotactic and syndiotactic monoolefin polymer resins, but representative resins of these are commercially available.

As a suitable raw material olefin of the crystalline polyolefin resin (A), specifically, ethylene,
Propylene, 1-butene, 1-hexene, 1-pentene, 1-heptene, 2-methyl-1-propene, 3-methyl-1-pentene,
4-Methyl-1-pentene, 5-methyl-1-hexene, 1-octene, 1-decene and mixed olefins obtained by mixing two or more kinds of these olefins can be mentioned.

The polymerization mode may be a random type or a block type, and any polymerization mode capable of obtaining a resinous material may be adopted. The crystalline polyolefin resin (A) used in the present invention has a melt index (ASTM D 1
238-65T, 230 ° C) is 0.01 to 100 g / 10 minutes,
Particularly, it is preferably in the range of 0.05 to 50 g / 10 minutes.

The crystalline polyolefin resin (A) is
It has the role of 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, 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 proportions by weight.

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

Higher α-olefin Copolymer (B) The higher α-olefin copolymer rubber (B) used in the present invention comprises a specific higher α-olefin, a specific aromatic ring-containing vinyl monomer, and It is a copolymer in which a specific non-conjugated diene is present in a specific ratio.

[Higher α-Olefin] The higher α-olefin used in the present invention is a higher α-olefin having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Hexene-1, Heptene-1, Octene-
1, nonene-1, decene-1, undecene-1, dodecene-1,
Tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, nonadecene-1, eicosene-1,9-methyl-decene-1,11-methyl-dodecene-1,12-
Ethyl-tetradecene-1 and the like.

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

[Aromatic Ring-Containing Vinyl Monomer] The aromatic ring-containing vinyl monomer used in the present invention is represented by the following general formula [I].

[0027]

[Chemical 5]

(In the formula, n is an integer of 0 to 5, R ¹ ,
R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) Specific examples of the aromatic ring-containing vinyl monomer include styrene, allylbenzene and 4- Phenylbutene
-1,3-phenylbutene-1,4- (4-methylphenyl) butene-1,4- (3-methylphenyl) butene-1,4- (2-methylphenyl) butene-1,4- (4 -Ethylphenyl) butene-
1,4- (4-butylphenyl) butene-1,5-phenylpentene-1,4-phenylpentene-1,3-phenylpentene-
1,5- (4-methylphenyl) pentene-1,4- (2-methylphenyl) pentene-1,3- (4-methylphenyl) pentene-1,6-phenylhexene-1,5-phenylhexene- 1,
4-phenylhexene-1,3-phenylhexene-1,6- (4-
Methylphenyl) hexene-1,5- (2-methylphenyl)
Hexene-1,4- (4-methylphenyl) hexene-1,3-
(2-Methylphenyl) hexene-1,7-phenylheptene
-1,6-phenylheptene-1,5-phenylheptene-1,4-
Phenylheptene-1,8-phenyloctene-1,7-phenyloctene-1,6-phenyloctene-1,5-phenyloctene-1,4-phenyloctene-1,3-phenyloctene-
Examples include 1,10-phenyldecene-1.

In the present invention, the aromatic ring-containing vinyl monomer as described above may be used alone or as a mixture of two or more kinds. Of the above aromatic ring-containing vinyl monomers, allylbenzene and 4-phenylbutene-1
Is preferred, and 4-phenylbutene-1 is particularly preferred.

[Non-Conjugated Diene] The non-conjugated diene used in the present invention is represented by the following general formula [II].

[0031]

[Chemical 6]

(Wherein n is an integer of 1 to 5, R ⁴ is an alkyl group having 1 to 4 carbon atoms, R ⁵ and R ⁶ are hydrogen atoms or an alkyl group having 1 to 8 carbon atoms. , R ⁵
Neither R ⁶ nor R ⁶ is a hydrogen atom. ) As the non-conjugated diene as described above, specifically, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,
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 can be mentioned.

In the present invention, the above non-conjugated dienes may be used alone or as a mixture of two or more kinds. In addition to the non-conjugated dienes as described above, other copolymerizable monomers such as ethylene,
Propylene, 1-butene, 4-methyl-1-pentene, etc.
You may use it in the range which does not impair the objective of this invention.

The molar ratio of the higher α-olefin constituting the higher α-olefin copolymer rubber (B) used in the present invention and the aromatic ring-containing vinyl monomer (higher α-olefin / aromatic ring-containing vinyl monomer) is , 30 / 70-95
/ 5, preferably 40/60 to 90/10, more preferably 50/50 to 80/20.

The value of the above molar ratio is a value obtained by measurement by the ¹³ C-NMR method. In the present invention, a higher α-olefin copolymer rubber (B) having excellent processability can be obtained by copolymerizing a higher α-olefin with an aromatic ring-containing vinyl monomer.

The content of the non-conjugated diene constituting the higher α-olefin copolymer (B) used in the present invention is 0.
01 to 30 mol%, preferably 0.05 to 25 mol%,
It is particularly preferably in the range of 0.1 to 20 mol%.

The intrinsic viscosity [η] of the higher α-olefin copolymer rubber (B) used in the present invention measured in a decalin solvent at 135 ° C. is 0.1-10.0 dl / g, preferably 1. It is in the range of 5 to 7.0 dl / g. This characteristic value is a measure showing the molecular weight of the higher α-olefin copolymer rubber (B) used in the present invention. When the molecular weight is in the above range, properties such as tensile strength and elongation at break are obtained. An excellent copolymer can be obtained.

The higher α-used in the present invention as described above
The olefin-based copolymer rubber (B) can be produced by the following method. The higher α-olefin copolymer rubber (i) used in the present invention is represented by the higher α-olefin having 6 to 20 carbon atoms and the above general formula [I] in the presence of an olefin polymerization catalyst. It is obtained by copolymerizing an aromatic ring-containing vinyl polymer with a non-conjugated diene represented by the above general formula [II].

The olefin polymerization catalyst used in the present invention is composed of, for example, 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 flow chart of a method for preparing an olefin polymerization catalyst component 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 is
It is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such 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, examples of the titanium compound used for preparing the solid titanium catalyst component (a) include Ti (OR) gX
_4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be mentioned.

More specifically, TiCl ₄ , TiBr ₄ ,
Titanium tetrahalides such as TiI ₄ ; Ti (OC
H ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O-n-C ₄
H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C
₄ H ₉ ) Br _{3 and} other trihalogenated alkoxy titanium; T
i (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , T
_{i (O-n-C 4} H 9) 2 Cl 2, Ti (OC 2 H 5) 2 Br 2
Dihalogenated dialkoxytitanium such as; Ti (OC
H ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-n-C
₄ H ₉ ) ₃ Cl, monohalogenated trialkoxy titanium such as 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-
Examples thereof include tetraalkoxytitanium such as C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Among these, halogen-containing titanium compounds,
In particular, titanium tetrahalide is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds 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.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such reducing magnesium compounds include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, 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 organoaluminum compound described later. Further, these magnesium compounds may be liquid or solid.

Specific examples of the magnesium compound having no reducing property include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, magnesium ethoxy chloride, and magnesium isopropoxy 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 Alkoxy magnesium such as;
Examples thereof include allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylates 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 preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reducible magnesium compound is prepared from polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, etc. It may be brought into contact with the compound.

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

In the present invention, among these, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferably used. To be

In the present invention, examples of the electron donor used for the preparation of the solid titanium catalyst component (a) include organic carboxylic acid esters and polyvalent carboxylic acid esters which will be described later. Specifically, they are represented by the following formula. And a compound having a skeleton.

[0051]

[Chemical 7]

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. At least one of R ³ and R ⁴ is preferably a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a ring structure. Examples of the substituted hydrocarbon group include substituted hydrocarbon groups containing a hetero atom such as N, O and S, and examples thereof include -COC- and-.
_{COOR, -COOH, -OH, -SO 3} H, -C-N
-C -, - and hydrocarbon group substituted with a structure such as NH _2.

Of 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, diisobutyl α-methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, butyl. Diethyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyl diisobutylmalonate, diethyl dinormalbutylmalonate, dimethyl maleate,
Monooctyl maleate, diisooctyl maleate,
Diisobutyl maleate, butyl diisobutyl maleate, diethyl butyl maleate, diisopropyl β-methyl glutarate, diallyl ethyl succinate, di fumarate
-2-Ethylhexyl, diethyl itaconate, diisobutyl itaconate, diisooctyl citracone, dimethyl citracone and other fatty acid polycarboxylic acid esters;
Aliphatic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, phthalate Acid monoisobutyl,
Diethyl phthalate, ethyl isobutyl phthalate, mononormal butyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n phthalate -Heptyl, di-2-ethylhexyl phthalate,
Aromatic polycarboxylic acid esters such as didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate; 3,4-furandicarboxylic acid, etc. Examples thereof include esters derived from heterocyclic polycarboxylic acids.

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

Among these polyvalent carboxylic acid esters,
A compound having a skeleton represented by the above-mentioned general formula is preferable, more preferably an ester derived from phthalic acid, maleic acid, substituted malonic acid and the like and an alcohol having 2 or more carbon atoms, and phthalic acid and a carbon atom. Number 2
Diesters obtained by the reaction with the above alcohols are particularly preferable.

As the polyvalent carboxylic acid ester, it is not always necessary to use the polyvalent carboxylic acid ester as described above as a starting material, and the polyvalent carboxylic acid ester may be used in the process of preparing the solid titanium catalyst component (a). A compound capable of inducing an ester may be used to form a polyvalent carboxylic acid ester in the step of preparing the solid titanium catalyst component (a).

In the present invention, electron donors other than polyvalent carboxylic acids that can be used when preparing the solid titanium catalyst component (a) include alcohols, amines, amides, as described below. Ethers, ketones, nitriles, phosphines, stipines, arsines, phosphoramides, esters, thioethers,
Organosilicon compounds such as thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, and 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 magnesium metal), electron donor and titanium compound into contact with each other. In order to produce the solid titanium catalyst component (a), a known method of preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor can be adopted. The above components may be contacted in the presence of other reaction reagents such as silicon, phosphorus and aluminum.

The production method of these solid titanium catalyst components (a) will be briefly described below with some examples. (1) A method of reacting a magnesium compound or a complex compound composed of a magnesium compound and an electron donor with a titanium compound in a liquid phase.

This reaction may be carried out in the presence of a grinding aid or the like. Further, when the reaction is performed as described above, the solid compound may be pulverized. Furthermore, each component may be pretreated with an electron donor and / or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound when the reaction is carried out as described above. In addition,
In this method, the electron donor is used at least once. (2) Liquid magnesium compound having no reducing property,
A method of reacting a liquid titanium compound in the presence of an electron donor to deposit a solid titanium composite agent. (3) A method of further reacting the reaction product obtained in (2) with a titanium compound. (4) In the reaction product obtained in (1) or (2),
A method of further reacting an electron donor and a titanium compound. (5) A solid compound obtained by pulverizing a magnesium compound or a complex compound composed of a magnesium compound and an electron donor in the presence of a titanium compound is treated with halogen, a halogen compound or an aromatic hydrocarbon. Method. In this method, the magnesium compound or the complex compound composed of the magnesium compound and the electron donor may be ground in the presence of a grinding aid. Alternatively, the magnesium compound or the complex compound composed of the magnesium compound and the electron donor may be pulverized in the presence of the titanium compound, pretreated with a reaction aid, and then treated with halogen or the like. Examples of the reaction aid include organic aluminum compounds and halogen-containing silicon compounds. In this method, the electron donor is used at least once. (6) A method of treating the compound obtained in (1) to (4) above with halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of bringing a reaction product of a metal acid compound, dihydrocarbyl magnesium and a halogen-containing alcohol into contact with an electron donor and a titanium compound. (8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium 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 (1) to (8) above, a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a titanium compound is used. When using the compound, a method using a halogenated hydrocarbon is preferable.

The amount of each of the above-mentioned 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 1 mole of the magnesium compound. 0.01-5
The amount of the titanium compound is about 0.01 to 500 mol, preferably 0.05 to 30 mol, preferably in an amount of 0.05 to 2 mol.
Used in an amount of 0 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 0.1-10,
Desirably, 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 magnesium halide having a smaller crystal size than that of commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 1000 m ^2. / G,
More preferably, it is about 100 to 800 m ² / g. Since the solid titanium catalyst component (a) forms the catalyst component by integrating the above components, the composition thereof is not substantially changed by washing with hexane.

Such solid titanium catalyst component (a) is
Although it can be used alone, it can also be used by diluting it with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound or a polyolefin. When a diluent is used, it exhibits high catalytic activity even if it has a specific surface area smaller than that described above.

The method of preparing such a high activity titanium catalyst component is described in, for example, JP-A-50-108385 and JP-A-5-108385.
0-126590, 51-20297, 51-28189, 51-64586, 51-92885, 51-13662.
No. 5, gazette 52-87489 gazette, gazette 52-100596 gazette, gazette 52
-147688, 52-104593, 53-2580, 53-40093, 53-40094, 53-43094
No. 55, No. 55-135102, No. 55-135103, No. 55
-152710, 56-811, 56-11908,
56-18606, 58-83006, 58-138705, 58-138706, 58-138707, 58-1.
38708, 58-138709, 58-138710, 58-138715, 60-23404, 61-2110
No. 9, No. 61-37802, No. 61-37803.

As the organoaluminum compound catalyst component (b) used in the present invention, a compound having at least one aluminum-carbon bond in the molecule can be used.
Such compounds include, for example, (a) general formula (R ¹ ) m Al (O (R ² )) n Hp Xq (wherein R ¹ and R ² have usually 1 to 15 carbon atoms, preferably Is a hydrocarbon group containing 1 to 4, which may be the same or different from each other, X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, and p is 0 ≦ p <3. , Q
Is a number 0 ≦ q <3, and m + n + p + q = 3
An organic aluminum compound represented by the formula: (b) a general formula (M ¹ ) Al (R ¹ ) ₄ (wherein M ¹ is Li, Na, K, and R ¹ is the same as above) Examples thereof include complex alkylated products of a Group 1 metal and aluminum.

Examples of the organoaluminum compound belonging to (a) above include the following compounds. General formula (R ¹ ) n Al (O (R ² )) _3-m (wherein R ¹ and R ² are the same as above. M is preferably a number of 1.5 ≦ m ≦ 3), Formula (R ¹ ) m AlX _3-m (wherein R ¹ is the same as described above, X is halogen, and m is preferably 0 <m <3), general formula (R ¹ ) m AlH _3-m ( In the formula, R ¹ is the same as above, and m is preferably 2 ≦ m <3.
Of the general formula (R ¹ ) m Al (OR ² ) n Xq (wherein R ¹ and R ² are the same as above. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
And the like.

As the aluminum compound belonging to (a), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkenyl aluminum such as triisoprenyl aluminum; diethyl aluminum ethoxide, dibutyl aluminum butoxide and the like. Dialkyl aluminum alkoxide; ethyl aluminum sesquiethoxide,
Alkyl aluminum sesquialkoxides such as butyl aluminum sesquibutoxide, (R ¹ ) _2.5 Al (O
(R ² )) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; Ethylaluminum sesquichloride, butylaluminum sesquichloride Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum hydride, dibutyl aluminum hydride Dialkyl aluminum hydride such as; ethyl aluminum dihydride, Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ropylaluminium dihydride; partially alkoxylated and halogenated such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide Alkyl aluminum can be mentioned.

As a compound similar to the above (a)
Is 2 or more aluminum via oxygen atom or nitrogen atom
Can include organoaluminum compounds bound to
It Examples of such a compound include (C₂H_Five)₂
AlOAl (C₂H_Five)₂, (C_FourH₉)₂AlOAl (C_Four
H₉)₂, (C ₂H_Five)₂AlN (C₂H_Five) Al (C
₂H_Five)₂, Methylaminooxane, etc.
Wear.

As the compound belonging to (b) above, Li
Al (C₂H_Five)_Four, LiAl (C₇H ₁₅)_FourGive up
be able to. Among these, especially trialkylal
Minium or two or more aluminum compounds mentioned above
It is preferable to use an alkylaluminum having a bound substance.
Good

As the electron donor catalyst component (c), alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid or inorganic acid esters, ethers, acid amides, acid anhydrides, alkoxysilanes and other oxygen-containing compounds are used. An electron donor, a nitrogen-containing electron donor such as ammonia, amine, nitrile, or isocyanate, or the polyvalent carboxylic acid ester as described above 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 and isopropylbenzyl alcohol. Alcohols having 1 to 18 atoms; phenol, cresol, xylenol, ethylphenol, propylphenol,
6 to 20 carbon atoms which may have a lower alkyl group, such as nonylphenol, cumylphenol and naphthol
Phenols; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, and other ketones having 3 to 15 carbon atoms;
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, propionic acid. Ethyl, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, -n-butyl maleate, methylmalon Diisobutyl, cyclohexene carboxylic di -n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di -n
-Butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and other organic acid esters having 2 to 30 carbon atoms;
Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; number of carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether 2 to 20 ethers; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine, etc. Amines; nitriles such as acetonitrile, benzonitrile, tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride, etc. are used.

As the electron donor (c), an organosilicon compound represented by the following general formula [1] can be used. Rn Si (OR ') _4-n ... [1] (In the formula, R and R'are hydrocarbon groups, and n is 0 <n.
It is a number that satisfies <4. ) Specific examples of the organosilicon compound represented by the above general formula [1] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyl Dimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane Silane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-
Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane,
Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like are used.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p -
Tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane,
Diphenyldiethoxysilane is preferred.

Further, as the electron donor catalyst component (c),
It is also possible to use an organosilicon compound represented by the following general formula [2]. SiR ¹ R ² m (OR ³ ) _3-m ... [2] (In the formula, R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is an alkyl group, a cyclopentyl group or an alkyl group. It is 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. R ¹ has an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, and a 2,3-dimethylcyclopentyl group, in addition to the cyclopentyl group. A cyclopentyl group can be mentioned.

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

In the 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.

Of 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, especially a methyl group or an ethyl group.

Specific examples of such organosilicon compounds 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, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane,
Examples thereof include monoalocoxysilanes such as dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. 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) as described above, the organoaluminum compound catalyst component (b), and the electron donor catalyst component (c). According to the present invention, the olefin polymerization catalyst is used to polymerize a higher α-olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene. -After prepolymerizing an olefin, a higher α-olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene can be polymerized (main polymerization) using this catalyst.

In the prepolymerization, a catalyst having a much 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
It is usually about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, and particularly preferably 1 to 5 in terms of titanium atom per liter of an inert hydrocarbon medium described later.
It is desirable to set it in the range of 0 mmol.

The amount of the organoaluminum catalyst component (b) is
The amount may be such that 0.1 to 500 g, preferably 0.3 to 300 g of polymer is produced per 1 g of the solid titanium catalyst component (a), and it is per mol of titanium atom in the solid titanium catalyst component (a). The amount is usually about 0.1 to 100 mol, preferably about 0.5 to 50 mol, particularly preferably 1 to 20 mol.

The electron donor catalyst component (c) is contained in an amount of 0.1 to 5 per mol 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 higher α-olefin and the above catalyst component to an inert hydrocarbon medium. Examples of the inert hydrogen medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Examples thereof include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.
The olefin or higher α-olefin itself may be prepolymerized in a solvent, or may be prepolymerized 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 in the prepolymerization is usually about −20 to + 100 ° C., preferably about −2.
It is desirable that the temperature is in the range of 0 to + 80 ° C, more preferably 0 to + 40 ° C.

A molecular weight modifier such as hydrogen may be used in the prepolymerization. Such a molecular weight modifier has an intrinsic viscosity [η] of a polymer obtained by prepolymerization measured in a decalin solvent at 135 ° C. of about 0.2 or less.
It is desirable to use it in an amount of dl / g or more, preferably about 0.5 to 10 dl / g.

The prepolymerization is carried out so that about 0.1 to 500 g, preferably about 0.3 to 300 g, particularly preferably 1 to 100 g of a polymer is produced per 1 g of the solid titanium catalyst component (a), as described above. It is desirable to do this. 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 ( in the presence of an olefin polymerization catalyst formed from
Copolymerization (main polymerization) of an olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene is performed.

In the copolymerization (main polymerization) of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene, in addition to the above olefin polymerization catalyst, an olefin polymerization as an organoaluminum compound catalyst component is carried out. The same thing as the organoaluminum compound catalyst component (b) used when producing the catalyst for use can be used. Also high-class α
-An electron donor catalyst used in producing an olefin polymerization catalyst as an electron donor catalyst component in the copolymerization (main polymerization) of an olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene The same thing as the component (c) can be used. In addition, the organoaluminum compound and the electron donor used in the copolymer (main polymerization) of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene do not necessarily prepare the above-mentioned olefin polymerization catalyst. It need not be the same as the organoaluminum compound and electron donor used in the process.

The copolymerization (main polymerization) of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene is usually carried out in the liquid phase. As the reaction medium for the main polymerization, the above-mentioned inert hydrocarbon medium may be used, or an olefin which is liquid at the reaction temperature may be used.

In the copolymerization (main polymerization) of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene, the solid titanium catalyst component (a) is converted into titanium atom per 1 liter of the polymerization volume, Usually, it is used in an amount of about 0.001 to about 1.0 mmol, preferably about 0.005 to 0.5 mmol. Further, the organoaluminum catalyst component (b) is the organoaluminum compound catalyst component (b) based on 1 mol of titanium atom in the solid titanium catalyst component (a).
The metal atom therein is usually used in an amount of about 1 to 2000 mol, preferably about 5 to 500 mol. Further, the electron donor catalyst component (c) is usually about 0.001 to 10 mol, preferably 0.01 to 2 mol, per mol of the metal atom in the organoaluminum compound catalyst component (b).
It is particularly preferably used in an amount of 0.05 to 1 mol.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted. In the present invention, the polymerization temperature of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene is usually about 20 to 20.
0 ° C., to preferably about 40 to 100 ° C., the pressure is usually preferably atmospheric pressure to 100 kg / cm ² is set to the normal pressure to 50 kg / cm ^2. In the copolymerization (main polymerization) of the higher α-olefin, the aromatic ring-containing vinyl monomer and the 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 olefinic thermoplastic elastomer composition according to the present invention contains, in addition to the crystalline polyolefin resin (A) and the higher α-olefinic copolymer rubber (B),
A softening agent (C) and / or an inorganic filler (D) may be included.

As the softening agent (C) used in the present invention, a softening agent usually used for rubber can be used,
Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and 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, lanolin; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate or metal salts thereof; petroleum resin, coumarone Synthetic polymeric substances such as indene resin and atactic polypropylene; ester-based plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol Can be mentioned.

In the present invention, the softening agent (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 an amount of 00 parts by weight or less, preferably 2 to 100 parts by weight. In the present invention, when the amount of the softening agent (C) used exceeds 200 parts by weight, the heat resistance and heat aging resistance of the obtained thermoplastic elastomer composition tend to be lowered.

Specific examples of the inorganic filler (D) used in the present invention include calcium carbonate, calcium silicate, clay, carion, talc, silica, diatomaceous earth,
Examples thereof include mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass spheres, 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 amount 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) used exceeds 100 parts by weight, the rubber elasticity and molding processability of the resulting thermoplastic elastomer composition tend to decrease.

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

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

In the present invention, the above-mentioned copolymer rubber includes the crystalline polyolefin resin (A) and 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, fasfawite-based or amine-based stabilizers, antiaging agents, weathering stabilizers, antistatic agents, metals Lubricants such as soap and wax can be used within a range that does not impair the object of the present invention.

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-olefinic copolymer rubber (B), if necessary. A softening agent (C) and / or an inorganic filler (D), and the above ethylene / α
-Olefin copolymer rubber, ethylene / α-olefin /
It can be obtained by dynamically heat treating after mixing with a non-conjugated diene copolymer rubber or the like.

The partially crosslinked olefinic thermoplastic elastomer composition according to the present invention requires the above-mentioned crystalline polyolefin resin (A) and a higher α-olefinic copolymer rubber (B). A softening agent (C) and / or an inorganic filler (D) blended according to the above, and the above ethylene / α-olefin copolymer rubber, ethylene.
It can be obtained by dynamically heat-treating a mixture of an α-olefin / non-conjugated diene copolymer rubber and 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-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t -Butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxine) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-Dimethyl-2,5-mono (t-butylperoxy) -hexane, α, α'-bis (t-butylperoxy)
-m-isopropyl) benzene and the like. Among them, dicumyl peroxide, di-t-butylperoxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used.

These organic peroxides are used alone or in combination of two or more. In the present invention, the total amount of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B) is 100% by weight. 0.02-3.0 for a part
It is used in parts by weight, preferably in the range of 0.05 to 1.0 parts by weight, but it is desirable to appropriately determine the optimum amount according to the required physical property values.

When the blending amount of the organic peroxide is less than the above range, the thermoplastic elastomer composition obtained has a low degree of crosslinking, and therefore the heat resistance, tensile strength, elastic recovery and the like are not sufficient. On the other hand, if the blending amount is more than the above range, the thermoplastic elastomer composition obtained has an excessively high degree of cross-linking, resulting in deterioration of moldability, which is not preferable.

In the present invention, it is preferable to use a crosslinking aid or a polyfunctional vinyl monomer together in the partial crosslinking treatment with the organic peroxide. Specifically, sulfur; quinonedioxime compounds such as p-quinonedioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; other maleimide compounds; divinylbenzene. And so on.

A uniform and mild crosslinking reaction can be expected by using the above-mentioned crosslinking aid or a compound such as a polyfunctional vinyl monomer. Such a crosslinking aid or a polyfunctional vinyl monomer is 2.0 parts by weight or less based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B), More preferably, it is used in an amount so as to be 0.3 to 1.0 part by weight.

In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, A decomposition accelerator such as a naphthenate such as zirconium, manganese, magnesium, lead or 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 from the melting point of the crystalline polyolefin resin (A) to 30
The temperature is in the range of 0 ° C, usually 150 to 250 ° C, preferably 170 ° C to 225 ° C. Kneading time is usually 1 to 20
Minutes, preferably 1 to 10 minutes. The shearing force applied is usually 10 to 100,000 as a shearing rate.
sec ^-1, preferably 100~50,000sec ^-1.

As the kneading device, a mixing roll, an intensive mixer such as a Banbury mixer, a kneader, a single-screw or twin-screw extruder can be used, but a non-open type device is preferable.

According to the present invention, the non-cross-linked or partially cross-linked crystalline polyolefin resin (A) and the higher α-olefin copolymer (B) is cross-linked by the above-mentioned dynamic heat treatment. An olefinic thermoplastic elastomer composition is obtained.

[0114]

The olefinic thermoplastic elastomer composition according to the present invention contains a specific crystalline polyolefin resin (A) and a specific higher α-olefinic copolymer rubber (B) in a specific ratio. Therefore, even when it is used in a non-crosslinked state, it is excellent in tensile strength, elongation at break, rubber properties and heat resistance.

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

[0116]

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

[0117]

Reference Example 1 (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 at 130 ° C. for 2 hours to form a uniform solution. 21.3 g of phthalic anhydride was added to the solution, and the mixture was stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 200 ml of titanium tetrachloride having 75 ml maintained at -20 ° C.
The entire amount was added dropwise into the flask over 1 hour. After charging,
The temperature of this mixed solution was raised to 110 ° C. over 4 hours, and 1
When the temperature reached 10 ° C, diisobutyl phthalate 5.2
2 g was added, and the mixture was kept at the same temperature for 2 hours with stirring. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration,
This solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated and reacted again at 110 ° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, and thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing liquid. 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 titanium catalyst component (a) thus obtained was as follows: titanium 2.5% by weight, chlorine 65% by weight,
It was 19% by weight of magnesium and 13.5% by weight of diisobutyl phthalate. (Polymerization) Using a 4-liter glass polymerization vessel equipped with a stirring blade, hexene-1,4-phenylbutene-1,
A copolymerization reaction with 7-methyl-1,6-octadiene was performed.

That is, from the top of the polymerization vessel, hexene-1,4-
A hexane solution of phenylbutene-1 and 7-methyl-1,6-octadiene was added in the polymerization vessel at a concentration of hexene-1 of 132 g /
Liter, 4-phenylbutene-1 concentration 39g / liter,
2.1 liters / hour so that the concentration of 7-methyl-1,6-octadiene was 10 g / liter, and a hexane slurry solution of a solid titanium catalyst component [a] as a catalyst had a titanium concentration of 0.04 mmol in the polymerization vessel. / l, so that 0.
4 liters, hexane solution of triisobutylaluminum so that the aluminum concentration in the polymerization vessel is 4 mmol / l, 1 liter / hour, hexane solution of trimethylmethoxysilane has a silane concentration of 1.3 mmol / l in the polymerization vessel It was continuously fed into each of the polymerization vessels at a rate of 0.5 liter per hour so that the amount became 1. On the other hand, the polymerization solution in the polymerization vessel was continuously withdrawn from the lower portion of the polymerization vessel so as to always have a volume of 2 liters. Further, from the upper part of the polymerization vessel, hydrogen was supplied at 0.8 liters per hour and nitrogen was supplied at 50 liters per hour.
The copolymerization reaction was carried out at 50 ° C. by circulating warm water in a jacket attached outside the polymerization vessel.

Next, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the copolymerization reaction, and this polymerization solution was poured into a large amount of methanol to precipitate the copolymer. The copolymer was thoroughly washed with methanol, and then dried under reduced pressure at 130 ° C for 24 hours to obtain hexene-1,4-phenylbutene-1,7-methyl-1,6-octadiene copolymer at a rate of 122 g / hr. It was

With hexene-1 which constitutes the obtained copolymer
The molar ratio with 4-phenylbutene-1 (hexene-1 / 4-phenylbutene-1) is 75/25, and the iodine value is 9.4.
Met. The intrinsic viscosity [η] measured in decalin at 135 ° C was 5.7 dl / g. The above polymerization conditions are shown in Table 1.

[0121]

[Table 1]

[0122]

Example 1 50 parts by weight of the higher α-olefin copolymer rubber (Copolymer A) obtained in Reference Example 1, MFR (ASTM D 1238-65T, 230 ° C.) 11 g / 10 min, density 0.
50 parts by weight of 91 g / cm ³ polypropylene were kneaded with a Banbury mixer at 180 ° C. for 10 minutes, and the kneaded product was passed through an open roll and cut with a sheet cutter to obtain square pellets.

Next, using this square pellet, a predetermined test piece was produced by injection molding, and its physical properties were evaluated. The results are shown in Table 2.

[0124]

Example 2 An olefinic thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the copolymer B was used in place of the copolymer A, and its physical properties were measured. It was measured.

The results are shown in Table 2.

[0126]

Example 3 An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the copolymer C was used in place of the copolymer A, and its physical properties were measured. It was measured.

The results are shown in Table 2.

[0128]

Comparative Example 1 In Example 1, instead of the copolymer A, an ethylene / propylene / ethylidene norbornene copolymer rubber having an iodine value of 10 and an intrinsic viscosity [η] of 4.6 (ethylene content 80 mol %) Except that
An olefinic thermoplastic elastomer composition was prepared in the same manner as in Example 1, and its physical properties were measured.

The results are shown in Table 2.

[0130]

Example 4 An olefinic thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the copolymer A was 75 parts by weight and the polypropylene was 25 parts by weight. Was measured.

The results are shown in Table 3.

[0132]

Comparative Example 2 Example 1 was repeated except that the ethylene / propylene / ethylidene norbornene copolymer rubber used in Comparative Example 1 was used in place of the copolymer A in Example 4.
In the same manner as above, an olefinic thermoplastic elastomer composition was prepared and its physical properties were measured.

The results are shown in Table 3.

[0134]

Example 5 In Example 1, 40 parts by weight of a mineral oil softener (PW-380 manufactured by Idemitsu Kosan Co., Ltd.) in addition to the copolymer A and polypropylene, and talc (Matsumura Sangyo Co., Ltd.) Manufactured, ET-5) except that an olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that 20 parts by weight was blended.

The results are shown in Table 4.

[0136]

Comparative Example 3 An olefin-based thermoplastic elastomer was prepared in the same manner as in Example 5, except that the ethylene-propylene-ethylidene-norbornene copolymer rubber of Comparative Example 1 was used instead of the copolymer A of Example 5. A composition was prepared and its physical properties were measured.

The results are shown in Table 4.

[0138]

Example 6 Copolymer A 50 obtained in Reference Example 1
11 parts by weight and MFR (ASTM D 1238-65T, 230 ° C)
/ 10 minutes, polypropylene 50 with a density of 0.91 g / cm ³
Parts by weight were kneaded with a Banbury mixer at 180 ° C. for 10 minutes, and the kneaded product was passed through an open roll and cut with a sheet cutter to obtain square pellets.

Next, 100 parts by weight of the square pellets,
1,3-bis (tert-butylperoxyisopropyl)
0.3 parts by weight of benzene and 0.5 parts by weight of divinylbenzene were mixed by stirring with a Henschel mixer, and a predetermined test piece was produced by injection molding, and the physical properties thereof were measured.

The results are shown in Table 5. [Measurement method of physical properties] Test items of physical properties are tensile strength, elongation at break, Heat Sag and permanent elongation. The measurement was performed by the following method. (1) Tensile strength was measured according to JIS K6301 at a breaking speed of 200 mm / min. (2) The breaking elongation was measured according to JIS K6301 at a breaking speed of 200 mm / min. (3) For Heat Sag, the test piece was held horizontally on a cantilever fixing jig, left at 90 ° C. or 120 ° C. for 1 hour, and then the amount of deformation of the hanging free end was measured with a caliper. (4) Permanent elongation was measured according to JIS K6301. However, the retained length was set to a length corresponding to an elongation of 100%.

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for preparing an olefin polymerization catalyst used in the production of the higher α-olefin copolymer rubber used in the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masaaki Kawasaki Aki 6-1-2 Waki, Waki-cho, Kuchi-gun, Yamaguchi Mitsui Petrochemical Industries Ltd. (72) Inventor Yuichi Ito Ichihara, Chiba Prefecture Chikusaigan No. 3 Mitsui Oil & Chemicals Co., Ltd.

Claims (4)

[Claims] 1. A crystalline polyolefin resin (A) 10-6.
0 parts by weight and higher α-olefin copolymer rubber (B)
90 to 40 parts by weight [total amount of (A) and (B) is 10]
0 parts by weight]
-Based elastomeric composition, wherein the higher α-olefin copolymer rubber (B) is a higher α-olefin having 6 to 20 carbon atoms, and
An aromatic ring-containing vinyl monomer represented by the formula [I], and
A high-class compound consisting of a non-conjugated diene represented by the general formula [II]
It is an α-olefin copolymer rubber, and is (i) higher α-o
Molar ratio of reffin and vinyl monomer containing aromatic ring
α-olefin / vinyl monomer containing aromatic ring] is 95 /
5-30 / 70, (ii) the content of the non-conjugated diene is 0.01
~ 30 mol%, (iii) measured in decalin solvent at 135 ° C
The determined intrinsic viscosity [η] is in the range of 0.1-10.0 dl / g
Olefinic thermoplastic elastomer characterized in that
Mer composition;(In the formula, n is an integer of 0 to 5, and R¹, R²And R
³Are each independently a hydrogen atom or a C 1-8
Represents an alkyl group),(In the formula, n is an integer of 1 to 5, and R^FourHas 1 to 4 carbon atoms
Alkyl group of R^FiveAnd R⁶Is a hydrogen atom or carbon number 1
Represents an alkyl group of ~ 8. However, R^FiveAnd R ⁶Gato
It is never a hydrogen atom). 2. The total amount 1 of the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B).
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) with respect to 00 parts by weight. Composition. 3. An olefinic thermoplastic elastomer composition, wherein the olefinic thermoplastic elastomer composition according to claim 1 or 2 is in a non-crosslinked state. 4. An olefinic thermoplastic elastomer composition in a partially crosslinked state, which is obtained by partially crosslinking the olefinic thermoplastic elastomer composition according to claim 1 or 2.