JPH061887A - Thermoplastic olefin elastomer composition and its production - Google Patents

Abstract

PURPOSE:To obtain the title compsn. excellent in tensile strength, elongation at break. rubbery properties, and heat resistance by partially crosslinking a mixture comprising a crystalline polyolefin resin and a specific higher-alpha-olefin copolymer rubber. CONSTITUTION:A mixture comprising 10-60 pts.wt. crystalline polyolefin resin and 90-40 pts.wt. higher-alpha-olefin copolymer rubber which is obtd. from a 6-20C higher alpha-olefin, at least one monomer selected from the group consisting of ethylene, propylene, and 1-butene, and a nonconjugated diene of the formula (wherein n is 1-5; R<1> is 1-4C alkyl; and R<2> and R<3> are each H or 1-8C alkyl provided that they are not simultaneously H) and has an iodine value of 0.1-50 and an intrinsic viscosity [eta] (measured at 135 deg.C in decalin) of 1.0-10.0dl/g is partially crosslinked by the dynamic thermal treatment in the presence of an org. peroxide, thus giving the title compsn. excellent in tensile strength, elongation at break, rubbery properties, and heat resistance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin-based thermoplastic elastomer composition and a method for producing the same, and more specifically, it has a tensile strength and a breaking elongation which comprise a crystalline polyolefin resin and a higher α-olefin-based copolymer rubber. TECHNICAL FIELD The present invention relates to an olefin-based thermoplastic elastomer composition excellent in degree and rubber elasticity and a method for producing the same.

[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.

Olefinic thermoplastic elastomers can be divided into cross-linking type and non-crosslinking type. Non-crosslinking type thermoplastic elastomers have little variation in quality because they do not undergo a crosslinking reaction and are inexpensive to produce, but comparing the two in terms of performance, tensile strength, elongation at break, or rubber properties (for example, permanent In terms of elongation, compression set) and heat resistance, the crosslinkable olefinic thermoplastic elastomer is superior to the noncrosslinkable olefinic thermoplastic elastomer. This is because AY Coran et al. (Rubber Chemistry and Technology, 53 (1980),
It is widely known, as detailed in (Page 141).

Regarding the non-crosslinked or partially crosslinked olefinic thermoplastic elastomer, for example, Japanese Patent Publication No. 53-21021, Japanese Patent Publication No. 55-18448, Japanese Patent Publication No. 56-15741 and Japanese Patent Publication No. 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 publication and the like.

As described above, the olefinic thermoplastic elastomers include non-crosslinking type thermoplastic elastomers and crosslinkable type thermoplastic elastomers. In the case of noncrosslinking type thermoplastic elastomers, conventionally known noncrosslinking type thermoplastic elastomers are used. It has been desired to develop an olefin-based thermoplastic elastomer composition having excellent tensile strength, elongation at break, rubber properties (permanent elongation, compression set, etc.), heat resistance, etc., as compared with a plastic elastomer, and crosslinking. In the case of type thermoplastic elastomer,
It has been desired to develop an olefin-based thermoplastic elastomer composition which is superior to conventionally known vulcanized rubbers in tensile strength, elongation at break and rubber-like properties.

[0006]

The object of the present invention is to obtain excellent tensile strength, elongation at break, rubber properties and heat resistance even in the case of the non-crosslinked type, and in the case of the crosslinked type, conventional vulcanization An object of the present invention is to provide an olefin-based thermoplastic elastomer composition which is superior to rubber in tensile strength, elongation at break and rubber-like properties.

Another object of the present invention is to provide a partially crosslinked olefinic thermoplastic elastomer composition which is excellent in the above properties.

[0008]

SUMMARY OF THE INVENTION The olefinic thermoplastic elastomer composition according to the present invention comprises a crystalline polyolefin resin (A) 1
An olefin heat composed of 0 to 60 parts by weight and a 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, ethylene, propylene and 1
-Composed of at least one monomer selected from the group consisting of butene 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 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]

[Chemical 3]

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

The olefinic thermoplastic elastomer composition according to the present invention has a tensile strength,
It has excellent elongation at break, rubber properties and heat resistance. In addition, 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 partially crosslinked.

The method for producing the partially crosslinked olefinic thermoplastic elastomer composition described above comprises 10 to 60 parts by weight of the crystalline polyolefin resin (A) and the above-mentioned higher α.
-Olefin-based copolymer rubber (B) 90 to 40 parts by weight [the total amount of (A) and (B) is 100 parts by weight]
It is characterized in that the mixture with and is subjected to dynamic heat treatment to partially crosslink in the presence of an organic peroxide.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The olefinic thermoplastic elastomer composition and the method for producing the same 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.

Specific examples of suitable raw material olefins for the crystalline polyolefin resin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 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 random type 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 MFR (ASTM D 1238-65T,
230 ° C.) is usually 0.01 to 100 g / 10 minutes, preferably 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 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-olefins 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-Eicosen, 9-
Methyl-1-decene, 11-Methyl-1-dodecene, 12-
Ethyl-1-tetradecene and the like can be mentioned.

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.

The above non-conjugated dienes are represented by the following general formula [I].

[0025]

[Chemical 4]

In the general formula [I], n is an integer of 1 to 5, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are hydrogen atoms or 1 to 4 carbon atoms.
8 represents an alkyl group, 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-
Examples include methyl-1,8-undecadiene. 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 kinds. Examples of the above monomer include ethylene, propylene and 1-butene. These monomers may be used alone or as a mixture of two or more kinds. The molar ratio of the higher α-olefin and the monomer (higher α-olefin / monomer) is 10/90 to 9
It is preferably within the range of 5/5.

The iodine value of the higher α-olefin copolymer rubber (B) used in the present invention is in the range 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) is a crystalline polyolefin resin (A) and a 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 higher α-olefin copolymer rubber (B) as described above can be produced by the following method.
The higher α-olefin copolymer rubber (B) used in the present invention is 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 a 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 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) _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 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 , 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 (O-n-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 , tetraalkoxy titanium such as Ti (O-2-ethylhexyl) _{4, and the} like.

Of these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred. Above all,
Titanium tetrachloride is particularly preferably used. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds are
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.

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 non-reducing magnesium compound 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, etc. Alkoxy magnesium; phenoxy magnesium, dimethylphenoxy magnesium, and other allyloxy magnesium; magnesium laurate, magnesium stearate, and other carboxylates of magnesium.

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 complex compound or a complex compound of the above-mentioned magnesium compound with another metal, in addition to the above-mentioned reducible magnesium compound and non-reducible magnesium compound. 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, and 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 in the preparation of the solid titanium catalyst component (a) include organic carboxylic acid esters and polycarboxylic acid esters described later, and they are specifically represented by the following formula. And a compound having a skeleton.

[0044]

[Chemical 5]

[0045]

[Chemical 6]

[0046]

[Chemical 7]

[0047]

[Chemical 8]

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 heteroatom such as N, O and S, and 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.

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 polyvalent carboxylic 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, diethyl diisobutylmalonate, diethyl dinormal butylmalonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, diisobutyl butyl maleate, butyl maleate Fatty acid polycarboxylic acid esters such as diethyl acidate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citracone, dimethyl citracone; 1,2-cyclohexanecarboxylic Diethyl acid,
Aliphatic polycarboxylic acid esters such as diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, phthalate Acid ethyl isobutyl, phthalic acid 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, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate; 3 Examples thereof include esters derived from heterocyclic polycarboxylic acids such as 1,4-furandicarboxylic acid.

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 polycarboxylic 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 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, the electron donors other than the polyvalent carboxylic acid 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,
Thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes and other organosilicon compounds, 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 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 mol per mol of the magnesium compound. 0.01-5
The titanium compound is present in an amount of about 0.01-500 moles, preferably 0.05-3, in an amount of about 0.05-2 moles.
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 0.1-10,
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 60-1, 000m
² / g, more preferably 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.

A method for preparing such a highly active titanium catalyst component is described in, for example, JP-A-50-108385.
50-126590, 51-20297, 51-28189, 51-64586, 51-92885, 51-1366
25, 52-87489, 52-100596, and
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,
55-152710, 56-811, 56-11908, 56-18606, 58-83006, 58-1387.
05 publication, 58-138706 publication, 58-138707 publication,
58-138708, 58-138709, 58-1387
No. 10, gazette 58-138715 gazette, gazette 60-23404 gazette, the same
No. 61-21109, No. 61-37802, No. 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 compounds include (i) the general formula (R ¹ ) _m Al (O (R ² )) _n H _p X _q (wherein, R ¹ and R ² usually have 1 to 15 carbon atoms). ,
It is preferably a hydrocarbon group containing 1 to 4 groups, which may be the same or different from each other. X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <
3 and q are numbers satisfying 0 ≦ q <3, and m +
an organic aluminum compound represented by the formula (n + p + q = 3), (ii) the general formula (M ¹ ) Al (R ¹ ) ₄ (wherein M ¹ is Li, Na, K, and R ¹ is the above (i). And a complex alkylated product of a group I metal represented by R ¹ ) and aluminum.

Examples of the organoaluminum compound belonging to the above (i) include the following compounds. 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) and the like.

Specific examples of the aluminum compound belonging to (i) above include trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkenyl aluminum such as triisoprenyl aluminum; diethyl aluminum ethoxide and dibutyl aluminum butoxide. Aluminum alkyl sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; (R ¹ ) _2.5 A
a partially alkoxylated alkylaluminum having an average composition such as 1 (O (R ² )) _0.5 ;
Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide Partially halogenated alkyl aluminum such as alkyl aluminum dihalide; Dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride; Alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum 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.

As a compound similar to the aluminum compound belonging to the above (i), an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can be mentioned. Examples of such a compound include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (C ₄ H ₉ ) ₂ A
_{lOAl (C 4 H 9) 2} , (C 2 H 5) 2 AlN (C 2 H 5) A
1 (C ₂ H ₅ ) ₂ , methylaminooxane and the like can be mentioned.

The compounds belonging to (ii) above include L
Examples thereof include iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more kinds of aluminum compounds described above are bound.

The electron donor catalyst component (c) includes oxygen-containing compounds such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes. 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,
Nonylphenol, cumylphenol, naphthol, and other phenols having 6 to 20 carbon atoms which may have a lower alkyl group; acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, benzoquinone and the like having 3 to 15 carbon atoms Ketones; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms; 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 Chill, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, maleic acid- n-Butyl, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di2 phthalate -Ethylhexyl, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and other organic acid esters having 2 to 30 carbon atoms; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and the like having 2 carbon atoms ~ Acid halides of 5; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acids such as acetic acid amide, benzoic acid amide, 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 Acid anhydrides such as benzoic anhydride are used.

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] (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-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, methyltriallyloxy silane, vinyl tris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used. To be

Of these, ethyltriethoxysilane, n
-Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane, p-trilylmethyldimethoxy Silane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane and diphenyldiethoxysilane are 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. And R ¹ is a cyclopentyl group having an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, and a 2,3-dimethylcyclopentyl group as R ^1. Can be mentioned.

In the above 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, An allyl group such as an isopropyl group, a butyl group, and a hexyl group, or a cyclopentyl group exemplified as R ¹ and a cyclopentyl group having an alkyl group can be similarly mentioned.

[0073] In the above formula [2], R ³ is a hydrocarbon group, the R ^3, can be exemplified an alkyl group, a cycloalkyl group, an aryl group, a hydrocarbon group such as 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, particularly 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 catalyst for olefin polymerization is used to polymerize a higher α-olefin, at least one monomer selected from the group consisting of ethylene, propylene and 1-butene, and a non-conjugated diene. However, using this olefin polymerization catalyst, α-
After preliminarily polymerizing the olefin or higher α-olefin, the higher α-olefin, the above monomer and the non-conjugated diene can be polymerized (main polymerization) using this catalyst. During the prepolymerization, per 1 g of the 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 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
The amount is usually about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, and particularly preferably 1 to 50, in terms of titanium atom, per liter of an inert hydrocarbon medium described later.
It is desirable to set it in the millimolar 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 0.3 to 300 g of a polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.1 per mol of titanium atom in the solid titanium catalyst component (a). An amount of 5 to 50 mol, particularly preferably 1 to 20 mol is desirable.

The electron donor catalyst component (c) is used 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 regulator has an intrinsic viscosity [η] of a polymer obtained by prepolymerization of about 0.
It is desirable to use it in an amount of 2 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, and 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, the above monomer, and a non-conjugated diene.

In the copolymerization (main polymerization) of the higher α-olefin, the above monomer and the 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 when producing the catalyst can be used. Also, 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 when 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 do not necessarily prepare the above-mentioned olefin polymerization catalyst. It does not have to be the same as the organoaluminum compound and electron donor used here.

The copolymerization (main polymerization) of the higher α-olefin, the above-mentioned 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 above-mentioned monomer and the non-conjugated diene, the solid titanium catalyst component (a) is usually converted into titanium atom per 1 liter of polymerization volume, Is about 0.001 to about 1.0 mmol,
It is preferably used in an amount of about 0.005-0.5 mmol. Further, an organoaluminum compound catalyst component (b)
Is usually about 1 to 2,000 mol, preferably about 5 to about 5 mol of metal atom in the organoaluminum compound catalyst component (b), relative to 1 mol of titanium atom in the solid titanium catalyst component (a).
It is used in an amount such that it is 500 mol. Further, the electron donor catalyst component (c) is usually about 0.005 mol per 1 mol 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.

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 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 atmospheric pressure to 50 kg / cm ² . In the copolymerization (main polymerization) of the higher α-olefin, the above-mentioned monomer and the non-conjugated diene, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In the olefinic thermoplastic elastomer composition according to the present invention, 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 indene Resins, synthetic polymeric substances such as atactic polypropylene; ester-based plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate; other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene,
Examples include liquid thiocol.

In the present invention, the softening agent (C) is 2 parts with respect to 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.

As the inorganic filler (D) used in the present invention, specifically, 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 resin (A), a higher α-olefinic copolymer rubber (B), a softening agent (C) and an inorganic filler ( In addition to D), an ethylene / α-olefin copolymer rubber in which the α-olefin has 3 to 5 carbon atoms, and an ethylene / α-olefin / non-conjugated diene copolymer in which the α-olefin has 3 to 5 carbon atoms A polymeric rubber can be included.

Specific examples of the 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 is 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-resistant stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, antiaging agents, weathering 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-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 / non-conjugated diene copolymer rubber, etc. are mixed and then dynamically heat-treated.

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) compounded according to the above, and further 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. Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide and 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-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide, etc. Is mentioned.

Such an organic peroxide is added to the entire object to be treated, that is, the crystalline polyolefin resin (A) and the higher α-olefin copolymer rubber (B) in a total amount of 100.
0.02 to 3 parts by weight, preferably 0.05
It is used in an amount such that it is about 1 part by weight. If the blending amount is less than the above range, the resulting thermoplastic elastomer composition has a low degree of cross-linking, and therefore the heat resistance, tensile properties, elastic recovery, impact resilience, etc. are not sufficient. If the amount is more than the above range, the thermoplastic elastomer composition obtained may have a too high degree of cross-linking, resulting in deterioration of moldability.

In the present invention, in the partial crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime,
p, p'-dibenzoylquinone dioxime, N-methyl-
Peroxy crosslinking aids such as N, N'-m-phenylene dimaleimide, or polyfunctional methacrylates such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and acrylic methacrylate. Monofunctional, polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate may be incorporated.

A uniform and mild crosslinking reaction can be expected by using a compound such as the above-mentioned crosslinking aid.
Such a crosslinking aid or a compound such as a polyfunctional vinyl monomer may be added to 100 parts by weight of 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
-A tertiary amine such as tri (dimethylamino) phenol, or a decomposition accelerator such as a naphthenate such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead or mercury may be used.

The dynamic heat treatment in the present invention is preferably carried out in a non-open type apparatus, and is preferably carried out in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature is 3 from the melting point of the crystalline polyolefin resin (A).
The temperature 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.
It is 0 minutes, preferably 1 to 10 minutes. The shearing force applied is 10 to 100,000 se as the shearing rate.
c ⁻¹ , preferably 100 to 50,000 sec ⁻¹ .

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

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

In the present invention, the fact 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 45 to 98%. Measurement of gel content 100 mg of a sample of the thermoplastic elastomer composition was weighed and cut into 0.5 mm × 0.5 mm × 0.5 mm strips. After soaking at 48 ° C. for 48 hours, the sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained.

From the weight of this dry residue, the weight of all cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component and the weight of the crystalline polyolefin resin (A) in the sample before immersion in cyclohexane were calculated. The subtracted amount is referred to as “corrected final weight (Y)”.

On the other hand, the higher α-olefin copolymer (B) in the sample is designated as "corrected initial weight (X)".
Here, the gel content is calculated by the following formula.

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

[0112]

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 in the case of non-crosslinked, it is excellent in tensile strength, elongation at break, rubber property and heat resistance as compared with the conventionally known non-crosslinked thermoplastic elastomer.

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 partially crosslinked, it is superior to the 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, it is possible to provide a partially crosslinked olefinic thermoplastic elastomer composition having the above effects.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The methods for measuring the physical properties of the olefinic thermoplastic elastomer compositions of Examples and Comparative Examples are as follows.

[Measurement method of physical properties] (1) Tensile strength: 200 in accordance with JIS K 6301
Tensile strength at break was measured at a pull rate of mm / min. (2) Elongation at break: 200 in accordance with JIS K 6301
The breaking elongation at the breaking point was measured at a tensile speed of mm / min. (3) Heat Sag: a test piece (size 128 mm x 25 mm x 3 mm, length 128 m on a cantilever fixing jig)
(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 hanging free end was measured with a caliper. (4) Permanent elongation: Measured according to JIS K 6301. However, the retained length was set to a length corresponding to 100% elongation.

[Examples etc. relating to non-crosslinked thermoplastic elastomer composition]

[0118]

[Reference Examples 1 to 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 give a uniform solution. Thereafter, 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. The homogeneous solution thus obtained was cooled to room temperature and then 75 ml of titanium tetrachloride 2 kept at -20 ° C.
The total amount was added dropwise to 00 ml over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate was added, and the mixture was kept at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, hot filtration is performed again to collect a solid portion, and 1
It was sufficiently washed with 10 ° C decane and hexane 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 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 diisobutylphthalate. [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).
(1 mmol converted to titanium atom) is charged, and the temperature is 30 ° C.
The temperature was raised to. Then add 1-octene 8.4 to this solution.
ml was added dropwise over 1 hour, and the reaction was continued for another hour. After completion of the reaction, this 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 and 7
-Copolymerization reaction with methyl-1,6-octadiene was performed.

That is, a decane solution of 1-octene and 7-methyl-1,6-octadiene was added from the top of the polymerization vessel,
The concentration of 1-octene in the polymerization vessel is 200 ml / l, 7-
The decane slurry solution of the solid titanium catalyst component (a), which had been prepolymerized as a catalyst at 1.4 liter / hour so that the concentration of methyl-1,6-octadiene was 6 ml / l, was adjusted to the titanium concentration in the polymerization vessel. Is 0.03 mmol / l, 0.4 liter / hour, and decane solution of triisobutylaluminum is 1.2 liter / hour, trimethyl, so that the aluminum concentration in the polymerization vessel is 3 mmol / l. A solution of methoxysilane in decane was added at a rate of 1 per hour so that the concentration of silane in the polymerization vessel was 1 mmol / l.
It was continuously fed into the polymerizer at a rate of 1 liter. On the other hand, the polymerization solution in the polymerization vessel from the bottom of the polymerization vessel is always 2
It was continuously withdrawn so as to obtain liter. Further, propylene was supplied at 20 liters / hour, hydrogen was supplied at 1 liter / hour, and nitrogen was supplied at 50 liters / hour from the upper portion of the polymerization vessel. 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 isobutyl alcohol was added to the polymerization solution extracted 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 thoroughly washing the copolymer with methanol, it was dried under reduced pressure at 120 ° C for one day to give 1-octene.
Propylene-7-methyl-1,6-octadiene copolymer rubber (A-1) was obtained at a rate of 195 g / hr.

Obtained 1-octene / propylene / 7-
Methyl-1,6-octadiene copolymer rubber (A-1)
Has a molar ratio of 1-octene and 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. The intrinsic viscosity [η] and iodine value of these copolymer rubbers are also shown in Table 1.

[0123]

[Table 1]

[0124]

Example 1 50 parts by weight of 1-octene / propylene / 7-methyl-1,6-octadiene copolymer rubber (B-1) obtained in Reference Example 1 and MFR (ASTM D 12
38-65T, 230 ° C.) 11 g / 10 min, and a density of 0.91 g / cm ³ 50 parts by weight of polypropylene,
After kneading at 180 ° C. for 10 minutes using a Banbury mixer, 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 prepared by injection molding, and its physical properties were measured according to the above measuring methods. The results are shown in Table 2.

[0126]

Comparative Example 1 In Example 1, instead of 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] 4.6 dl
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (/ g) was used, and its physical properties were measured.

The results are shown in Table 2.

[0128]

[Table 2]

[0129]

[Example 2] In Example 1, 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 and its physical properties were measured in the same manner as in Example 1 except that 5 parts by weight and 25 parts by weight were used.

The results are shown in Table 3.

[0131]

[Comparative Example 2] In Example 2, instead of the 1-octene / propylene / 7-methyl-1,6-octadiene copolymer rubber (B-1), ethylene / propylene / 5-ethylidene-of Comparative Example 1 was used. 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.

The results are shown in Table 3.

[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 [made by Idemitsu Kosan Co., Ltd. , PW-380] 40 parts by weight, and talc [Matsumura Sangyo KK, ET-5] 20 parts by weight were added to prepare an olefinic thermoplastic elastomer composition in the same manner as in Example 1. , Its physical properties were measured.

The results are shown in Table 4.

[0136]

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

The results are shown in Table 4.

[0138]

[Table 4]

[Examples etc. Regarding Partially Crosslinked Thermoplastic Elastomer Compositions]

[0140]

Example 4 50 parts by weight of 1-octene / propylene / 7-methyl-1,6-octadiene copolymer rubber (B-1) obtained in Reference Example 1 and 50 parts by weight of polypropylene of Example 1 In addition, organic peroxide (2,5-dimethyl-2,
5-di- (tert-butylperoxy) hexyne-3)
After 0.2 parts by weight and 0.3 parts by weight of divinylbenzene were added and thoroughly mixed in a Henschel mixer, after kneading at 180 ° C. for 10 minutes using a Banbury mixer,
This 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 prepared by injection molding, and its physical properties were measured according to the above measuring methods. The results are shown in Table 5.

[0142]

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

The results are shown in Table 5.

[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 and its physical properties were measured in the same manner as in Example 4 except that 5 parts by weight and 25 parts by weight were used.

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-of Comparative Example 1 was used. An olefin-based thermoplastic elastomer composition was prepared and its physical properties were measured in the same manner as in Example 5 except that the 2-norbornene copolymer rubber was used.

The results are shown in Table 6.

[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 softener [made by Idemitsu Kosan Co., Ltd. , PW-380], and 20 parts by weight of talc [ET-5, manufactured by Matsumura Sangyo Co., Ltd.] were added to prepare an olefinic thermoplastic elastomer composition in the same manner as in Example 4. , Its physical properties were measured.

The results are shown in Table 7.

[0152]

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

The results are shown in Table 7.

[0154]

[Table 7]

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Kawasaki Aki 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (5)

[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], wherein the higher α-olefin copolymer rubber (B) is a higher α-olefin having 6 to 20 carbon atoms, It is composed of at least one monomer 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 in the range 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
Neither R ³ nor R ³ is 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. The thermoplastic resin composition according to claim 1 or 2, wherein the olefinic thermoplastic elastomer composition is non-crosslinked.
The olefinic thermoplastic elastomer composition described in 1. 4. The olefinic thermoplastic elastomer composition according to claim 1, wherein the olefinic thermoplastic elastomer composition is partially crosslinked. 5. Crystalline polyolefin resin (A) 10-6
Represented by the following general formula [I]: 0 parts by weight, a higher α-olefin having 6 to 20 carbon atoms, at least one monomer selected from the group consisting of ethylene, propylene and 1-butene. It is composed of a non-conjugated diene, has an iodine value in the range of 0.1 to 50, and has 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 the higher α-olefin copolymer rubber (B) in the range of 1 / g [the total amount of (A) and (B) is 100 parts by weight] with an organic peroxide. In the presence of a substance, a method for producing an olefin-based thermoplastic elastomer composition, characterized by dynamically heat-treating 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 are not both hydrogen atoms].