JP2992308B2 - Method for producing thermoplastic elastomer composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a thermoplastic elastomer composition, and more particularly, to a method for producing a thermoplastic elastomer composition which is excellent in heat resistance, tensile properties, weather resistance, flexibility and rebound resilience, and has excellent fluidity. The present invention relates to a method for producing a thermoplastic elastomer composition capable of providing a molded article having good appearance and excellent appearance.

BACKGROUND OF THE INVENTION Thermoplastic elastomers have been widely used as automotive parts such as bumper parts. This thermoplastic elastomer has characteristics of both thermoplasticity and elasticity, and has heat resistance,
It can be formed into a molded product excellent in tensile properties, weather resistance, flexibility and elasticity.

For example, Japanese Patent Publication No. 53-34210 discloses a thermoplastic elastomer obtained by dynamically partially curing 60 to 80 parts by weight of a monoolefin copolymer rubber and 40 to 20 parts by weight of a polyolefin plastic. I have. In addition, Tokiko Sho 53-
Japanese Patent No. 21021 discloses a thermosetting method comprising (a) a partially crosslinked copolymer rubber composed of an ethylene-propylene-nonconjugated polyene copolymer rubber having a gel content of 30 to 90% by weight, and (b) a polyolefin resin. A plastic elastomer is disclosed. Furthermore, Japanese Patent Publication No. 55-18448 discloses a thermoplastic elastomer in which an ethylene-propylene copolymer rubber and a polyolefin resin are dynamically partially or completely crosslinked.

Incidentally, JP-A-58-187412 discloses a propylene homopolymer block, and propylene and ethylene or
50 to 70 parts by weight of one or more of blocks [A] having a propylene content of 100 to 60% by weight selected from binary random copolymer blocks with a C _{4 to} C ₁₂ α-olefin,
The ethylene content is 30 to 85% by weight derived from an olefin-based block copolymer containing 30 to 50 parts by weight of one or two or more of binary random copolymer blocks [B] of ethylene and propylene. A crosslinked block copolymer characterized by having a content of a hot xylene-insoluble component and a specific fluidity is disclosed.

JP-A-63-165414, JP-A-63-165115, JP-A-63-161516 and U.S. Pat.
No. 6, the propylene homopolymer block [A] produced using a specific Ziegler catalyst, a propylene-ethylene binary random copolymer block [B],
An olefin block copolymer composed of a propylene / ethylene binary random copolymer block [C] is mixed with an organic peroxide, a divinyl compound and an antioxidant.
There is disclosed a method for producing a crosslinked olefin block copolymer, which comprises kneading and crosslinking at a temperature of 0 ° C. or lower.

Further, JP-A-48-21731 discloses that 3 to 30% by weight of a copolymer part mainly containing ethylene and 70% by weight or less of another α-olefin and 97 to 70% by weight of a polymer part mainly composed of propylene. % Of a block copolymer comprising an organic peroxide and a heat treatment at 180 to 270 ° C. is disclosed.

The present inventors studied to economically produce a high-quality thermoplastic elastomer.When polymer particles having a specific morphology were used, excellent elasticity was obtained even with a small rubber content. In addition, it is possible to obtain a molded article having excellent strength, and furthermore excellent appearance when molded into a molded article, particularly after coating, and the thermoplastic elastomer particles and a crosslinked polyolefin and / or a non-crosslinked polyolefin. The present invention has found that a thermoplastic elastomer composition containing not only has excellent heat resistance, tensile properties, weather resistance, flexibility and rebound resilience, but also can provide a molded article having good fluidity and excellent appearance. It was completed.

An object of the present invention is to provide a method for producing a thermoplastic elastomer composition which is excellent in heat resistance, tensile properties, weather resistance, flexibility and rebound resilience, and which can give a molded article having good fluidity and excellent appearance. It is intended to provide.

SUMMARY OF THE INVENTION The method for producing a thermoplastic elastomer composition according to the present invention comprises a polymer particle comprising a crystalline olefin polymer portion and an amorphous olefin polymer portion that has not undergone a heat history that impairs the particle shape. It is characterized by obtaining a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and / or a non-crosslinked polyolefin.

Examples of the method for producing such a thermoplastic elastomer composition include the following three kinds of production methods.

(1) A polymer particle comprising a crystalline olefin polymer portion and an amorphous olefin polymer portion, which has not undergone a heat history that impairs the particle shape, and which is not crosslinked, is used as a crosslinking agent. And a melt-kneading process in the presence of a polyolefin and a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and / or a non-crosslinked polyolefin.

(2) Cross-linking obtained by cross-linking polymer particles composed of a crystalline olefin polymer portion and an amorphous olefin polymer portion without undergoing a thermal history that impairs the particle shape, at least in the presence of a cross-linking agent. A method for producing a thermoplastic elastomer composition, comprising melt-kneading a polymer and a polyolefin to obtain a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and / or a non-crosslinked polyolefin.

(3) Gas-phase crosslinked polymer particles comprising a crystalline olefin polymer part and an amorphous olefin polymer part, which have not undergone a heat history that impairs the particle shape, wherein the crystalline olefin polymer part and the non-crystalline olefin polymer part The polymer particles comprising the crystalline olefin polymer part, at least in the presence of a crosslinking agent, a temperature lower than the higher of the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer. A thermoplastic elastomer composition characterized by melt-kneading the gas-phase crosslinked polymer particles obtained by contacting with each other in the presence of a polyolefin to obtain a thermoplastic elastomer composition containing a crosslinked polymer and a polyolefin. Method of manufacturing a product.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing the thermoplastic elastomer composition according to the present invention will be specifically described.

Polymer particles The polymer particles used in the present invention are polymer particles composed of a crystalline olefin polymer portion and an amorphous olefin polymer portion that have not undergone heat history that impairs the particle shape, and are crosslinked. There are two types of polymer particles that are not crosslinked and polymer particles that are crosslinked.

The above-mentioned crosslinked polymer particles may be obtained by mixing a polymer particle comprising a crystalline olefin polymer part and an amorphous olefin polymer part, and a crosslinking agent with the melting point of the crystalline olefin polymer or the amorphous olefin. Intraparticle crosslinked thermoplastic elastomer particles obtained by contacting at a temperature less than the higher of the glass transition points of the polymer. In the present specification, such intraparticle crosslinking may be referred to as gas-phase crosslinking, and such thermoplastic elastomer particles may be referred to as gas-phase crosslinked polymer particles.

The average particle diameter of the polymer particles before melt-crosslinking or before gas-phase crosslinking (hereinafter sometimes simply referred to as “polymer particles”) used in the present invention is usually 10 μm or more, preferably 10 to 10 μm.
It is in the range of 8000 μm, more preferably 100 to 4000 μm, particularly preferably 300 to 3000 μm. The geometric standard deviation indicating the particle size distribution of the polymer particles used in the present invention is usually in the range of 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.5, and particularly preferably 1.0 to 1.3. . Further, the apparent bulk density of the polymer particles used in the present invention by natural fall is usually 0.2 g / ml or more, preferably 0.2 g / ml.
0.70.7 g / ml, more preferably 0.3 to 0.7 g / ml, particularly preferably 0.35 to 0.60 g / ml.

Further, in the polymer particles used in the present invention, particles passing through a 150-mesh sieve are preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 2% by weight. In addition, such polymer particles have a drop time of 5 to 25 seconds, preferably 5 to 5, as defined below.
20 seconds, particularly preferably 5 to 15 seconds.

The average particle size, apparent bulk density, and falling seconds of the polymer particles as described above are measured as described below.

Average particle diameter: 300 g of polymer particles with a diameter of 200 mm and a depth of 45 mm
Stainless steel sieve made by Nippon Riken Kikai (7,1
After adding seven kinds of sieves of 0, 14, 20, 42, 80, and 150 mesh in this order from the top to the bottom and further stacking a saucer at the bottom, cover the lid and then IIDA SIEVE SHAKER (Iida Seisakusho) ) And shaken for 20 minutes. After shaking for 20 minutes, weigh the polymer on each sieve,
The measurements were plotted on log-established paper. The plot was connected by a curve, and the particle diameter (D ₅₀ ) at an integrated weight of 50% by weight was determined based on the curve, and this value was defined as the average particle diameter.

Meanwhile regard to geometric standard deviation, as well as that obtained from the value of the D ₅₀ small integrated from particle size 16% by weight of the particle diameter (D _16). (Geometric standard deviation = D ₅₀ / D ₁₆ ) Apparent bulk density: Measured in accordance with JIS K 6721-1977. (However, the inner diameter of the inlet of the funnel used was 92.9 mmφ and the inner diameter of the outlet was 9.5 mmφ.) Falling seconds: Using the device for measuring the bulk density as it was, the sample was dropped into the receiver and raised from the receiver. The sample contained in a 100 ml container was transferred to the funnel with the damper again by scraping the sample with a glass rod, then the damper was pulled, and the time (second) required for the sample to completely drop from the bottom of the funnel was dropped. Number of seconds.

However, in measuring the number of seconds of falling, polymer particles obtained by removing particles having a mean particle size of 1.5 to 1.6 times or more by sieving were used.

When measuring the number of seconds dropped, set the receiver on the shaking table of the powder test (Type PT-D manufactured by Hosokawa Micro, SER. No. 71190) and adjust the rheostat voltage so that the amplitude of the diaphragm becomes 1 mm. Then, the polymer particles were dropped while being vibrated.

The polymer particles used in the present invention are composed of a crystalline olefin polymer portion and an amorphous olefin polymer portion as described above, and often have a so-called sea-island structure,
The amorphous olefin polymer part forms an island part in the polymer particle. The average particle size of the island portion composed of the amorphous olefin polymer portion (including some crystalline olefin polymer portions in some cases) is 0.5 μm or less, preferably 0.1 μm or less, and more preferably 0.00001 to 0.05μm
It is desirable that In some cases, the island portion and the sea portion may have a compatible structure in which they cannot be distinguished.

The average particle size of the island portion composed of the amorphous olefin polymer portion in the polymer particles is measured as described below.

Using an ultramicrotome, 500 to 100 polymer particles
Slice at 0 ° C at 0 ° C. Then, in the gas phase in about 1 sealed container containing 200 ml of 0.5% RuO ₄ aqueous solution,
The sliced sample is left for 30 minutes to stain the amorphous olefin polymer part in the sample. Next, the dyed sample is reinforced with carbon, and then observed with a transmission microscope. The particle size of the island is obtained for at least 50 particles, and the average value is defined as the average particle size of the island.

The polymer particles used in the present invention, it is preferable to use particles having the above properties, the method for producing particles having such properties is not particularly limited,
It is preferable to produce by adopting a method as described below, the polymer particles obtained by employing this method, the transition metal content in the ash content is usually 100 ppm or less, preferably 10 ppm or less, particularly preferably Is contained at a ratio of 5 ppm or less and a halogen content of usually 300 ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less.

In the present invention, when a polymer is referred to, the polymer is used in a concept including both a homopolymer and a copolymer.

The polymer particles having the above properties can be obtained, for example, by polymerizing or copolymerizing an α-olefin having 2 to 20 carbon atoms.

Examples of such α-olefins include ethylene,
Propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-
Methylpentene-1,4-methylpentene-1,3,3-
Dimethylbutene-1, heptene-1, methylhexene-
1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene
1, dimethylhexene-1, trimethylpentene-1,
Ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1,
Examples thereof include α-olefins such as methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, and hexadodecene-1.

Among them, α-olefins having 2 to 8 carbon atoms are preferably used alone or in combination.

In the present invention, polymer particles containing a repeating unit derived from the above α-olefin usually at least 50 mol%, preferably at least 80 mol%, more preferably at least 90 mol%, particularly preferably at least 100 mol%. Is used.

In the present invention, examples of other compounds that can be used in addition to the above-mentioned α-olefin include a chain polyene compound and a cyclic polyene compound. In the present invention, as the polyene compound, a polyene having two or more conjugated or non-conjugated olefinic double bonds is used. As such a chain polyene compound,
Specifically, 1,4-hexadiene, 1,5-hexadiene,
1,7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, 1,5,9-decatriene, divinylbenzene and the like are used. Specific examples of the cyclic polyene compound include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, and dicyclopentadiene. Cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3
-Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-
Propenyl-2,5-norbornadiene and the like are used.

In the present invention, a polyene compound obtained by condensing a cyclopentadiene such as cyclopentadiene with an α-olefin such as ethylene, propylene, and butene-1 using a Diels-Alder reaction can also be used. .

Furthermore, in the present invention, a cyclic monoene can be used. Specific examples of such a cyclic monoene include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, Monocycloalkenes such as cyclododecene, tetracyclodecene, octacyclodecene, cycloeicosene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-
Norbornene, 5-isobutyl-2-norbornene, 5,
6-dimethyl-2-norbornene, 5,5,6-trimethyl-
Bicycloalkenes such as 2-norbornene and 2-bornene, 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H- In addition to tricycloalkenes such as indene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, and these compounds, 2-methyl-1 , 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene,
2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8- Dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-stearyl-1,4,
5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,
4a, 5,8,8a-octahydronaphthalene, 2-methyl-3
-Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene,
2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8
Tetra cycloalkenes such as a- octahydronaphthalene, hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecene -4 pentacyclo [8.8.1 ^2.9 1 ^2,9. 1 ^4,7 .1
^11,18 .0.0 ^3,8 .0 ^12,17] henicosenoic -5, octacyclo [8.8.1 ^4,7 .1 ^11,18 .1 ^13,16 .0.0 ^3,8 .0 ^12,17] docosenoic -5 And cyclic monoene compounds such as polycycloalkenes.

Furthermore, in the present invention, styrene and substituted styrene can also be used.

The polymer particles used in the present invention are obtained by polymerizing or copolymerizing at least the α-olefin as described above in the presence of a catalyst as described below. It can be carried out in the gas phase (gas phase method) or in the liquid phase (liquid phase method).

The polymerization reaction or the polymerization reaction by the liquid phase method is preferably performed in a suspended state so that the polymer particles to be produced are obtained in a solid state.

In the case of this polymerization reaction or copolymerization reaction, an inert hydrocarbon can be used. Further, an α-olefin as a raw material may be used as a reaction solvent. The above polymerization or copolymerization may be performed by combining a liquid phase method and a gas phase method. In the production of the polymer particles used in the present invention, the polymerization or copolymerization is a gas phase method,
Alternatively, it is preferable to adopt a method of performing a reaction using an α-olefin as a solvent and then combining the gas phase method.

In the present invention, when producing polymer particles used as a raw material, a method of simultaneously producing a crystalline olefin polymer portion and an amorphous olefin polymer portion by supplying two or more types of monomers to a polymerization vessel, or And a method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion are performed separately and in series using at least two or more polymerization kettles.
In this case, the molecular weight, composition,
The latter method is preferred from the viewpoint that the amount can be freely changed.

The most preferred method is to synthesize a crystalline olefin polymer part by gas phase polymerization and then synthesize an amorphous olefin polymer part by gas phase polymerization, or a method of synthesizing a crystalline olefin polymer part using a monomer as a solvent. After the synthesis, a method of synthesizing an amorphous olefin polymerization portion by gas phase polymerization may be mentioned.

In the present invention, when performing the above-mentioned polymerization reaction or copolymerization reaction, usually, a catalyst component [A] containing a transition metal and an organometallic compound catalyst component [B] ] Is used.

Examples of the catalyst component [A] include Group IVB of the Periodic Table of the Elements.
A catalyst containing a VB group transition metal atom is preferred, and among these, a catalyst component containing at least one atom selected from the group consisting of titanium, zirconium, hafnium, and vanadium is more preferred.

Further, as another preferred catalyst component [A], a catalyst component containing a halogen atom and a magnesium atom in addition to the above transition metal atom, and having a conjugated π electron in a transition metal atom of Group IVB or VB of the periodic table. A catalyst component containing a compound to which a group is coordinated is exemplified.

In the present invention, the catalyst component [A] is present in the reaction system in a solid state during the above-mentioned polymerization reaction or copolymerization reaction, or is present in a solid state by being supported on a carrier or the like. It is preferred to use a catalyst prepared so that

Hereinafter, a solid catalyst component [A] containing a transition metal atom, a halogen atom and a magnesium atom as described above.
This will be described in more detail with reference to an example.

The average particle diameter of the solid catalyst component [A] as described above is preferably 1 to 200 μm, more preferably 5 to 100 μm.
μm, particularly preferably in the range from 10 to 80 μm. The geometric standard deviation (δ _g ) as a scale for observing the particle size distribution of the solid catalyst [A] is preferably in the range of 1.0 to 3.0, more preferably 1.0 to 2.1, and particularly preferably 1.0 to 1.7.

Here, the average particle size and the particle size distribution of the catalyst component [A] can be measured by a light transmission method. Specifically, the dispersion prepared by adding the catalyst component [A] to the decalin solvent so as to have a concentration of 0.1% by weight is taken into a measuring cell, and the cell is irradiated with a fine light, and the particles are irradiated with the fine light. The particle size distribution is measured by continuously measuring the change in the intensity of light passing through.
The standard deviation (δ _g ) is determined from the lognormal distribution function based on the particle size distribution. More specifically, the standard deviation (δ _g ) is determined as the ratio (θ ₅₀ / θ ₁₆ ) between the average particle diameter (θ ₅₀ ) and the particle diameter (θ ₁₆ ) which becomes 16% by weight based on the small particle diameter. Can be The average particle size of the catalyst is a weight average particle size.

The catalyst component [A] preferably has a shape such as a true sphere, an oval sphere, or a granule, and the particle has an aspect ratio of preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. It is.

The aspect ratio can be determined by observing a group of catalyst particles with an optical microscope and measuring the major axis and the minor axis of 50 catalyst particles arbitrarily selected at that time.

When the catalyst component [A] has a magnesium atom, a titanium atom, a halogen atom, and an electron donor, the ratio of magnesium / titanium (atomic ratio) is preferably larger than 1, and this value is usually 2 to 50, preferably The halogen / titanium (atomic ratio) is usually in the range of 6 to 30.
-100, preferably 6-40, and the electron donor / titanium (molar ratio) is usually 0.1-10, preferably 0.2-2.
-6. The specific surface area of the catalyst component [A] is usually 3m ² / g or more, preferably 40 m ² / g or more, more preferably in the range of 100~800m ² / g.

Such a catalyst component [A] generally does not desorb the titanium compound in the catalyst component by a simple operation such as hexane washing at room temperature.

In addition, the catalyst component [A] used in the present invention may contain other atoms and metals in addition to the above components, and further, a functional group or the like is introduced into the catalyst component [A]. May be further diluted with an organic or inorganic diluent.

The catalyst component [A] as described above includes, for example, an average particle diameter,
The particle size distribution is in the above-mentioned range, and furthermore, after forming the magnesium compound as described above, a method of preparing a catalyst, or contacting a liquid magnesium compound and a liquid titanium compound to form the particles as described above. It can be manufactured by employing a method such as a method of forming a solid catalyst so as to have properties.

Such a catalyst component [A] can be used as it is, or can be used after supporting a magnesium compound, a titanium compound and, if necessary, an electron donor on a carrier having a uniform shape. It is also possible to prepare a fine powder catalyst in advance, and then to granulate the fine powder catalyst into the above-mentioned preferable shape.

Such a catalyst component [A] is disclosed in JP-A-55-13.
Nos. 5102, 55-135103, 56-811 and 56-67311 and Japanese Patent Application Nos. 56-1811019 and 61-21109.

An example of a method for preparing the catalyst component [A] described in these publications or specifications will be described.

(1) A solid magnesium compound / electron donor complex having an average particle diameter of 1 to 200 μm and a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less is converted into an electron donor and / or an organoaluminum compound or halogen-containing silicon. It is reacted with a liquid titanium halide compound, preferably titanium tetrachloride, under the reaction conditions, with or without pretreatment with a reaction auxiliary such as a compound.

(2) A liquid magnesium compound having no reducing ability and a liquid titanium compound are preferably reacted in the presence of an electron donor to give an average particle diameter of 1 to 200 μm.
m, a solid component having a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less is precipitated. Further, if necessary, the reaction is carried out with a liquid titanium compound, preferably titanium tetrachloride, or with a liquid titanium compound and an electron donor.

(3) By pre-contacting a liquid magnesium compound having a reducing ability and a reaction aid capable of eliminating the reducing ability of a magnesium compound such as a polysiloxane or a halogen-containing silicon compound, the average particle diameter is reduced. 1 to 200 μm, geometric standard deviation of particle size distribution (δ
_g ) After depositing a solid component having a value of 3.0 or less, the solid component is reacted with a liquid titanium compound, preferably titanium tetrachloride, or a titanium compound and an electron donor.

(4) A magnesium compound having a reducing ability is brought into contact with an inorganic carrier such as silica or an organic carrier, and then the carrier is brought into contact with a halogen-containing compound. Contacting titanium chloride or a titanium compound and an electron donor to react a magnesium compound supported on a carrier with a titanium compound or the like.

(5) In the method of (2) or (3), the Mg compound is supported on an inorganic carrier such as silica or alumina or an organic carrier such as polyethylene, polypropylene or polystyrene in the presence of these carriers.

Such a solid catalyst component [A] has a property that a polymer having high stereoregularity can be produced with high catalytic efficiency. For example, when propylene homopolymerization is carried out using this solid catalyst component [A], polypropylene having an isotacticity index (boiling n-heptane insoluble matter) of 92% or more, particularly 96% or more, is added to 1 mmol of titanium. The amount can be usually 3000 g or more, preferably 5000 g or more, and particularly preferably 10,000 g or more.

Examples of a magnesium compound, a halogen-containing silicon compound, a titanium compound, and an electron donor that can be used in the preparation of the catalyst component [A] as described above are shown below. The aluminum component used in the preparation of the catalyst component [A] is a compound exemplified in the later-described organometallic compound catalyst component [B].

Specific examples of the magnesium compound include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide and hydrotalcite, carboxylate salts of magnesium, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, and magnesium dichloride. In addition to halides, organic magnesium compounds such as dialkyl magnesium, Grignard reagent, and diaryl magnesium are used.

As the titanium compound, specifically, titanium tetrachloride,
Titanium halides such as titanium trichloride, alkoxytitanium halide, allyloxytitanium halide, alkoxytitanium, allyloxytitanium and the like are used. Among these, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred.

As the electron donor, specifically, oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes; Nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates are used.

Specific examples of the compound that can be used as such an electron donor include methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, and isopropyl alcohol. , Cumyl alcohol and isopropylbenzyl alcohol having 1 to 18 carbon atoms
Phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol (these phenols may have a lower alkyl group); C3-15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; C2-15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolylaldehyde and naphthaldehyde; Methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, benzoate Methyl acrylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, anisic acid Methyl, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, Rusanji n- butyl phthalate, di n- pentyl, diisopentyl phthalate, di n
-Hexyl, diisohexyl phthalate, di-n-phthalate
Organic acid esters having 2 to 30 carbon atoms such as heptyl, diisoheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and anisole and diphenyl ether 2-20 ethers; for example (Wherein, 2 ≦ n ≦ 10, and R ^{1 to} R ²⁵ are substituents having at least one element selected from carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, boron and silicon, R ^{1 to} R ²ⁿ are bonded to the main chain by a carbon-carbon bond,
Arbitrary R ^{1 to} R ²⁶ may together form a ring other than a benzene ring, and an element other than carbon may be contained in the main chain. Polyethers represented by). More specifically, 2- (2-ethylhexyl) -1,
3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-
Cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3
-Dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, -(1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1
-Decahydronaphthyl) -1,3-dimethoxypropane,
2- (pt-butylphenyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2
-Dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3- Dimethoxypropane, 2-methyl-2-
Ethyl-1,3-dimethoxypropane, 2-methyl-2-
Isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane,
2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3
-Dimethoxypropane, 2-methyl-2-isobutyl-
1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxy Propane, 2,2-dibenzyl-1,3-
Dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-
1,3-diethoxypropane, 2,2-diisobutyl-1,3-
Dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-s-butyl-
1,3-dimethoxypropane, 2,2-di-t-butyl-1,3
-Dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl -2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3
-Dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-diethoxybutane, 2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane,
2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-
1,5-dimethoxypentane, 2,4-diisoamyl-1,5-
Dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisoamyloxypropane, 1,2-diisobutoxypropane,
1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane, 2 , 2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane,
2,2-hexamethylene-1,3-dimethoxypropane, 1,2
-Bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5.5] undecane, 3,7-dioxabicyclo [3.3.1] nonane, 3,7-dioxabicyclo [3.3.0] octane, 3,3- Diisobutyl-1,5-oxononane, 6,6
-Diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis [dimethoxymethyl]
Cyclohexane, 1,1-bismethoxymethyl] bicyclo [2.2.1] heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxy Methyl-1,3-diethoxypropane, 2-cyclohexyl-
2-methoxymethyl-1,3-dimethoxypropane, 2,2-
Diisobutyl-1,3-dimethoxycyclohexane, 2-
Isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2 -Methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2- Ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2- Ethoxymethyl-1,3-dimethoxycyclohexene Emissions can be exemplified tris (p- methoxyphenyl) phosphine. Of these, 1,3-diethers are preferable, and in particular, 2,2-diisobutyl-1,3-dimethoxypropane,
5 to 40 carbon atoms such as -isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane Acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile and tolunitrile; P- such as trimethyl phosphite and triethyl phosphite
Organic phosphorus compounds having an OC bond; Ethyl silicate and alkoxysilanes such as diphenyldimethoxysilane are used. These electron donors can be used alone or in combination.

Among such electron donors, preferred electron donors include esters of organic acids or inorganic acids, alkoxy (aryloxy) silane compounds, ethers, ketones, tertiary amines, acid halides, and active hydrogens such as acid anhydrides. These compounds are compounds having no organic acids, and particularly preferred are organic acid esters and alkoxy (aryloxy) silane compounds. Among them, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms, malonic acid, substituted malonic acid, substituted succinic acid and maleic acid Particularly preferred are esters and diethers of acids, substituted maleic acids, dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and phthalic acid with alcohols having 2 or more carbon atoms. Of course, these electron donors do not need to be added to the reaction system at the time of preparing the catalyst component [A]. For example, a compound which can be converted to these electron donors is added to the reaction system, and this compound is prepared in the catalyst preparation process. Can be converted to the above-mentioned electron donor.

The catalyst component [A] obtained as described above can be purified by sufficiently washing it with a liquid inert hydrocarbon compound after preparation. Specific examples of the hydrocarbon that can be used in this washing include n-pentane, isopentane, n-hexane, isohexane, and n-pentane.
-Aliphatic hydrocarbon compounds such as heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene, and liquid paraffin; alicyclic hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; Aromatic hydrocarbon compounds such as toluene, xylene, and cymene; and halogenated hydrocarbon compounds such as chlorobenzene and dichloroethane.

Such compounds can be used alone or in combination.

In the present invention, as the organometallic compound catalyst component [B], it is preferable to use an organoaluminum compound having at least one A-carbon bond in the molecule.

Examples of such organoaluminum compounds include: (i) the formula R ¹ _mA (OR ² ) _{n Hp} X _q (where R ¹ and R ² usually have 1 to 15 carbon atoms, preferably X is a halogen atom, and m is 0 ≦ m.
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <
A number of 3, yet m + n + p + organoaluminum compound represented by q = a 3), and (ii) formula M ¹ AR ¹ ₄ (wherein M ¹ is Li, Na, K, and the R ¹ is the The same meaning), and a complex alkylated product of aluminum and a metal of Group I of the periodic table.

Specific examples of the organoaluminum compound represented by the above formula (i) include the compounds described below.

A compound represented by the formula R ¹ _mA (OR ² ) _3-m (where R ¹ and R ² have the same meaning as described above, and m is preferably 1.5 ≦
m ≦ 3).

A compound represented by the formula R ¹ _m AX _3-m (where R ¹ has the same meaning as described above, X is a halogen, and m is preferably 0 <m
<3. ) A compound represented by the formula R ¹ _m AX _3-m (where R ¹ has the same meaning as described above, and m is preferably 2 ≦ m <3). Formula R ¹ _m A (OR ² ) _n X a compound represented by _q (where R ¹ and R ² are the same as above; X is a halogen, 0 <m ≦ 3, 0 ≦
n <3, 0 ≦ q <3, and m + n + q = 3).

Specific examples of the organoaluminum compound represented by the above formula (i) include trialkylaluminums such as triethylaminium, tributylaluminum, and triisopropylaluminum; trialkenylaluminums such as triisoprenylaluminum; and diethylaluminumethoxy. de, partially with dialkylaluminum alkoxides such as dibutyl aluminum butoxide, ethyl aluminum sesqui ethoxide, alkyl sesquichloride alkoxides such as butyl sesquichloride butoxide, an average composition represented by such formula _{^{R 1 2.5 a (OR 2)}} 0.5 Alkyl aluminums, such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, etc. Alkyl aluminum sesquihalides such as alkyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, and partial alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dibromide Alkyl aluminum halides, dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride, and alkyl aluminums such as ethyl aluminum dihydride and propyl aluminum dihydride partially alkylated alkyl aluminum dihydride Aluminum, ethylaluminum ethoxychloride, butylaluminum Kishikurorido, partially alkoxylated and halogenated alkylaluminum such as such as ethyl aluminum ethoxy bromide is used.

The organoaluminum compound used in the present invention is a compound similar to the compound represented by the formula (i) such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. You may. Specific examples of such compounds include (C ₂ H ₅ ) ₂ AOA (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AOA (C ₄ H ₉ ) ₂ , and And the like.

Examples of the organoaluminum compound represented by the above formula (ii) include LiA (C ₂ H ₅ ) ₄ and L
iA (C ₇ H ₁₅ ) _{4 and the} like. Among these, it is particularly preferable to use a trialkylaluminum, a mixture of a trialkylaluminum and an aluminum halide, and a mixture of a trialkylaluminum and an alkylaluminum halide.

When performing the polymerization reaction, it is preferable to use an electron donor [C] in addition to the catalyst component [A] and the organometallic compound catalyst component [B].

As such an electron donor [C], specifically,
Amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoamides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates , Alkoxy (aryloxy) silanes, organic acids, groups I, II, III and IV of the periodic table
Examples include amides of metals belonging to the group, and acceptable salts thereof. The salts can also be formed in a reaction system by a reaction between an organic acid and an organometallic compound used as the catalyst component [B].

Specific examples of these electron donors include the compounds exemplified above as the catalyst component [A]. Among these electron donors, particularly preferred electron donors include organic acid esters, alkoxy (aryloxy) silane compounds, ethers, ketones, acid anhydrides and amides. In particular, when the electron donor in the catalyst component [A] is a monocarboxylic acid ester, the electron donor is preferably an alkyl ester of an aromatic carboxylic acid.

When the electron donor in the catalyst component [A] is a dicarboxylic acid and an alcohol or ester having 2 or more carbon atoms, the electron donor [C] may be represented by the formula R _n Si (OR ¹ ) _4-n (However, in the above formula, R and R ¹ represent a hydrocarbon group, and 0 ≦ n <4). It is preferable to use an alkoxy (aryloxy) silane compound represented by the formula or an amine having a large steric hindrance.

Specific examples of such an alkoxy (aryloxy) silane compound include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, and t-butylmethyldisilane. Ethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane,
Bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolylmethoxysilane,
Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxy Silane, decylmethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso- Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane , Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyl Triallyloxy silane, vinyl tris (β-methoxyethoxy silane), dimethyltetraethoxydisiloxane and the like are used. Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane,
Phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolylmethoxysilane, p-
Preferred are tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, ethyl silicate and the like.

As the amine having a large steric hindrance, 2,2,6,6
-Tetramethylpyridine, 2,2,5,5-tetramethylpyrrolidine or derivatives thereof, tetramethylmethylenediamine and the like are particularly preferred. Among these compounds, as the electron donor used as a catalyst component, an alkoxy (aryloxy) silane compound and the aforementioned polyethers are particularly preferable.

Further, in the present invention, a catalyst component [i] containing a transition metal atom compound of Groups IVB and VB of the Periodic Table of the Elements having a group having a conjugated π electron as a ligand, and an organometallic compound catalyst component [ii] ] Can be preferably used.

Here, examples of the transition metals of Groups IVB and VB of the periodic table include metals such as zirconium, titanium, hafnium, chromium, and vanadium.

Examples of the ligand having a group having a conjugated π electron include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a t-butylcyclopentadienyl group, and a dimethylcyclopentadienyl group. Groups, alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl group, indenyl group, fluorenyl group and the like.

Further, at least two ligands having a cycloalkadienyl skeleton have a lower alkylene group or silicon,
Preferable examples include a group bonded through a group containing phosphorus, oxygen, and nitrogen.

Examples of such a group include groups such as an ethylenebisindenyl group and an isopropyl (cyclopentadienyl-1-fluorenyl) group.

One or more ligands having such a cycloalkadienyl skeleton coordinate with the transition metal, and
One is coordinated.

The ligand other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like.Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.Examples of the aryl group include a phenyl group and a tolyl group.Examples of the aralkyl group include a benzyl group, A neofil group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

 Such a cycloalkadienyl used in the present invention
A transition metal compound containing a ligand having a skeleton is, for example,
When the valence of the transition metal is 4, more specifically, the formula R^Two _kR^Three R^Four _mR^Five _nM (where M is zirconium, titanium, hafnium,
Is vanadium, etc., and R^TwoIs the cycloalkadienyl bone
Group with a case, R^Three, R^FourAnd R^FiveIs cycloalkadi
Group having an enyl skeleton, alkyl group, cycloalkyl
Group, aryl group, aralkyl group, alkoxy group, aryl
A roxy group, a halogen atom or hydrogen, and k is 1 or more
And k ++ m + n + =).
You.

Particularly preferably, in the above formula, R ² and R ³ are groups having a cycloalkadienyl skeleton, and the two groups having a cycloalkadienyl skeleton are preferably a lower alkyl group or silicon, phosphorus, oxygen, nitrogen Is a compound bonded via a group containing

Hereinafter, specific examples of the transition metal compound containing a ligand having a cycloalkadienyl skeleton in which M is zirconium will be described.

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis ( Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium Monochloride hydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) dichloride Ruconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium Monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride bis (indenyl) zirconium dichloride, bis (indenyl) zirconium Dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadi Nil) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (methylcyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium phenoxycyclolide Bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) diethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium, ethylenebis (indenyl) ethylzirconium monochloride, ethylenebis (indenyl) zirconium dichloride, Isopropyl bisindenyl zirconium dichloride, isopropyl (cyclopentadienyl) -1 Fluorenyl zirconium chloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) zirconium methoxymonochloride, ethylenebis (indenyl) zirconium ethoxymonochloride, ethylenebis (indenyl) zirconium phenoxymonochloride, ethylenebis (cyclopentane Dienyl) zirconium dichloride, propylene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (t-butylcyclopentadienyl) zirconium dichloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) dimethyl Zirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ) Zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) Zirconium dichloride, ethylene bis (6-methyl-1-indenyl) zirconium dichloride, ethylene bis (7-methyl-1-indenyl) zirconium dichloride, ethylene bis (5-methoxy-1-indenyl) zirconium dichloride, ethylene bis (2, 3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl) zirconium dichloride.

In the above zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, vanadium metal, or the like can also be used.

In this case, the organometallic compound catalyst component [ii]
For example, a conventionally known aluminoxane or organic aluminum oxy compound is used. The organoaluminum oxy compound is obtained, for example, by a reaction between an organoaluminum compound and water or a reaction between aluminoxane dissolved in a hydrocarbon solution and water or an active hydrogen-containing compound.

In the present invention, the amount of the catalyst used varies depending on the type of the catalyst to be used and the like. For example, the catalyst component [A], the organometallic oxide catalyst component [B] and the electron donor [C] are used as described above. In the case or when the catalyst components (i) and (ii) are used, the catalyst component [A] or the catalyst component (ii) is usually used in an amount of 0.001 to 0.5 mmol, in terms of transition metal, per polymerization volume. Preferably 0.005-
The amount of the organometallic compound catalyst [B] used is 0.5 mmol, and the amount of the organometallic compound catalyst [B] used is 1 mole of the transition metal atom of the catalyst component [A] in the polymerization system.
Is usually used in an amount of 1 to 10,000 mol, preferably 5 to 500 mol. Further, when the electron donor [C] is used, the electron donor [C] is used in an amount of 100 mol or less, per 1 mol of the transition metal atom of the catalyst component [A] in the polymerization system.
It is preferably used in an amount of 1 to 50 mol, particularly preferably 3 to 20 mol.

The polymerization temperature at the time of performing polymerization using the above-mentioned catalyst is usually 20 to 200 ° C., preferably 50 to 100 ° C., and the pressure is normal pressure to 100 kg / cm ² , preferably ^{2 to} 50 kg / cm ² It is.

In the present invention, it is preferable to carry out preliminary polymerization prior to main polymerization. When performing prepolymerization,
As the catalyst, at least the catalyst component [A] and the organometallic compound catalyst component [B] are used in combination, or the catalyst component (i) and the catalyst component (ii) are used in combination.

When titanium is used as the transition metal, the polymerization amount in the prepolymerization is usually 1 per 1 g of the titanium catalyst component.
~ 2000g, preferably 3 ~ 1000g, particularly preferably 10 ~ 50g
It is 0g.

The prepolymerization can be performed using an inert hydrocarbon solvent. Such inert hydrocarbon solvents include:
Specifically, propane, butane, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane,
n-octane, i-octane, n-decane, n-dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, benzene, toluene, xylene; Halogenated hydrocarbon compounds such as aromatic hydrocarbons, methylene chloride, ethyl chloride, ethylene chloride and chlorobenzene are used. Among them, aliphatic hydrocarbons are preferred, and aliphatic hydrocarbons having 4 to 10 carbon atoms are particularly preferred. Further, a monomer used in the reaction can be used as a solvent.

As the α-olefin used for the prepolymerization,
Specifically, ethylene, propylene, 1-butene, 1-
Pentene, 4-methyl-1-pentene, 3-methyl-1
Α-olefins having 10 or less carbon atoms, such as -pentene, 1-heptene, 1-octene, and 1-decene, are used, among which α-olefins having 3 to 6 carbon atoms are preferable, and propylene is particularly preferable. These α-olefins can be used alone or in combination of two or more as long as a crystalline polymer is produced.

In particular, polymer particles containing a large amount of the amorphous olefin polymer part and having good particle properties, for example, polymer particles containing the amorphous olefin polymer part in an amount of 30% by weight or more and having good particle properties. Is obtained by pre-polymerization, for example from 70 to
A method is proposed in which propylene and ethylene are copolymerized using a mixed gas consisting of 98 mol% of propylene and 30 to 2 mol% of ethylene.

The polymerization temperature in the prepolymerization differs depending on the α-olefin used and the use of the inert solvent and cannot be unconditionally specified, but is generally -40 to 80 ° C, preferably -20 to
It is 40 ° C, particularly preferably -10 to 30 ° C. For example, when propylene is used as the α-olefin, -40 to
70 ° C, -40 to 40 ° C when using 1-butene, 4
-Methyl-1-pentene and / or 3-methyl-1
-When pentene is used, it is in the range of -40 to 70 ° C. It should be noted that a hydrogen gas can also be allowed to coexist in the reaction system for this preliminary polymerization.

Producing polymer particles by conducting the polymerization reaction (main polymerization) by introducing the above-mentioned monomer into the reaction system after or without the preliminary polymerization as described above, and then performing the preliminary polymerization. Can be.

The monomer used in the main polymerization may be the same as or different from the monomer used in the prepolymerization.

The polymerization temperature of the main polymerization of such an olefin is usually
The temperature is from -50 to 200C, preferably from 0 to 150C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm
² , and the polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system.

The molecular weight of the obtained olefin polymer is hydrogen and / or
Or it can be adjusted by the polymerization temperature.

The polymer particles thus obtained contain a crystalline olefin polymer part and an amorphous olefin polymer part. And, in the present invention, the amorphous olefin polymer portion in the polymer particles is usually 20 to 80% by weight,
Preferably, it is contained in the range of 25 to 70% by weight, more preferably 30 to 60% by weight, particularly preferably 33 to 55% by weight. In the present invention, the content of such an amorphous olefin polymer can be determined by measuring the amount of a component soluble in n-decane at 23 ° C.

Further, the polymer particles used in the present invention, of the polymer constituting the polymer particles, the higher of the melting point of the crystalline olefin polymer portion or the glass transition point of the amorphous olefin polymer portion, whichever is higher. It is preferable that the polymer particles have not been substantially heated.

The term “amorphous olefin polymer part” as used herein means a polymer that is soluble in n-decane at 23 ° C., and specifically refers to a polymer part separated by a solvent according to the following method.
That is, in the present specification, n with the addition of the polymer particles (3 g) is used.
After dissolving the decane (500 ml) solution at 140 to 145 ° C with stirring, stop stirring, cool to 80 ° C in 3 hours, cool to 23 ° C in 5 hours, and keep at 23 ° C for 5 hours, G-
A polymer obtained by filtering and separating using a 4-glass filter and removing n-decane from the obtained filtrate is referred to as “amorphous olefin polymer part”.

Among the polymer particles used in the present invention, non-crosslinked polymer particles are polymer particles as described above, and gas-phase crosslinked polymer particles are polymer particles as described above,
Crosslinked polymer particles (intraparticle crosslinking) produced by contacting a crosslinking agent at a temperature lower than the higher of the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer. Thermoplastic elastomer).

As the cross-linking agent used in the present invention (including the case where it is used in the production of gas-phase cross-linked polymer particles), organic peroxides, sulfur, phenolic vulcanizing agents, oximes, polyamines and the like are used. Among them, organic peroxides and phenolic vulcanizing agents are preferred from the viewpoint of the physical properties of the obtained thermoplastic elastomer. Particularly, an organic peroxide is preferable.

Specific examples of the phenolic vulcanizing agent include an alkylphenol formaldehyde resin, a triazine-formaldehyde resin, and a melamine-formaldehyde resin.

As the organic peroxide, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,2
5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (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, dibenzoyl peroxide, tert-butylperoxybenzoate Are used. Of these, dibenzoyl peroxide and 1,3-bis (tert-butylperoxyisopropyl) benzene are preferred from the viewpoints of crosslinking reaction time, odor, and scorch stability.

Further, in order to realize the crosslinking reaction uniformly and moderately, it is preferable to add a crosslinking assistant. Specific examples of the crosslinking assistant include sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, and trimethylolpropane. A peroxy crosslinking auxiliary such as -N, N'-m-phenylenedimaleimide or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc. And polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate. By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is easy to handle, has good compatibility with polymer particles, has an organic peroxide solubilizing effect, and also acts as a peroxide dispersing agent. This is most preferable because a thermoplastic elastomer having a balance between properties and physical properties can be obtained.

In the present invention, such a crosslinking aid is used in an amount of 0.1 to 2 parts by weight, particularly 0.3 to 1 part by weight, based on 100 parts by weight of the polymer particles.
A thermoplastic elastomer having excellent fluidity and having no change in physical properties due to the heat history at the time of processing and molding the thermoplastic elastomer can be obtained.

In the present invention, when producing a thermoplastic elastomer composition or gas-phase crosslinked polymer particles, polymer particles,
In addition to a crosslinking agent and a crosslinking assistant, a crosslinking reaction of the polymer particles may be carried out in the presence of a peroxide non-crosslinked hydrocarbon rubber-like substance represented by polyisobutylene, butyl rubber and / or a mineral oil-based softening agent, if necessary. You can do it.

Mineral oil-based softeners usually weaken the intermolecular force of rubber when rolling rubber to facilitate the processing, help disperse carbon black, white carbon, etc., or harden the vulcanized rubber. This is a high-boiling oil fraction used for the purpose of decreasing its hardness and increasing its flexibility or elasticity, and specifically, paraffinic, naphthenic or aromatic mineral oils are used.

Such a mineral oil-based softener, in order to further improve the flow properties of the thermoplastic elastomer, that is, moldability,
The amount is 1 to 100 parts by weight, preferably 3 to 90 parts by weight, more preferably 5 to 80 parts by weight, based on 100 parts by weight of the polymer particles.

In the production of the gas-phase crosslinked polymer particles, a crosslinking agent, and if necessary, a crosslinking aid and a mineral oil-based softening agent may be diluted with a swelling solvent before use. The swelling solvent dilutes the cross-linking agent and, if necessary, the cross-linking aid to aid dispersion on the polymer particle surface, and swells the polymer particles,
At that time, since a cross-linking agent and a cross-linking aid are transported into the polymer particles, the use of a swelling solvent enables a uniform cross-linking reaction even to the inside of the polymer particles. If a poor solvent for the olefin polymer is used as the swelling solvent, it is also possible to cause a selective cross-linking reaction near the surface of the polymer particles. In any case, what kind of swelling solvent is selected in the reaction depends on the kind of the polymer particles used and the like. Of course, the crosslinking reaction is possible without using any swelling solvent.

Specific examples of such a swelling solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane; cyclohexane, and methyl. Aliphatic hydrocarbon solvents such as cyclohexane and decahydronaphthalene, chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, dichloroethylene, and trichloroethylene Solvent, methanol,
Ethanol, n-propanol, iso-propanol,
alcohol solvents such as n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; dimethyl ether, diethyl ether and di-n- Ether solvents such as amyl ether, tetrahydrofuran, dioxane and anisole are used.

It is desirable that such a swelling solvent be used in an amount of 1 to 100 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the polymer particles.

The swelling solvent as described above, when contacted with the polymer particles used in the present invention, swells the polymer particles, particularly the amorphous olefin polymer portion of the polymer particles, and a crosslinking agent and a crosslinking aid are used. It plays a role in facilitating penetration into the particles.

However, the amount of the swelling solvent used in the present invention is 200 parts by weight or less based on 100 parts by weight of the polymer particles, and the gas phase crosslinking reaction in the present invention is a solvent suspension reaction using a large excess of a solvent. different.

The gas-phase crosslinking reaction in the present invention is performed at a temperature at which the polymer particles are melted and the polymer particles do not fuse with each other. Generally, the above reaction is carried out at a temperature in the range from 0 ° C. to a temperature lower than the higher of the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer. For example, when the polymer having the high melting point is polypropylene, high-density polyethylene, or low-density polyethylene, the temperature is about 150 ° C. and 120 ° C., respectively.
A temperature around 90 ° C. is the upper limit of the reaction temperature.

In addition, the reaction time is 1 to 30 times, preferably 2 to 10 times the half-life time of the crosslinking agent at the temperature at which the gas phase crosslinking reaction is performed,
More preferably, the time is 3 to 7 times, and the pressure is from 0 to
50 kg / cm ^2, preferably 1~20kg / cm ^2, more preferably 1-5 kg / cm ^2. The gas-phase crosslinking reaction can be performed in any of a batch system and a continuous system.

During the production of the gas-phase crosslinked polymer particles, the polymer particles, a crosslinking agent, and if necessary, a crosslinking aid, a mineral oil-based softening agent,
It is most preferable to carry out a gas-phase crosslinking reaction by contacting at the same time, but a gas-phase crosslinking reaction can also be carried out by separately contacting a crosslinking agent, a crosslinking aid, and a mineral oil-based softener with the polymer particles.

When the polymer particles comprising the crystalline olefin polymer portion and the amorphous olefin polymer portion are crosslinked in this manner,
A cross-linking reaction occurs inside the polymer particles, and particularly a cross-linking reaction occurs in the amorphous olefin polymer portion of the polymer particles, and the amorphous olefin polymer portion (rubber component) is fixed in the particles at the molecular segment level. Is done.

The reactor used in the present invention is a device capable of mixing at least polymer particles, and may be either a vertical reactor or a horizontal reactor. When performing heat treatment, a reactor capable of mixing and heating the polymer particles is used. As the reactor used in the present invention, specifically, a fluidized bed, a moving bed, a loop reactor, a horizontal reactor with a stirring blade,
Examples include a rotating drum and a vertical reactor with a stirring blade.

In the crosslinked polymer particles composed of a thermoplastic elastomer crosslinked in a particle, the insoluble gel fraction not extracted into cyclohexane measured as described below is 10% by weight or more, preferably 40 to 100% by weight, more preferably Is 60-9
It is desirable that the content be 9% by weight, particularly preferably 80 to 98% by weight.

The above gel content of 100% by weight indicates that the obtained thermoplastic elastomer is completely crosslinked.

Here, the measurement of the cyclohexane-insoluble gel content is performed as follows. Approximately 100 mg of thermoplastic elastomer sample pellets (size of each pellet: 1 mm x 1 mm x 0.5 mm)
Is weighed and immersed in 30 cc of cyclohexane at 23 ° C. for 48 hours in a closed container, and then the sample is taken out and dried. If the thermoplastic elastomer contains cyclohexane-insoluble fillers, pigments, etc., the weight of this dry residue minus the cyclohexane-insoluble fillers, pigments, and other components other than the polymer component is reduced to dryness. This is the corrected final weight (Y). On the other hand, when cyclohexane-soluble components other than the ethylene / α-olefin copolymer are contained in the sample pellets, for example, a cyclohexane-insoluble filler or pigment is contained in the plasticizer and the cyclohexane-soluble rubber component and the thermoplastic elastomer. , The initial weight (X) obtained by subtracting the weight of these components other than the polyolefin resin, such as the cyclohexane-insoluble filler and pigment, is used as the corrected initial weight.

From these values, the cyclohexane-insoluble gel fraction is determined by the following equation.

Preferred crosslinked polymer particles composed of a thermoplastic elastomer produced as described above, the average particle diameter is 100 to 5
000 μm, preferably 200 to 4000 μm, more preferably
It is in the range of 300-3000 μm. Further, the crosslinked polymer particles used in the present invention, the geometric display deviation indicating the particle size distribution of the particles, 1.0 to 3.0, preferably 1.0 to 2.0, more preferably
1.0 to 1.5, more preferably 1.0 to 1.3. The crosslinked polymer particles used in the present invention have an apparent bulk specific gravity of 0.25 to 0.70, preferably 0.30 to 0.60, more preferably
It is in the range of 0.35 to 0.50. The aspect ratio of the crosslinked polymer particles used in the present invention is in the range of 1.0 to 3.0, preferably 1.0 to 2.0, and more preferably 1.0 to 1.5. In the crosslinked polymer particles used in the present invention, the amount of fine particles having a particle diameter of 100 μm or less is 20% by weight or less, preferably 0 to 10% by weight, and more preferably 0 to 2% by weight.

The crosslinked polymer particles (thermoplastic elastomer particles) produced as described above include fillers such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, Barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, carbon fiber or colorant such as carbon black,
Titanium oxide, zinc white, red iron, ultramarine, navy blue, azo dyeing, nitroso dye, lake pigment, phthalocyanine pigment and the like can also be blended.

Since the crosslinked polymer particles used in the present invention are polymer particles obtained by performing a crosslinking reaction (gas phase crosslinking reaction) of the polymer particles at a low temperature, thermal decomposition of the polymer particles can be suppressed. A molded article excellent in strength physical properties such as impact strength and tensile strength, toughness, heat resistance, flexibility at low temperature, surface smoothness, and paintability can be provided.

In particular, the crosslinked polymer particles (thermoplastic elastomer) in which the amorphous olefin polymer portion (rubber component) is fixed in the particles at the molecular segment level are more improved in flexibility at low temperatures, surface smoothness and coatability. It can give excellent molded products.

Polyolefin As the polyolefin used in the present invention, specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl Homopolymers or copolymers of α-olefins such as -1-pentene and 1-octene, or copolymers of α-olefins with a small amount of another polymerizable monomer of, for example, 10 mol% or less, for example, ethylene-
Polyolefins such as a vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-methacrylic acid copolymer are exemplified.

In the present invention, the polyolefin has a weight ratio (crosslinked polymer / crosslinked polyolefin and / or non-crosslinked polyolefin) of 90/10 between the crosslinked polymer and the crosslinked polyolefin and / or non-crosslinked polyolefin constituting the thermoplastic elastomer composition. It is used in such a ratio as to become 5/95.

In the present invention, when the polyolefin is used in the above-described mixing ratio, a thermoplastic elastomer composition which can provide a molded article having better fluidity and excellent appearance can be obtained.

In the present invention, the weight ratio (crosslinked polymer / crosslinked polyolefin and / or noncrosslinked polyolefin) of the crosslinked polymer constituting the thermoplastic elastomer composition to the crosslinked polyolefin and / or non-crosslinked polyolefin is 5 /
When a polyolefin is used in a ratio of 95 to 49/51, preferably 10/90 to 40/60, it prevents shrinkage, which is a drawback of polyethylene, and improves properties such as impact resistance and cold resistance. be able to. In addition, unlike the conventional polyolefin-rubber composition, there is no possibility that the fluidity is extremely deteriorated to cause poor appearance. Especially soft polyolefins,
For example, for low-density polyolefin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, it is not only possible to prevent sink marks, but also to improve rubber properties such as heat resistance and permanent elongation. it can.

On the other hand, in the present invention, the weight ratio of the crosslinked polymer to the crosslinked polyolefin and / or non-crosslinked polyolefin (crosslinked polymer / crosslinked polyolefin and / or non-crosslinked polyolefin) is 90/10 to 50/50, preferably 77/23.
The thermoplastic elastomer composition of ~ 67/33 can be molded by the equipment used for molding ordinary thermoplastics, and is suitable for extrusion molding, calender molding and especially injection molding. Further, the thermoplastic elastomer composition has a weight ratio of a crosslinked polymer to a crosslinked polyolefin and / or a noncrosslinked polyolefin (crosslinked polymer / crosslinked polyolefin and / or noncrosslinked polyolefin).
Compared with 5/95 to 49/51 polyolefin-rich thermoplastic elastomer composition, heat resistance, tensile properties, flexibility and rubber properties such as rebound resilience are more excellent,
In addition, it is possible to provide a large-sized thick product having better fluidity and excellent appearance without flow marks or sink marks.

In the present invention, in addition to the above polymer particles (including gas-phase crosslinked polymer particles) and polyolefin, conventionally known heat stabilizers, weather stabilizers, antioxidants, antistatic agents,
Additives such as pigments, dyes, fillers, flame retardants, nucleating agents, lubricants, slip agents, and antiblocking agents can be added as long as the objects of the present invention are not impaired.

Production Method In the present invention, a thermoplastic elastomer composition is produced by melt-kneading a mixture containing, for example, the above-mentioned non-crosslinked polymer particles, a crosslinking agent, and a polyolefin, and partially or completely. Crosslinking may be performed.

The crosslinking agent is about 0.0 parts by weight based on 100 parts by weight of the polymer particles.
It is used in an amount of 1 to 2 parts by weight, preferably 0.03 to 1.0 part by weight, more preferably 0.05 to 0.5 part by weight.

As the kneading apparatus used for the above-mentioned melt kneading, an open apparatus such as a mixing roll or a non-open apparatus such as a Banbury mixer, an extruder, a kneader or a continuous mixer can be used. Among such kneading apparatuses, an extruder is particularly preferably used.

The kneading is preferably performed in a non-release type device, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature is usually 150-280 ° C, preferably 17
The temperature is 0 to 240 ° C, and the kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes.

According to this production method, a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and / or a noncrosslinked polyolefin is obtained.

Further, in the present invention, a crosslinked polymer obtained by crosslinking the non-crosslinked polymer particles as described above in the presence of at least a crosslinking agent and a polyolefin are kneaded, and partially or completely crosslinked. By carrying out, a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and / or a non-crosslinked polyolefin can also be produced.

The apparatus used for the above-mentioned melting and kneading and the melt-kneading conditions are the same as the above-mentioned kneading apparatus and melt-kneading conditions.

Further, in the present invention, a thermoplastic elastomer composition containing a crosslinked polymer and a polyolefin can also be produced by melt-kneading a mixture containing the above-mentioned gas-phase crosslinked polymer particles and a polyolefin.

The apparatus used for the melting and kneading is the same as the above-described kneading apparatus.

The kneading is preferably performed in a non-release type device, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature is usually 150-280 ° C, preferably 17
The temperature is 0 to 240 ° C, and the kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes.

Effects of the Invention According to the present invention, there is provided a thermoplastic elastomer composition which is excellent in heat resistance, tensile properties, weather resistance, flexibility and rebound resilience, and which can provide a molded article having good fluidity and excellent appearance. be able to.

In the thermoplastic elastomer composition obtained by the production method according to the present invention, the weight ratio of the crosslinked polymer to the crosslinked polyolefin and / or the non-crosslinked polyolefin (crosslinked polymer / crosslinked polyolefin and / or non-crosslinked polyolefin) is 5 /. The 95 to 49/51 thermoplastic elastomer composition has an effect of preventing sink marks, which is a drawback of polyolefin, and an effect of improving properties such as impact resistance and cold resistance. In addition, unlike the conventional polyolefin-rubber composition, there is no possibility that the fluidity is extremely deteriorated to cause poor appearance. In particular, as a polyolefin, a thermoplastic elastomer composition using a soft polyolefin such as low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, has a rubber having anti-sink effect, heat resistance and permanent elongation. Has the effect of improving the mechanical properties.

In the thermoplastic elastomer composition obtained by the production method according to the present invention, the weight ratio of the crosslinked polymer to the crosslinked polyolefin and / or the non-crosslinked polyolefin (crosslinked polymer / crosslinked polyolefin and / or non-crosslinked polyolefin) is A thermoplastic elastomer composition rich in thermoplastic elastomer (crosslinked polymer) of 90/10 to 50/50 can be molded by an apparatus used for molding ordinary thermoplastics, such as extrusion molding, calender molding, and the like. Particularly suitable for injection molding. In addition, the thermoplastic elastomer composition has a polyolefin having a weight ratio of a crosslinked polymer to a crosslinked polyolefin and / or a non-crosslinked polyolefin (crosslinked polymer / crosslinked polyolefin and / or noncrosslinked polyolefin) of 5/95 to 49/51. Compared with the rich thermoplastic elastomer composition, the rubber properties such as heat resistance, tensile properties, flexibility and rebound resilience are more excellent, and the fluidity is better, and there is no flow mark or sink mark. There is an effect that a large-sized thick product excellent in appearance can be provided.

The thermoplastic elastomer composition according to the present invention having the above effects can be used as a body panel, a bumper part, a side shield, an automobile part such as a steering wheel, a shoe sole, a footwear such as a sandal, an electric wire covering, a connector, a cap plug and the like. Electrical parts, golf club grips, baseball bat grips, swimming fins, underwater glasses and other leisure goods, waterproof sheets, waterproof materials, joint materials, architectural window frames, architectural gaskets, decorative hardwood covering materials, etc. Used for civil engineering and construction material parts, gaskets, waterproof fabrics, garden hoses, belts and other applications.

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

[Adjustment of the catalyst component [A]] A high-speed stirrer (manufactured by Tokushu Kika Kogyo Co., Ltd.) with an internal volume of 2 is sufficient.
After replacing with N ₂ , 700 ml of purified kerosene, 10 g of commercially available MgC ₂ , 24.2 g of ethanol and ₃ g of Emazol 320 (trade name, sorbitan distearate, manufactured by Kao Atlas Co., Ltd.) were added. The mixture was stirred at 800 rpm for 30 minutes. Under high-speed stirring, the solution was transferred to a glass flask 2 (with a stirrer) into which purified kerosene 1 previously cooled to −10 ° C. was charged using a Teflon tube having an inner diameter of 5 mm. The resulting solid was collected by filtration and washed sufficiently with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was treated with 120 ml of titanium tetrachloride.
The temperature was raised to ° C. After stirring and mixing at 120 ° C. for 2 hours, a solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and again stirred and mixed at 130 ° C. for 2 hours. Further, a solid substance was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component (A). This component is composed of titanium 2.2% by weight, chlorine 63% by weight, magnesium 20% by weight, diisobutyl phthalate 5.5% in atomic conversion.
% By weight. A spherical catalyst having an average particle size of 64 μm and a geometric standard deviation (δ _g ) of the particle size distribution of 1.5 was obtained.

[Preliminary polymerization] The following preliminary polymerization was performed on the catalyst component [A].

After charging 200 ml of purified hexane into a 400 ml glass-made reactor purged with nitrogen, 20 mmol of triethylaluminum, 4 mmol of diphenyldimethoxysilane and
After charging 2 mmol of the Ti catalyst component [A] in terms of titanium atoms, propylene was supplied at a rate of 5.9 N / hour over 1 hour to polymerize 2.8 g of propylene per 1 g of the Ti catalyst component [A]. . The temperature was kept at 20 ± 2 ° C. during the polymerization. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

[Polymerization] Production of copolymer (1) 2.0 kg of propylene and hydrogen
After adding 9N liter, the temperature was raised, and at 50 ° C., 15 mmol of triethylaluminum, dicyclohexyldimethoxysilane
1.5 mmol, 0.05 mmol of the prepolymerized product of the catalyst component [A] was added in terms of titanium atom, and the temperature in the polymerization vessel was reduced to 70%.
C. Thirty minutes after the temperature reached 70 ° C., the vent valve was opened, and propylene was homogenized by purging propylene until the pressure in the polymerization vessel became normal pressure. After purging, copolymerization was subsequently carried out. That is, ethylene was supplied to the polymerization reactor at a rate of 480 N / hour and propylene was supplied at a rate of 720 N / hour. The vent opening of the polymerization vessel was adjusted so that the pressure in the polymerization vessel was 10 kg / cm ² · G. The temperature during the copolymerization was kept at 70 ° C. The copolymerization was performed with a copolymerization time of 150 minutes.

 Table 1 shows the physical properties of the obtained copolymer (1).

Production of Copolymers (2) and (3) In the production of the copolymer (1), the copolymerization conditions were changed as follows, and the copolymerization conditions were changed as shown in Table 1. Copolymers (2) and (3) were produced in the same manner as in producing polymer (1).

Table 1 shows the physical properties of the obtained copolymers (1) to (3).

[Preliminary polymerization] The following preliminary polymerization was performed on the catalyst component [A]. 400 ml of purified hexane was charged into one glass reactor purged with nitrogen, and 1.32 mmol of triethylaluminum, 0.27 mmol of cyclohexylmethyldimethoxysilane and
After charging 0.132 mmol of Ti catalyst component [A] in terms of titanium atom, propylene gas and ethylene gas were each added in 8.
The mixture was fed at a rate of 4 N / hr and 1.0 N / hr to the liquid phase of the polymerization vessel for 100 minutes while mixing. The prepolymerization temperature is 20
It was kept at ± 2 ° C. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

As a result of the analysis, in the prepolymerized solid catalyst, about 92 g of the polymer was present on 1 g of the used Ti catalyst component [A], while in the separated filtrate, the used Ti catalyst component [A] was contained. Per 1g
There was 6.2 g of solvent soluble polymer.

Example 1 Powder 100 of copolymer (3) obtained as described above
Parts by weight of a solution in which 0.2 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene was dissolved and dispersed in 0.3 parts by weight of divinylbenzene and 5 parts by weight of a paraffinic process oil were mixed by a tumbler blender. The solution was uniformly attached to the powder surface of the copolymer (3).

The powder of the above copolymer (3) has an average particle size of 2000 μm.
m, the apparent density was 0.40 g / ml, the particles passing through 150 mesh were 0.2% by weight, and the falling time was 10.3 seconds. The geometric standard deviation of the polymer particles was 1.6.

Then, the powder was extruded at 210 ° C. under a nitrogen atmosphere using an extruder to obtain thermoplastic elastomer pellets.

100 parts by weight of the obtained pellets and MFR (ASTMD 1238 230
° C) 13, the density of 0.91 g / cm ³ , the initial flexural modulus of elasticity 9,000 kg / cm ³ Polypropylene 40 parts by weight was extruded at 210 ° C with an extruder. The procedure was as follows.

First, the pellets were injection-molded using the following apparatus and conditions to produce square plates having a thickness of 3 mm and 8 mm, and the moldability was evaluated. In addition, a test piece was cut from the 3 mm-thick square plate thus obtained, and the tensile properties, initial flexural modulus,
Izod impact strength was measured.

Molding conditions Molding machine: Dynamelter (manufactured by Meiki Seisakusho) Molding temperature: 200 ° C Injection pressure: Primary pressure 1300kg / cm ² Secondary pressure 700kg / cm ² Injection speed: Maximum molding speed: 90 seconds / cycle Gate: Direct gate (Land length: 10mm, width: 10mm, depth: 3mm) Moldability criteria 1) Flow mark 1: Flow mark markedly large 2: Flow mark markedly visible over molded product 3: Flow mark marked over molded product 4: Slight flow mark only on the opposite side of the gate 5: No flow mark at all 2) Sink 1: 1: All over the surface 2: On the other side of the gate Items 3: No sink mark observed Physical properties Tensile properties: 100% tensile stress (M100, kg / cm ² ) Tensile strength at break (Tb, kg / cm ² ) Elongation at break (Eb,%) JIS K- Measured according to 6301.

Initial flexural modulus (FM, kg / cm ² ) Measured according to ASTM D790.

Izod impact strength (IZOD kg · cm / cm) Measured according to ASTM D256.

(With notch) Example 2 In Example 1, after mixing the powder of the copolymer (3) obtained by mixing with a tumbler blender and polypropylene, the mixture was extruded at 210 ° C. under a nitrogen atmosphere using an extruder to obtain heat. The procedure was the same as in Example 1, except that a plastic elastomer composition was obtained.

The results are shown in Table 2. Example 3 The procedure of Example 1 was repeated, except that the copolymer (2) was used instead of the copolymer (3).
Was obtained.

The powder of the copolymer (2) has an average particle diameter of 2100 μm.
m, apparent density was 0.43 g / ml, particles passing through 150 mesh were 0.1% by weight, and fall time was 9.3 seconds. The geometric standard deviation of the polymer particles was 1.5.

Example 4 The procedure of Example 1 was repeated, except that low-density polyethylene (melt index (190 ° C.): 23, density 0.916 g / cm ³ ) was used instead of polypropylene. The result was obtained.

Example 5 In Example 1, an ethylene-vinyl acetate copolymer (melt index (190
° C): 15, vinyl acetate content 14% by weight), and using the same procedure as in Example 1 except that the copolymer (1) was used instead of the copolymer (3). Was.

The powder of the copolymer (1) has an average particle diameter of 2200 μm.
, The apparent density was 0.45 g / ml, the particles passing through 150 mesh were 0.1% by weight, the number of drops was 8.3 seconds, and the geometric standard deviation was 1.6.

Example 6 In Example 1, a linear low-density polyethylene (melt index (190 ° C.): 2,
Except for using the density of 0.720 g / cm ³ ), the same procedure as in Example 1 was carried out, and the results shown in Table 2 were obtained.

Example 7 In Example 1, an ethylene-propylene copolymer (melt index (190
° C): 4, density: 0.925 g / cm ³ ) The same procedure as in Example 1 was carried out except that 150 parts by weight were used.

 Table 3 shows the results.

Example 8 In Example 7, low-density polyethylene (melt index (19) was used instead of the ethylene-propylene copolymer.
0 ° C): 23, Example 7 except that the density was 0.916 g / cm ³ ).
Was performed in the same manner as described above.

 Table 3 shows the results.

Example 9 In Example 7, an ethylene-vinyl acetate copolymer (melt index (190 ° C.): 15, vinyl acetate content: 15% by weight, average particle diameter: 1200 μm) was used in place of the ethylene-propylene copolymer. Other than that, it carried out similarly to Example 7.

 Table 3 shows the results.

Example 10 Equipped with a stirring blade having a helical double ribbon
3 kg of the copolymer (3) particles obtained as described above were charged into a 15 stainless steel autoclave, and the system was completely replaced with nitrogen. Thereafter, a mixture for crosslinking (0.15% by weight of benzoyl peroxide (BPO), 0.15% by weight of divinylbenzene (DVB), 500 ml of toluene and 6% by weight of oil) was added to the polymer particles at room temperature while stirring the polymer particles. Dropping was performed in 10 minutes, and stirring was further performed for 30 minutes to impregnate the polymer particles with these reagents. Then, the temperature in the system was set to 100 ° C., and the reaction was carried out for 4 hours. After the reaction, the temperature in the system was lowered to 80 ° C., and the system was dried under reduced pressure.

A thermoplastic elastomer composition obtained by extruding 100 parts by weight of the obtained thermoplastic elastomer and 40 parts by weight of MAR13, polypropylene having a density of 0.91 g / cm ³ and an initial flexural modulus of 9000 kg / cm ² at 210 ° C. with an extruder is implemented. Evaluation was performed in the same manner as in Example 1.

 Table 4 shows the results.

Example 11 Example 10 was repeated except that low-density polyethylene (melt index (190 ° C.): 23, density 0.916 g / cm ³ ) was used instead of polypropylene. The result was obtained.

Example 12 In Example 10, an ethylene-vinyl acetate copolymer (melt index (190
C): 15, the vinyl acetate content was 14% by weight), and the results were as shown in Table 4.

Example 13 In Example 10, linear low density polyethylene (melt index (190 ° C.):
2, except that density of 0.920 g / cm ³ ) was used, and the results in Table 4 were obtained.

Example 14 In Example 10, an ethylene-propylene copolymer (melt index (190
° C): 4, density 0.925 g / cm ³ ) The same procedure as in Example 10 was carried out except that 150 parts by weight were used.

 Table 5 shows the results.

Example 15 In Example 14, low-density polyethylene (melt index (19) was used instead of the ethylene-propylene copolymer.
0 ° C): 23, Example 14 except that the density was 0.916 g / cm ³ ).
Was performed in the same manner as described above.

 Table 5 shows the results.

Example 16 Example 16 was repeated except that an ethylene-vinyl acetate copolymer (melt index (190 ° C.): 15, vinyl acetate content: 15% by weight) was used in place of the ethylene-propylene copolymer. Same as 14

 Table 5 shows the results.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08J 3/00-3/28 C08L 23/10, 51/06

Claims (5)

(57) [Claims] 1. A polymer particle comprising a crystalline olefin polymer part and an amorphous olefin polymer part, which has not undergone a heat history that impairs the particle shape, wherein the polymer particles are not crosslinked. A method for producing a thermoplastic elastomer composition, comprising melt-kneading in the presence of a crosslinking agent and a polyolefin to obtain a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and / or a non-crosslinked polyolefin. 2. A polymer particle comprising a crystalline olefin polymer portion and an amorphous olefin polymer portion, which has not undergone a heat history that impairs the particle shape, is obtained by crosslinking in the presence of at least a crosslinking agent. Producing a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and / or a non-crosslinked polyolefin by melt-kneading the crosslinked polymer and a polyolefin. Method. 3. A gas-phase crosslinked polymer particle comprising a crystalline olefin polymer part and an amorphous olefin polymer part which has not undergone a heat history that impairs the particle shape, wherein the crystalline olefin polymer part And a polymer particle comprising an amorphous olefin polymer part, in the presence of at least a crosslinking agent, less than the higher of the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer. A gas phase crosslinked polymer particle obtained by contacting at a temperature of, melt kneading in the presence of a polyolefin to obtain a thermoplastic elastomer composition containing a crosslinked polymer and a polyolefin. A method for producing a plastic elastomer composition. 4. The weight ratio (crosslinked polymer / crosslinked polyolefin and / or noncrosslinked polyolefin) of the crosslinked polymer and the crosslinked polyolefin and / or non-crosslinked polyolefin constituting the thermoplastic elastomer composition is 90/1.
The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the ratio is 0 to 50/50. 5. The weight ratio (crosslinked polymer / crosslinked polyolefin and / or noncrosslinked polyolefin) of the crosslinked polymer and the crosslinked polyolefin and / or non-crosslinked polyolefin constituting the thermoplastic elastomer composition is 5/95.
The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the ratio is from 49 to 51/51.