JPH0425553A - Production of thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To improve tensile strength, flexibility, elasticity, impact resistance, surface flatness, coatability, thermal stability, and weather resistance by melt mixing specific polymer particles with a crosslinker and a phenolic stabilizer. CONSTITUTION:100 pts.wt. polymer particles each comprising a crystalline olefin polymer part and 20-80wt.% amorphous olefin polymer part and having a mean particle diameter of 10mum or higher, a geometric standard deviation of 1.0-3.0, and a bulk density of 0.2g/ml or higher are melt mixed with a crosslinker (e.g. dicumyl peroxide) and 0.01-10 pts.wt. phenolic stabilizer (e.g. 2,6-di-t-butyl-4-methylphenol) and, if necessary, with 0.01-10 pts.wt. at least one stabilizer selected from the group consisting of an org. thiol stabilizer, an org. phosphite stabilizer, a hindered amine stabilizer, and a metal salt of a higher fatty acid in an inert gas atmosphere at 150-280 deg.C for 1-20min.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention 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, and more particularly, for improving tensile strength properties, flexibility, elasticity, impact resistance at low temperatures, surface smoothness, and coating. The present invention relates to a method for producing a thermoplastic elastomer composition that has excellent properties, as well as excellent thermal stability during molding, long-term thermal stability, and weather resistance.

Thermoplastic elastomers have been widely used for automobile parts such as bumper parts.

This thermoplastic elastomer has both thermoplastic and elastic properties, and can be molded into molded products with excellent heat resistance, tensile properties, weather resistance, flexibility, and elasticity through injection molding and extrusion molding. can do.

For example, in Japanese Patent Publication No. 53-34210, 6o to 8
0 parts by weight of monoolefin copolymer rubber and 40 to 20 parts by weight
A thermoplastic elastomer is disclosed that is dynamically partially cured with parts by weight of a polyolefin plastic. Furthermore, Japanese Patent Publication No. 53-21021 discloses that (a) an ethylene-propylene-nonconjugated polyene copolymer rubber,
A thermoplastic elastomer comprising a partially crosslinked copolymer rubber having a gel content of 30 to 90% by weight and (b) a polyolefin resin is disclosed. Furthermore, Tokko Sho, 55-
Japanese Patent No. 18448 discloses a thermoplastic elastomer in which an ethylene-propylene copolymer rubber and a polyolefin resin are dynamically partially or completely crosslinked.

By the way, JP-A-58-187412 discloses a propylene homopolymer block and a binary random copolymer block of propylene and ethylene or an α-olefin of 04 to CI2 with a propylene content of 100 to 100.
60% by weight of one or more of the blocks [A]
Olefinic block copolymer containing 0 to 70 parts by weight and 30 to 50 parts by weight of one or more of two or more binary random copolymer blocks [B] of ethylene and propylene having an ethylene content of 30 to 85% by weight Crosslinked block copolymers derived from coalescence and characterized by having a specific content of thermally xylene-insoluble components and specific flow properties are disclosed.

Also, JP-A-63-165414, JP-A-63-1
No. 65115, JP-A No. 83-161516, and U.S. Patent No. 4,454.306 disclose a propylene homopolymer block [A] produced using a specific Ziegler catalyst, An olefinic block copolymer consisting of a binary random copolymer block [B] and a propylene/ethylene binary random copolymer block [C] is heated at 230°C together with an organic peroxide, a divinyl compound, and an antioxidant. A method for producing a crosslinked olefin block copolymer is disclosed, which is characterized by kneading and crosslinking at the following temperatures.

Furthermore, JP-A-4. ! No. 1-21731 discloses a block consisting of a copolymer portion consisting of 3 to 30% by weight of ethylene and containing 70% by weight or less of other α-olefins, and a polymer portion of 97 to 70% by weight mainly consisting of propylene. Mixing an organic peroxide with a copolymer, 180-27
A method for improving the processability of a block copolymer is disclosed, which is characterized by heat treatment at 0°C.

The inventors have developed polymer particles as an economical process.
When we investigated the possibility of producing a thermoplastic elastomer through heat treatment while maintaining the particle shape, we found that if polymer particles with a specific morphology were used, they would be extremely uniform;
This thermoplastic elastomer has excellent elasticity even with a small rubber content, has excellent strength, and when molded into a molded product, has an excellent appearance, especially after painting. Thermoplastic elastomer compositions containing various stabilizers such as phenolic stabilizers and phenolic stabilizers have excellent tensile strength properties, flexibility, elasticity, impact resistance at low temperatures, surface smoothness, and paintability. It was discovered that the material has excellent thermal stability during molding, long-term thermal stability, and weather resistance, leading to the completion of the present invention.

Purpose of the Invention The present invention provides a heat treatment resin that has excellent tensile strength properties, flexibility, elasticity, impact resistance at low temperatures, surface smoothness, and paintability, as well as excellent thermal stability during molding, long-term thermal stability, and weather resistance. It is an object of the present invention to provide a method for producing a plastic elastomer composition.

Summary of the Invention A first method for producing a thermoplastic elastomer composition according to the present invention includes crosslinking polymer particles comprising a crystalline olefin polymer portion and an amorphous olefin polymer portion in the presence of a crosslinking agent; A thermoplastic elastomer composition containing a crosslinked polymer and a phenolic stabilizer (A) is obtained by melt-kneading the thermoplastic elastomer composition.

Methods for producing such thermoplastic elastomer compositions include, for example, the following three production methods.

■) A crosslinked polymer obtained by crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, and a phenolic stabilizer (A) are melt-kneaded to form a crosslinked polymer. A method for producing a thermoplastic elastomer composition, which comprises preparing a thermoplastic elastomer composition containing a phenolic stabilizer (A).

2) Non-crosslinked polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are melt-kneaded in the presence of a crosslinking agent and a phenolic stabilizer (A) to form a crosslinked polymer. A method for producing a thermoplastic elastomer composition, the method comprising obtaining a thermoplastic elastomer composition comprising:

3) Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are heated to the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer in the presence of at least a crosslinking agent. The gas-phase crosslinked polymer particles obtained by contacting the particles at a temperature lower than the higher of the two are melt-kneaded in the presence of the phenolic stabilizer (A) to combine the crosslinked polymer and the phenolic stabilizer (A). A) A method for producing a thermoplastic elastomer composition, which comprises obtaining a thermoplastic elastomer composition comprising:

Moreover, the second thermoplastic elastomer composition according to the present invention
The manufacturing method includes crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part in the presence of a crosslinking agent, and melt-kneading the crosslinked polymer and a phenolic stabilizer. (A), an organic thioether stabilizer (B), and one or two selected from the group consisting of an organic phosphite stabilizer (C), a hindered amine stabilizer (D), and a higher fatty acid metal salt (E). The present invention is characterized by obtaining a thermoplastic elastomer composition containing the above stabilizers.

Examples of methods for manufacturing such thermoplastic elastomer compositions include the following three types of manufacturing methods.

1) A crosslinked polymer obtained by crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a phenolic stabilizer (A), and an organic thioether stabilizer (B) organic phosphite stabilizer (C),
A thermoplastic elastomer composition is obtained by melt-kneading one or more stabilizers selected from the group consisting of a hindered amine stabilizer (D) and a higher fatty acid metal salt (E). A method for producing a plastic elastomer composition.

2) Non-crosslinked polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are mixed with a crosslinking agent, a phenolic stabilizer (A), and an organic thioether stabilizer (B). 1 selected from the group consisting of organic phosphite stabilizers (C), hindered amine stabilizers (D) and higher fatty acid metal salts (E)
The crosslinked polymer, the phenol stabilizer (A), the organic thioether stabilizer (B), and the organic phosphite stabilizer (C) are melt-kneaded in the presence of a species or two or more stabilizers.
), a hindered amine stabilizer (D), and one or more stabilizers selected from the group consisting of higher fatty acid metal salts (E). A method for producing an elastomer composition.

3> Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are heated to the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer in the presence of at least a crosslinking agent. The gas-phase crosslinked polymer particles obtained by contacting the particles at a temperature lower than the higher of the following are combined with a phenolic stabilizer (A), an organic thioether stabilizer (B), and an organic posphite stabilizer (C). ), hindered amine stabilizer (D) and higher fatty acid metal salt (E) 1
The crosslinked polymer, the phenol stabilizer (A), the organic thioether stabilizer (B), and the organic phosphite stabilizer (C) are melt-kneaded in the presence of a species or two or more stabilizers.
), a hindered amine stabilizer (D), and one or more stabilizers selected from the group consisting of higher fatty acid metal salts (E). A method for producing an elastomer composition.

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

Polymer particles The polymer particles used in the present invention are polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion, which have not undergone a thermal history that would impair the particle shape, and are crosslinked. There are two types of polymer particles: non-crosslinked polymer particles and crosslinked polymer particles.

The above-mentioned crosslinked polymer particles are prepared by combining polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion, and a crosslinking agent at the melting point of the crystalline olefin polymer or the amorphous olefin. These are intraparticle crosslinked thermoplastic elastomer particles obtained by contacting the polymer at a temperature lower than the higher of the glass transition points of the polymer. In this specification,
The above-mentioned intraparticle crosslinking is sometimes referred to as gas phase crosslinking, and such thermoplastic elastomer particles are sometimes referred to as gas phase crosslinked polymer particles.

The average particle diameter of the polymer particles (hereinafter sometimes simply referred to as "polymer particles") used in the present invention before melt crosslinking or gas phase crosslinking is usually 10 μm or more, preferably 10 μm or more.
~8000μm1 More preferably 100~4000μm
m1 is particularly preferably within the range of 300 to 3000 μm. Further, the geometric standard deviation indicating the particle size distribution of the polymer particles used in the present invention is usually 160 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.5,
Particularly preferably, it is within the range of 1.0 to 1.3. Also,
The apparent bulk density of the polymer particles used in the present invention due to natural fall is usually 0.2 g/ml or more, preferably 0.
2-0, 7 g/ml, more preferably 0.3
~0.7g/ml, particularly preferably 0.35-0.60
g/ml.

Further, in the polymer particles used in the present invention, the 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 or less.
% by weight or less. Further, such polymer particles have a fall time defined as below in seconds of 5 to 25 seconds, preferably 5 to 20 seconds, particularly preferably 5 to 15 seconds.

Note that the average particle diameter, apparent bulk density, and falling seconds of the polymer particles as described above are measured as follows.

300 g of average particle diameter double coalescing particles were stacked in a Japan Rikagaku Instruments membrane stainless steel sieve with a diameter of 200 mm and a depth of 45+ nm (7 types of sieves with a mesh size of 7.10° and 14.20.42.80.150 mesh) in this order. 11DA 5IEVE 5HAKER (Iida Seisakusho)
and shaken for 20 minutes.

After shaking for 20 minutes, place on each sieve. Measure the weight of the polymer and compare the measurements. The numbers were plotted on established paper. the plot are connected by a curve, and this curve is multiplied by Hess. Particle size at 50% calculated weight (D5o) was determined, and this value was taken as the average particle diameter.

On the other hand, the same applies to the geometric standard deviation. In addition, the small particle size adds up to 16 layers. It was determined from the particle diameter (D16) in % and the above D5o value.

(Geometric standard deviation - D5o/D16) Apparent bulk density: Measured in accordance with JIS K 6721-1977. (The inlet inner diameter of the funnel used was 92.9+nmφ, and the outlet inner diameter was 9.5 mm.
There was φ. ) Falling seconds: Using the bulk density measuring device as is, the sample was dropped into a receiver, the sample that had risen from the receiver was scraped off with a crow bar, and the sample was placed in a 100m1 container and the damper was inserted again. After transferring to the funnel, the damper was pulled and the time (seconds) required for the entire sample to fall from the bottom of the funnel was defined as the number of seconds of falling.

However, when measuring the falling seconds, 1.5 to the average particle diameter of the sample By sieving particles that are 1.6 times larger The removed polymer particles were used.

In addition, when measuring the falling seconds, set the receiver on the vibration table of a powder tester (Type PT-D, SER, No. 71190 manufactured by Hosokawa Micro), and adjust the voltage of the rheostat so that the vibration width of the diaphragm is lllll11. Then, the polymer particles were allowed to fall without being vibrated.

As mentioned above, the polymer particles used in the present invention are composed of a crystalline olefin polymer part and an amorphous olefin polymer part, and in many cases have a so-called sea-island structure. The part forms a specific part in the polymer particle. The average particle size of the component consisting of the amorphous olefin polymer portion (including some crystalline olefin polymer portion in some cases) is 0.5 μm or less, preferably 0.1 μm or less, and more preferably 0.00001
It is desirable that the thickness is 0.05 μm.

In addition, there are cases where a compatible structure is formed in which the ingredient part and the sea part cannot be distinguished.

Note that the average particle diameter of the part consisting of the amorphous olefin polymer part in the polymer particles is measured as follows.

Using an ultramicrotome, the polymer particles were
Thinly slice at -140℃ to a thickness of 1,000 people. then 0.5
The thinly sliced sample is placed in the gas phase for 30 minutes in a closed container containing about 1 g of 200 ml of an aqueous solution of % RuO4 to stain the amorphous olefin polymer portion in the sample. Next, after reinforcing the dyed sample with carbon, it is observed using a transmission microscope, and the particle size of the topping part is determined for at least 50 particles, and the average value thereof is taken as the average particle diameter of the topping part.

It is preferable to use particles having the above-mentioned characteristics as the polymer particles used in the present invention, and there are no particular limitations on the method for producing particles having such characteristics, but the method described below may be used. It is preferable to manufacture the polymer particles by adopting this method, and the transition metal content in the ash of the polymer particles is usually 100 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less.
pm or less, the halogen content is usually 300 ppm or less, preferably 100 ppI or less, particularly preferably 50 ppm or less
pI)Ill or less.

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

Polymer particles having the above characteristics can be obtained, for example, by polymerizing or copolymerizing α-olefins 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-11 methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene-1, dimethyloctene-1,)limethylhebutene-1 , ethyl octene-1, methylethylhebutene-11 diethylhexene-1, dodecene-1 and hexadodecene-1.

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

In the present invention, polymer particles containing repeating units derived from the above-mentioned α-olefin are usually 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 100 mol%. or used.

In the present invention, other compounds that can be used in addition to the above a-olefin include, for example, linear polyene compounds and cyclic polyene compounds. In the present invention, as the polyene compound, a polyene having two or more conjugated or non-conjugated olefinic double bonds is used, and as such a chain polyene compound, specifically, ■, 4-hexadiene, 1.5-hexadiene, 1.7-octadiene, ■, 9-decadiene, 2.
4.6-octatriene, 1,3.7-octatriene, 1,5.9-decatriene, divinylbenzene, etc. are used. Further, specific examples of the cyclic polyene compound include ■, 3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene,
1.3-cyclohebutadiene, dicyclopentadiene,
Dicyclohexadiene, 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 addition, in the present invention, cyclopentadiene such as cyclopentadiene and ethylene, propylene, butene-
It is also possible to use a polyene compound obtained by condensing an α-olefin such as No. 1 using a Diels-Alder reaction.

Furthermore, in the present invention, cyclic monoenes may be used, and specific examples of such cyclic monoenes include cyclopropene, cyclobutene, cyclopentene,
Monocycloalkenes such as cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, cycloeicosene, norbornene, 5
-Methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-
Bicycloalkenes such as dimethyl-2-norbornene, 5,5.6-trimethyl-2-norbornene, 2-bornene, 2.3,3a,7a-tetrahydro-4,7-methano-IH-indene, 3a,5.6 , 7a-tetrahydro-4,7-methano-IH-indene, 1,4,5.8-dimethano-1,2,3,
4,4a,5,8,8a-octahydronaphthalene, and in addition to 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,
5,111-dimethano-1,2,3,4,4a, 5゜8
．． 8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5. L8a-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. Ba-octahydronaphthalene, 2,3-cyclo1.4.5.8-dimethano-1,2,3,4,4a
, 5,8.8a-Tetracycloalkenes such as octahydronaphthalene, hexacyclo[6,6°3.6 10
,13,o2,7.9,14],,,Futatese>-4
,1,1,1 Pentacyclo[8,8,12”9 ,■4,7.111
° 18,03.8 12.17 0. 0]]Henkokosen-5 octacyclo2
．． 9 4,7 11.18 13,16 3.8[8
, 8,1,1,1,1,0,0 012°17]F cosene-5 and other 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 can be obtained by polymerizing or copolymerizing at least the above α-olefin in the presence of the following catalyst, but the above polymerization reaction or copolymerization reaction It can be carried out in a gas phase (mostly A phase method), or in a liquid phase (liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is preferably carried out in a suspended state so that the resulting polymer particles can be obtained in a solid state.

In this polymerization reaction or copolymerization reaction, an inert hydrocarbon can be used. Further, the raw material α-olefin may be used as a reaction solvent. Note that the above polymerization or copolymerization may be carried out by a combination of a liquid phase method and a gas phase method. In the production of the polymer particles used in the present invention, the above polymerization or copolymerization is preferably carried out using a gas phase method, or a method in which a reaction is carried out using an α-olefin as a solvent followed by a gas phase method. .

In the present invention, when producing polymer particles used as raw materials, a method of simultaneously producing a crystalline olefin polymer portion and an amorphous olefin polymer portion by supplying two or more types of 7-mer to a polymerization pot. ,or,
One example is a method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion are carried out separately and in series using at least two or more polymerization vessels. In this case, the latter method is preferred from the viewpoint that the molecular weight, composition, and amount of the amorphous olefin polymer portion 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 to synthesize a crystalline olefin polymer part by using a monomer as a solvent. After synthesizing,
Examples include a method of synthesizing an amorphous olefin polymerization part by gas phase polymerization.

In the present invention, when carrying out the above polymerization reaction or copolymerization reaction, the catalyst component [A] containing a transition metal and the organometallic compound catalyst component [B ] is used.

The above catalyst component [A] is preferably a catalyst containing a transition metal atom of Group IVB or Group VB of the Periodic Table of the Elements, and among these, at least one selected from the group consisting of titanium, zirconium, hafnium, and vanadium. More preferred are catalyst components containing different types of atoms.

Other preferable catalyst components [A] include catalyst components containing a l\rogen atom and a magnesium atom in addition to the above-mentioned transition metal atoms, and conjugated π electrons in transition metal atoms of groups IVB and VB of the periodic table. Examples include catalyst components containing a compound coordinated with a group having

In the present invention, the catalyst component [A] is present in a solid state in the reaction system during the polymerization reaction or copolymerization reaction as described above, or is present in a solid state by being supported on a carrier or the like. It is preferable to use a catalyst prepared in such a way that it is possible to do so.

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

The average particle diameter of the solid catalyst component [A] as described above is:
Preferably 1 to 200 μm1, more preferably 5 to 10 μm
0 μm1, particularly preferably within the range of 10 to 80 μm. Further, the geometric standard deviation (δ) as a measure of the particle size distribution of the solid catalyst [A] is preferably 1.0 to 3.0.
, more preferably 1.0 to 2.1, particularly preferably 1
．． It is within the range of 0 to 1.7.

Here, the average particle size and particle size distribution of the catalyst component [A] are:
It can be measured by a light transmission method.

Specifically, a dispersion prepared by adding the catalyst component [,A] to a decalin solvent at a concentration of 0.1% by weight was placed in a measurement cell, and the cell was illuminated with a narrow light to detect particles. The particle size distribution is determined by continuously measuring changes in the intensity of light passing through the narrow beam. Based on this particle size distribution, the standard deviation (δ
) is calculated from the lognormal distribution. More specifically, 16% by weight considering the average particle size (θ50) and small particle size.
The standard deviation (δ) is determined as the ratio (θ5o/θ16) to the particle diameter (θ16). Note that the average particle diameter of the catalyst is the weight average particle diameter.

Further, the catalyst component [A] preferably has a shape such as a true sphere, an elliptical sphere, or a granular shape, and the aspect ratio of the particles is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. 5 or less.

The aspect ratio is determined by observing the catalyst particle group with an optical microscope,
At that time, it is determined by measuring the long axis and short axis of 50 arbitrarily selected catalyst particles.

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

In such a catalyst component [A], the titanium compound in the catalyst component is generally not desorbed by simple operations such as washing with hexane at room temperature.

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

The catalyst component [A] as described above can be prepared, for example, by a method in which a catalyst is prepared after forming a magnesium compound having an average particle size and a particle size distribution within the above-mentioned range and having a shape as described above, or by a method in which a catalyst is prepared after forming a magnesium compound having an average particle size and particle size distribution within the above-mentioned range. It can be produced by employing a method such as a method of bringing a compound into contact with a liquid titanium compound to form a solid catalyst having the particle properties as described above.

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 uniformly shaped carrier. It is also possible to prepare a finely powdered catalyst in advance and then granulate this finely powdered catalyst into the preferred shape described above.

Regarding such catalyst component [A], Japanese Patent Application Laid-Open No. 55-1
No. 35102, No. 55-135103, No. 5B-81
No. 1, Publication No. 5B-67311 and Patent Application No. 1982-1
No. 81019 and No. 6121109.

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

(1) A solid magnesium compound/electron donor complex with an average particle diameter of 1 to 200 μm and a geometric standard deviation (δ) of particle size distribution of 3.0 or less is combined with an electron donor and/or an organoaluminum compound or a halogen-containing complex. a halogenated titanium compound which is liquid under the reaction conditions, with or without pretreatment with a reaction aid such as a silicon compound;
Preferably, it is reacted with titanium tetrachloride.

(2) A liquid magnesium compound that has no reducing ability and a liquid titanium compound are reacted, preferably in the presence of an electron donor, and the average particle size is 1 to 200 μm.
Solid components with a geometric standard deviation (δ) of particle size distribution of 3.0 or less are precipitated.

Further, if necessary, it is reacted 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 with reducing ability and a reaction aid capable of eliminating the reducing ability of the magnesium compound, such as polysiloxane or a halokene-containing silicon compound, the average particle size can be reduced. is 1 to 200 μm, and the geometric standard deviation of the particle size distribution (
After precipitating a solid component with δ ) of 3.0 or less, this solid component is reacted with a liquid titanium compound, preferably titanium tetrachloride, or a titanium compound and an electron donor.

(4) After contacting a magnesium compound having reducing ability with an inorganic or organic carrier such as silica, the carrier is then brought into contact with a halogen-containing compound or without contacting with a liquid titanium compound, preferably The magnesium compound supported on the carrier is reacted with the titanium compound by contacting with titanium tetrachloride or a titanium compound and an electron donor.

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

Such a solid catalyst component [A] has the ability to produce a polymer having high stereoregularity with high catalytic efficiency. For example, this solid catalyst component [
When homopolymerizing propylene using A], polypropylene with an isotoughness index (insoluble content in boiling n-hebutane) of 92% or more, particularly 96% or more, is usually 3000 g or more per 1 mmol of titanium. , preferably 5000g or more, particularly preferably 10000g
or more can be manufactured.

Examples of magnesium compounds, silicon compounds containing siloxene, titanium compounds, and electron donors that can be used in the preparation of the catalyst component [A] as described above are shown below. Also,
The aluminum component used in the preparation of this catalyst component [A] is a compound exemplified in the organometallic compound catalyst component [B] described below.

Specifically, magnesium compounds include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide, and hydrotalcite, magnesium carboxylates, alkoxymagnesium, allyloxymagnesium,
In addition to alkoxymagnesium halide, allyloxymagnesium halide, and magnesium cybaride, organomagnesium compounds such as dialkylmagnesium, Grignard reagent, and diarylmagnesium are used.

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

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

Examples of compounds that can be used as such electron donors include methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, 1 to 1 carbon atoms, such as isopropyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol
8 Alcohols 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) : Ketones having 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, hensifhenone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms, 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, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, hensyl benzoate, toluyl Methyl acid, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, n-hexyl cyclohexenecarphonate, diethyl nadic acid, diisopropyl tetrahydrophthalate, phthalate Diethyl acid, diisobutyl phthalate, di-n-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, n-hexyl phthalate, diisohexyl phthalate, n-heptyl phthalate, diisoheptyl phthalate, di-n-phthalate N-octyl, diisooctyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate with 2 to 3 carbon atoms
0 organic acid esters; acid halides having 2 to 15 carbon atoms such as acetyl chloride, hendiyl chloride, toluyl chloride and anisyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and Ethers having 2 to 20 carbon atoms such as anisole and diphenyl ether; for example, (in the formula, 2≦n≦10, R-R25 is carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, boron and A substituent having at least one element selected from silicon, R, , R2n are bonded to the main chain through a carbon-carbon bond, and any R-R26 are jointly attached to a ring other than a benzene ring. may be formed,
Further, the main chain may contain elements other than carbon.

) Polyethers such as those represented by More specifically, 2-(2-ethylhexyl)-3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane,
2-Butyl-1,3-dimethoxypropane, 2-8-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, 2- (
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, 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-1,8-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, 3-dimethoxypropane, 2,2-phenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxy propane,
Dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-jethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2- Isobutyl-2isopropyl-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-pencyl-1,3
-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,
3-diphenyl-1,4-jethoxybutane, 2,3-
Dicyclohexyl-1,4-jethoxybutane, 2.2
-dibenzyl-1,4-jethoxybutane, 2,3-dicyclohexyl-1,4-jethoxybutane, 2,3-
Diisopropyl-1,4-jethoxybutane, 2,2-
Bis(p-methylphenyl) 1,4-dimethoxybutane, 2.3-bis(p-chlorophenyl)-1,4-dimethoxybutane, 2.3-bis(p-fluorophenyl)
1,4-dimethoxybutane, 2,4-diphenyl-1,
5-dimethoxypenkune, 2,5-diphenyl-1,5
-dimethoxyhexane, 2,4-diisopropyl-1,
5-dimethoxypentane, 2,4-diisobutyl-1,
5-dimethoxypentane, 2,4-diisoamyl-1,
5-dimethoxypenkune, 3-methoxymethyltetrahydrofuran, 3-methquinemethyldioxane, 1.3-
Diisoamyloxypropane, ■, 2-diisobutquine propane, ■, 2-diisobutoxyethane, 1,3 diisoamyloxyethane, ■, 3-diisoamyloxypropane, 1,3-diisoneopentyloxy Ethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-
1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, ■, 2-bis(methoxymethyl)cyclohexane, 2,8-dioxaspiro[ 5,5] undecane, 3,7-thioxabicyclo[3
,3,1]nonane, 3,7-thioxabicyclo[3,3
, 01 octane, 3.3-diisobutyl-1,5-oxononane, 6.6-dibutylcyoxyhbutane, ■
, 1-dimethoxymethylcyclopentane, 1.1-bis[dimethoxymethyl]cyclohexane, 1.1-bismethoxymethyl]bicyclo[2,2,1]hebutane,
1.1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-jethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3=dimethoxypropane, 2,2-diisobutyl-■, 3-dimethoxycyclohexane, 2-isopropyl-2-ynamyl-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-jethoxycyclohexane,
2-Cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-jethoxycyclohexane, 2-
Isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-jethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, Tris(p -methoxyphenyl)phosphine can be cited as an example. Among these, 1,3-diethers are preferred, particularly 2,2-diisobutyl-1,3-
Carbon such as dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, etc. Number 5 to 40 diethers; Acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; Methylamine, ethylamine, diethylamine, tributylamine, piperidine, tripentylamine, aniline, pyridine, picoline and tetramethylenecyamine Nitriles such as acetonitrile, hendinitrile and tolnitrile; po with trimethyl phosphite, triethyl phosphite, etc.
An organic phosphorus compound having a -c bond.

Alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane are used.

These electron donors can be used alone or in combination.

Among such electron donors, preferable electron donors are:
Esters of organic or inorganic acids, alkoxy(aryloxy)silane compounds, ethers, ketones, tertiary amines,
Compounds without active hydrogen such as acid halides and acid anhydrides, and organic acid esters and alkoxy(aryloxy)silane compounds are particularly preferred, and among them, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms,
malonic acid, substituted malonic acid, substituted succinic acid, maleic acid,
Particularly preferred are esters and diethers of dicarboxylic acids such as substituted maleic acid, 1,2-cyclohexanedicarboxylic acid, and phthalic acid and alcohols having 2 or more carbon atoms. Of course, these electron donors do not need to be added to the reaction system during the preparation of the catalyst component [A]; for example, compounds that can be converted into these electron donors are added to the reaction system and this compound is added during the catalyst preparation process can also be converted into the above electron donor.

The catalyst component [A] obtained as described above can be purified by washing thoroughly with a liquid inert hydrocarbon compound after preparation. Hydrocarbons that can be used in the second washing include, specifically, n-pentane, isopentane, n-hexane, isohexane, n-hebutane, n-octane, isooctane, n-decane, n-
- Aliphatic hydrocarbon compounds such as dodecane, kerosene, liquid paraffin; Alicyclic hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane; Aromatic hydrocarbon compounds such as Hensen, toluene, xylene, cymene, etc. Examples include chlorobenzene, dichloroethane, and other halogenated hydrocarbon compounds.

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 AΩ-carbon bond in the molecule.

Examples of such organoaluminum compounds include (where R1 and R2 usually have 1 to 15 carbon atoms).
, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is a halogen atom, m
is 0≦m≦3, n is 0≦n<3, p is 0≦p<3, q is a number of 0≦q<3, and m + n + p
+ q -3), and (ii) a periodic table represented by the formula MADR'4 (where Ml is Lj Na, and R1 has the same meaning as above) Examples include complex alkylation products of group (I) metals and aluminum.

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

m expressed by the formula RAj7(OR)
3-m compound (here, R and R2 have the same meaning as above, and m is preferably a number of 1.5≦m≦3).

A compound represented by the formula RAj7X (this
-ffl where R■ has the same meaning as above, X is halogen, and m preferably satisfies 0<m<3).

Compounds represented by formulas RA and QH (113-n, where R1 has the same meaning as above, and m is preferably 2≦
m < 3).

m expressed by the formula RAff(OR2)
nq compound (here R
and R2 are the same as above. X■ is halogen, 0<m≦3.0≦n<3.0≦q3,
m + n 1q = 3).

Specifically, the organoaluminum compound represented by the above formula (i) includes trialkylaluminums such as triethylaluminum, tributylaluminum, and triisopropylaluminium, trialkenylaluminums such as triisoprenylaluminum, and dibutylaluminum. dialkylaluminum alkoxides such as butoxide, dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminums having an average composition of Alkylaluminum sesquihalides such as aluminum sesquipromide; partially halokenated alkylaluminums such as alkylaluminum sybarite such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum bromide; dialkylaluminum hydrides such as dibutylaluminum hydride, partially hydrogenated alkylaluminums such as alkylaluminum dihydride, ethylaluminum dihydride, propylaluminum dichloride, ethylaluminum ethoxy chloride, butyl Partially alkoxylated and halokenated alkylaluminums are used, such as aluminum butoxychloride, ethylaluminum ethoxybromide, and the like.

Furthermore, the organoaluminum compound used in the present invention is
For example, it may be a compound similar to the compound represented by formula (i), such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Specific examples of such compounds include (C2H5)2AIIOAg (C2H5)2, (C4
H9)2AgOAΩ (C4H9)2, and the like.

Further, as the organoaluminum compound represented by the above formula (ii), specifically, LiAg(C2H5)
4 and LiAg (C7H15)4. Among these, it is particularly preferable to use trialkylaluminum, a mixture of trialkylaluminum and alkyl aluminum halide, and a mixture of trialkylaluminum and aluminum halide.

In addition, when carrying out the polymerization reaction, in addition to the catalyst component [A] and the organometallic compound catalyst component [B], an electron donor [C
] It is preferable to use them together.

Specifically, such electron donors [C] include amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoamides, esters, thioethers, thioesters,
Acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes, organic acids, amides of metals belonging to Groups 1, 2, 2, and 2 of the periodic table. and their acceptable salts. Note that the salts are organic acids and catalyst components [B
,, ] It can also be formed in the reaction system by reaction with an organometallic compound used as.

Specific examples of these electron donors include the compounds exemplified above for catalyst component [A]. Among such electron donors, particularly preferred electron donors are:
These include organic acid esters, alkoxy(aryloxy)silane compounds, ethers, ketones, acid anhydrides, amides, and the like.

In particular, when the electron donor in the catalyst component [A] is a monocarphonic acid ester, the electron donor is preferably an alkyl ester of an aromatic carboxylic acid.

In addition, when the electron donor in the catalyst component [A] is an ester of a dicarboxylic acid with an alcohol having 2 or more carbon atoms, the electron donor [C] is (in the above formula, R and R1 represents a hydrocarbon group, and 0≦n<4) or an amine with a large steric hindrance is preferably used.

Specifically, such alkoxy(aryloxy)silane compounds include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxyrane,
Dimethylethoxysilane, diisopropyldimethoxysilane, t-butylmethylnmethoxysilane, t-butylmethylshedquinonerane, t-amylmethylshedquinonerane, /phenylenemethoxy/rane, phenylmethyldimethoxyrane, cyphenylshedquinonerane, His-o-1-lylcymethoxine, His-m-tolyldimethoxine, His-p-tolyldimethoxine, Bis-p-tolylshedoxine, Bisnithylphenylmethoxine, Dicyclohexyldimethoxine, Cyclohexylmethylsilane. Toquinran, cyclohexylmethylshethoxynolane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxysilane, decylmethoxinlan, decyltriethoxinlan, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane Nidoxinlan, t-butyltriethoxysilane, n-
Butyltriethoxysilane, Iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane , 2-norbornane trimethoxysilane, 2-norbornane triethoxysilane,
2-norbornanemethyldimethoxycin, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(at Iyloxy)silane, vinyltris(β-methoxyethoxysilane), dimethyltetraethoxycycloxane, and the like are used.

Among these, especially ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane,
Vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-1)
-) Lylmethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, dichlorohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyljethoxysilane, ethyl silicate, and the like are preferred.

Further, as the amine with large steric hindrance, 2.2,6
．． Particularly preferred are 6-titramethylpipericine, 2,2.5.5-tetramethylpyrrolidine, or derivatives thereof, and tetramethylmethylenediamine. Among these compounds, alkoxy(aryloxy)silane compounds and the above-mentioned polyethers are particularly preferred as electron donors used as catalyst components.

(Left below) In addition, in the present invention, a catalyst component [il] containing a compound of a transition metal atom of Group IVB or Group VB of the Periodic Table of Elements having a group having conjugated π electrons as a ligand, and an organometallic compound catalyst component A catalyst consisting of [ii] can be preferably used.

Here, examples of the transition metals of Group IVB and Group VB of the Periodic Table of Elements include metals such as zirconium, titanium, hafnium, chromium, and vanadium.

In addition, examples of the group having a conjugated π electron as a ligand include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a t-butylcyclopentadienyl group, and a dimethylcyclopentadienyl group. Examples thereof include a group, an alkyl-substituted cyclopentagenyl group such as a pentamethylcyclopentagenyl group, an indenyl group, a fluorenyl group, and the like.

Preferred examples include a group in which at least two of these cycloalkagenyl skeleton-containing ligands are bonded via a lower alkylene group or a group containing silicon, phosphorus, oxygen, or nitrogen.

Examples of such groups include groups such as ethylenebisindenyl group and isopropyl (cyclopentagenyl-fluorenyl) group.

One or more, preferably two, such ligands having a cycloalkagenyl skeleton are coordinated to the transition metal.

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

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group; examples of the aryl group include a phenyl group and tolyl group; and examples of the aralkyl group include a benzyl group. , neophyll group, etc.

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

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

For example, when the valence of the transition metal is 4, the transition metal compound containing a ligand having a cycloalkagenyl skeleton used in the present invention has the following formula: R2R3R4R5M k l m n ( In the formula, M is zirconium, titanium, hafnium, or vanadium, R2 is a group having a cycloalkashenyl skeleton, RR and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cycloalkyl group, It is an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or hydrogen, and k is an integer of 1 or more, and is represented by k+, Q+m+n-4.

Particularly preferred is a group having an alkadienyl group skeleton in which R and R3 in the above formula, a group having two cycloalkagenyl skeletons, a lower alkyl group, or a group containing silicon, phosphorus, oxygen, or nitrogen. It is a compound that is bonded through a group.

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton in which M is zirconium will be exemplified.

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl) phenylzirconium hydride, bis(cyclopentagenyl)hensylzirconium hydride, bis(cyclopentagenyl)neopentylzirconium hydride, bis(methylcyclopentagenyl)zirconium monochloride hydride, bis( indenyl) zirconium monochloride monohydride, bis(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium dimethyl
bis(cyclopentagenyl)methylzirconium monochloride, bis(cyclopentagenyl)ethylzirconium monochloride, bis(cyclopentagenyl)cyclohexylzirconium monochloride, bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, bis(methylcyclopentagenyl)zirconium dichloride, bis(t-butylcyclopentagenyl)zirconium dichloride bis(indenyl)zirconium dichloride, bis(indenyl)silconium dibromide , bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconiumdiphenylbis(cyclopentagenyl)zirconium dibenzyl, bis(cyclopentagenyl)zirconium methoxychloride, bis(cyclopentagenyl)zirconium Methoxychloride, Bis(methylcyclopentagenyl)zirconium ethoxychloride, Bis(cyclopentagenyl)zirconium phenoxychloride, Bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylene Bis(indenyl)methylzirconium, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, isopropylbisindenylzirconium dichloride, isopropyl(cyclopentajenyl)-1-fluorenylzirconium chloride, ethylenebis (indenyl) zirconium compound, ethylene bis (indenyl) zirconium methoxy monochloride, ethylene bis (indenyl) zirconium ethoxy monochloride, ethylene bis (indenyl) zirconium phenoxy monochloride, ethylene bis (cyclopentajenyl) zirconium dichloride, propylene Bis(cyclopentagenyl)zirconium dichloride, ethylenebis(t-butylcyclopentagenyl)silconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4, 5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-titrahydro-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1) -indenyl) zirconium dichloride, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis (7-Methyl-1-indenyl) zirconium dichloride, ethylenebis(5-methoxy-[-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl- 1-indenyl) zirconium dichloride, ethylenebis(4,7-simethoxy1-indenyl)
Zirconium dichloride.

In the above zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, vanadium metal, etc. can also be used.

In this case, the organometallic compound catalyst component [i] may be a conventionally known aluminoxane or organoaluminumoxy compound. This organoaluminumoxy compound is obtained, for example, by reaction of an organoaluminum compound with water, or by reaction of an aluminoxane dissolved in a hydrocarbon solution with water or an active hydrogen-containing compound.

In the present invention, the amount of catalyst used varies depending on the type of catalyst used, but for example, the amount of the catalyst component [A
], organometallic oxide catalyst component [B] and electron donor [
C] or catalyst components (i) and (1
When using 1), the catalyst component [A] or catalyst component (i) is usually 0.001 to 0.5 mmol, preferably 0.001 to 0.5 mmol in terms of transition metal, per 1 p of polymerization volume.
．． The organometallic compound catalyst [B] is used in an amount of 0.005 to 0.5 mmol, and the amount of the organometallic compound catalyst [B] is determined based on 1 mole of transition metal atoms of the catalyst component [A] in the polymerization system. The metal atoms of B] are generally used in an amount of 1 to 10,000 mol, preferably 5 to 500 mol. Furthermore, when using the electron donor [C], the electron donor [C] is 100 mol or less, preferably 1 to 50 mol, per 1 mol of the transition metal atom of the catalyst component [A] in the polymerization system. , particularly preferably in amounts of 3 to 20 mol.

The polymerization temperature when performing polymerization using the above catalyst is usually 20 to 200°C, preferably 50 to 100°C, and the pressure is normal pressure to 100 kg/cd, preferably 2 to 5
It is 0 kg/c-.

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

When titanium is used as the transition metal, the amount of polymerization in prepolymerization is usually 1 g per 1 g of titanium catalyst component.
-2000g, preferably 3-1000g, particularly preferably 10-500g.

Prepolymerization can be carried out using inert hydrocarbon solvents. Specifically, such inert hydrocarbon solvents include propane, butane, n-pentane, i-pentane, 0-hexane, tohexane, n-hebutane, n-octane, i-octane, n-decane, Aliphatic hydrocarbons such as n-dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, and ethyl chloride. , ethylene chloride, and chlorobenzene. Among these, aliphatic hydrocarbons are preferred, and aliphatic hydrocarbons having 4 to 10 carbon atoms are particularly preferred. Furthermore, the monomer used in the reaction can also be used as a solvent.

Specifically, the α-olefin used in this prepolymerization includes ethylene, propylene, ■-butene, ■-pentene, 4-methyl-1-pentene, 3-methyl-1-
α-olefins having 10 or less carbon atoms such as pentene, -heptene, 1-octene, and 1-decene are used, and among these, α-olefins having 3 to 6 carbon atoms are preferred, and propylene is particularly preferred. These α-olefins can be used alone, or two or more types can be used in combination as long as a crystalline polymer is produced.

In particular, polymer particles containing a large amount of amorphous olefin polymer moiety and having good particle properties, such as polymer particles containing 30% by weight or more of amorphous olefin polymer moiety and having good particle properties. To obtain a prepolymerization of e.g.
A method has been proposed in which propylene and ethylene are copolymerized using a mixed gas consisting of ~98 mol% propylene and 30~2 mol% ethylene.

The polymerization temperature in the prepolymerization varies depending on the α-olefin used and the inert solvent used, and is generally between -40 and 80°C, preferably -22°C, although it cannot be generally specified.
The temperature is 0 to 40°C, particularly preferably -10 to 30°C. For example, when using propylene as the α-olefin, -40 to 70°C, and when using ■-butene,
-40 to 40°C, -40°C when using 4-methyl-1-pentene and/or 3-methyl-1-pentene
It is within the range of 0 to 70°C. Note that hydrogen sludge may be allowed to coexist in the reaction system of this prepolymerization.

After performing prepolymerization as described above, or without prepolymerization, the above-mentioned monomer is then introduced into the reaction system and a polymerization reaction (main polymerization) is performed to produce polymer particles. I can do it.

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

The polymerization temperature for the main polymerization of such olefins is usually -
The temperature is 50 to 200°C, preferably 0 to 150°C. The polymerization pressure is usually normal pressure to 100 kg/cd, preferably normal pressure to 50 kg/c, and the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods.

The molecular weight of the resulting olefin polymer can be controlled by hydrogen and/or polymerization temperature.

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

Furthermore, the polymer particles used in the present invention have a temperature that is higher than the melting point of the crystalline olefin polymer portion or the glass transition point of the amorphous olefin polymer portion of the polymers constituting the polymer particles. It is preferable that the particles be polymer particles that have not been substantially heated.

The "amorphous olefin polymer portion" referred to herein means a polymer that dissolves in n-decane at 23°C, and specifically refers to a polymer portion that has been subjected to solvent fractionation by the following method.

That is, in this specification, a solution of n-decane (500 ml) to which polymer particles (3 g) were added was heated to 140 ml while stirring.
After carrying out the dissolution reaction at ~145°C, stirring was stopped, and the mixture was cooled to 80°C in 3 hours, to 23°C in 5 hours, and after being kept at 23°C for another 5 hours, it was filtered and separated using a G-4 glass filter. A polymer obtained by removing n-decane from the obtained filtrate is referred to as an "amorphous olefin polymer portion."

Among the polymer particles used in the present invention, non-crosslinked polymer particles are the above-mentioned polymer particles, and gas-phase crosslinked polymer particles are the above-mentioned polymer particles and a crosslinking agent. Crosslinked polymer particles (particulate crosslinked thermoplastic elastomer).

The crosslinking agent used in the present invention (including when used in the production of gas-phase crosslinked polymer particles) includes organic peroxides, sulfur, phenolic vulcanizing agents, oximes, and polyamines. Among them, organic peroxide and phenolic vulcanizing agents are preferred from the viewpoint of the physical properties of the thermoplastic elastomer obtained. Particularly preferred are organic peroxides.

As the phenolic vulcanizing agent, specifically, an alkylphenol formaldehyde resin, a triazine-formaldehyde resin, and a melamine-formaldehyde resin are used.

In addition, specific examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane-3,1,3
-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)
-3,3,5-h-limethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy) halerate, dibenzoyl peroxyto, tert-butyl peroxyhensiatate, etc. are used. this house,
From the viewpoints of crosslinking reaction time, odor, and scorch stability, dibenzoyl peroxyto and 1,3-bis(tert-butylperoxyisopropyl)benzene are preferred.

Further, in order to realize the crosslinking reaction uniformly and moderately, it is preferable to mix a crosslinking auxiliary agent. Specific examples of crosslinking aids include sulfur, p-quinonedioxime, p,p'-cyhenzoylquinone quinone, N-methyl N, 4-dinitrosoaniline, nitrohensen, diphenylguanidine, and trimethylolpropane. Peroxy crosslinking aids such as N,N'-m-phinidine maleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol Polyfunctional methacrylate monomers such as propane trimethacrylate, allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butylade or vinyl stearate are used. By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylhensen is easy to handle, has good compatibility with polymer particles, has an organic peroxide solubilizing effect, and also works as a peroxide dispersion aid, so that the crosslinking reaction is carried out homogeneously. This is most preferable because a thermoplastic elastomer with well-balanced fluidity 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 parts by weight, based on 100 parts by weight of the polymer particles.
It is used in an amount of ~1 part by weight, and by blending within this range, a thermoplastic elastomer can be obtained which has excellent fluidity and whose physical properties do not change due to the thermal history during processing and molding of the thermoplastic elastomer.

In the present invention, when producing a thermoplastic elastomer composition or gas-phase crosslinked polymer particles, in addition to the polymer particles, crosslinking agent, and crosslinking aid, peroxide non-containers such as polyisobutylene and butyl rubber are optionally added. The crosslinking reaction of the polymer particles can also be carried out in the presence of a crosslinked hydrocarbon comb material and/or a mineral oil softener.

Mineral oil-based softeners usually weaken the intermolecular forces of rubber during roll processing, making processing easier.
A high boiling point petroleum distillate that is used to help disperse carbon black, white carbon, etc., or to reduce the hardness of vulcanized rubber and increase its flexibility or elasticity. , paraffinic, naphthenic,
Alternatively, aromatic mineral oil may be used.

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

Further, during the production of gas-phase crosslinked polymer particles, it is also possible to use a crosslinking agent, and if necessary, a crosslinking aid and a mineral oil softener diluted in a swelling solvent. The swelling solvent dilutes the crosslinking agent and, if necessary, the crosslinking co-agent to aid in dispersion onto the surface of the polymer particles, and also swells the polymer particles, at which time the crosslinking agent and crosslinking agent are incorporated into the polymer particles. Since it has the function of transporting the auxiliary agent, the use of a swelling solvent allows the crosslinking reaction to occur uniformly even inside the polymer particles. Furthermore, if a poor solvent for the olefin polymer is used as the swelling solvent, it is also possible to selectively carry out the crosslinking reaction near the surface of the polymer particles. In any case, the type of swelling solvent selected for the reaction depends on the type of polymer particles used. Of course, the crosslinking reaction is possible without using any swelling solvent.

Specifically, such swelling solvents include Hensen,
Aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene; Chlorinated hydrocarbon solvents such as chlorhensene, dichlorohenzene, trichlorhenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, dichloroethylene, trichlorethylene, methanol, ethanol, n-propanol, 1so-propanol, n
- Alcohol solvents such as butanol, 5ee-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, ethyl ether, and ethyl ether; , ether solvents such as tetrahydrofuran, dioxane, and anisole are used.

Such a swelling solvent is desirably used in an amount of 1 to 100 parts by weight, preferably 5 to 60 parts by weight, and more preferably 10 to 40 parts by weight, based on 100 parts by weight of the polymer particles.

When the swelling solvent as mentioned above comes into contact with the polymer particles used in the present invention, it swells the polymer particles, especially the amorphous olefin polymer portion of the polymer particles, and the crosslinking agent and crosslinking co-agent swell. Does it play a role in penetrating into the particles? ＝Doing.

However, the amount of swelling solvent used in the present invention is
The amount is 2.200 parts by weight or more per 100 parts by weight of the polymer particles, and the gas phase crosslinking reaction in the present invention is different from a solvent suspension reaction in which a large excess of solvent is used.

The gas phase crosslinking reaction in the present invention is carried out at a temperature at which the polymer particles are melted and the polymer particles do not fuse together. - The above reaction is carried out on the membrane surface at a temperature within the range from CJ°C to below the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer, whichever is higher. For example, the above-mentioned polymers with high melting points, polypropylene, high density polyethylene,
In the case of low density polyethylene, the upper limit of the reaction temperature is around 150°C, around 120°C, and around 90°C, respectively.

In addition, the reaction time is 1 to 30 times, preferably 2 to 10 times, more preferably 3 to 7 times the half-life time of the crosslinking agent at the temperature at which the gas phase crosslinking reaction is carried out, and the pressure is (
-)~50 kg/c11! , preferably 1-20
kg/cl! , more preferably l −5 kg
%'cJ. The gas phase crosslinking reaction can be carried out either batchwise or continuously.

During the production of gas-phase crosslinked polymer particles, polymer! , , l, a cross-linking agent and 1. If necessary, it is most preferable to carry out a gas phase crosslinking reaction by simultaneously contacting a crosslinking aid and a mineral oil softener. It is also possible to carry out a gas phase crosslinking reaction by bringing them into contact with each other separately.

When polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are crosslinked in this way, a crosslinking reaction occurs inside the polymer particles, and in particular, the amorphous olefin polymer part of the polymer particles A crosslinking reaction occurs in the r\ body part, and the amorphous olefin polymer part (rubber component) is fixed within the particle at the molecular segment level.

The reaction device used in the present invention is a device capable of mixing at least polymer particles, and may be either a vertical or horizontal reactor. When heat treatment is performed, the polymer position -r
A reactor capable of mixing and heat treatment is used. Specific examples of the reaction apparatus used in the present invention include a fluidized bed, a moving bed, a loop reactor, a stirring blade (=I) reactor, a rotating drum, and a stirring blade equipped reactor.

In addition, in crosslinked polymer particles consisting of intraparticle crosslinked thermoplastic ex-mers, the insoluble fraction that is not extracted by cyclohexane is measured as follows: 10% by weight?
6 or more, preferably 40 to 100% by weight, more preferably 60 to 99% by weight, particularly preferably 80 to 98% by weight.

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

Here, the measurement of the gel content insoluble in nclohexane is carried out as follows. Sample pellets of thermoplastic elastomer (size of each pellet + 1 mm x 1 mm x 0.
5mm) approx. 1. [Weigh out 10 mg, immerse it in 30 cc of cyclohexane in a closed container at 23°C for 48 hours, then take a sample and dry it. If the thermoplastic elastomer contains cyclohexane-insoluble fillers, pigments, etc., subtract the weight of the cyclohexane-insoluble fillers, pigments, etc. from the weight of this dry residue. Let be the corrected final weight (Y) after drying. On the other hand, based on the weight of the sample pellet, the amount of Nclohexane IIJ soluble components other than the ethylene/α-olefin copolymer, such as plasticizers and/
If chlorohexane-insoluble fillers, pigments, etc. are contained in The reduced weight is complemented by +-1' and set as t initial weight (X).

From these values, the cyclohexane insoluble fraction is determined by the following formula.

Corrected final weight (Y) Kel content (%) - X100 Corrected initial weight (X) Preferred crosslinked polymer particles made of the thermoplastic elastomer produced as described above have an average particle diameter of
5000 μm 1 is preferably in the range of 200 to 4000 μm, more preferably 300 to 3000 μm. Further, the crosslinked polymer particles used in the present invention have a geometric standard deviation indicating the particle size distribution of the particles, or 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.0. 5, more preferably within the range of 1.0 to 1.3.

Further, 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 0.6.
0, more preferably within the range of 0.35 to 0.50. Further, the crosslinked polymer particles used in the present invention have an aspect ratio of 1.0 to 3.0, preferably 1.0 to 2.0.
0, more preferably within the range of 1.0 to 1.5. Further, the crosslinked polymer particles used in the present invention have a particle size of 10
The amount of fine particles of 0 μm or less is 20% by weight or less, preferably 0
-10% by weight, more preferably 0-2% by weight.

In addition, the crosslinked polymer particles (thermoplastic elastomer particles) produced as described above contain fillers such as calcium carbonate, calcium silicate, flekaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, and barium sulfate. , aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass bulb, shirasu balloon, carbon fiber or coloring agent such as carbon black, titanium oxide, zinc white, red iron, ultramarine, navy blue, azo It is also possible to incorporate dyes, nitroso dyes, lake pigments, phthalocyanine pigments, etc.

The crosslinked polymer particles used in the present invention are polymer particles obtained by performing a crosslinking reaction (gas phase crosslinking reaction) of polymer particles at low temperatures, so thermal decomposition of the polymer particles can be suppressed. It is possible to provide molded products with excellent strength properties such as impact strength and bow tensile strength, toughness, heat resistance, flexibility at low temperatures, surface smoothness, and paintability.

In particular, crosslinked polymer particles (thermoplastic elastomer) that are fixed within the amorphous olefin polymer (rubber component) or particles at the molecular segment level have improved flexibility, surface smoothness, and paintability at low temperatures. Can give excellent molded products.

Phenol stabilizer (A) The phenol stabilizer (A) used in the present invention may be a conventionally known one or may be used without particular limitation; specifically, the following compounds may be used: .

2.6-di-t-butyl-4-methylphenol, 2.
6-di-tert-butyl-4-ethylphenol, 2.6-
Dicyclohexyl-4-methylphenol, 2.6-diisopropyl-4-ethylphenol, 2.6-sheet
-Amyl-4-methylphenol, 2.6-di-t-octyl-4-n-propylphenol, 2.6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-et- Butylphenol, 2-t-butyl-2-ethyl-6-1-octylphenol, 2-isobutyl-4-ethyl-6-1-hexylphenol, 2-cyclohexyl-4-n-butyl-6-ite Brobylphenol, dl-α-tocopherol, t-butylhydroquinone, 2.2-methylenebis(4-methyl-6-t-butylphenol) 4.4-butylidenebis(3-methyl-et-butylphenol), 4. 4-thiobis(3-methyl-6-t-butylphenol), 2.2-thiobis(4-methyl-6-t-butylphenol), 4.4-methylenebis(2,6-di-t-butylphenol), 2. 2-methylenebis[6-(1-methylcyclohexyl)-p-cresolco2,2-ethylidenebis(2,4-di-t-butylphenol), 2.2'-butylidenebis(2-t-butyl-4-methyl phenol), 1.1.3-)lis(2-methyl-4-hydroxy-5
-1-butylphenyl)butane, triethylene glycol-bis[3-(3-t-butyl 5-methyl-4-hydroquinphenyl)propionate] 1,6-hexanethiol bis[3-(3,5 -G-
t-butyl-4-hydroxyphenyl)propionate]2,2-thiodiethylenebis[3-(3,5-sheet t
-butyl-4-hydroxyphenyl)propionate]
N,N-hexamethylenebis(3,5-di-t-butyl 4-hydroquine-hydrocinnamide), 3,5-di-t-butyl
-Butyl-4-hytroquine benzylphosphonate diethyl ester, 1.3.54 lis(2,6-dimethyl-3-hydroxy-4t-butylpencyl)isocyanurate, 1.3.
54 Lis[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isonanurate, Tris(4-t-butyl-2,6-dimethyl-3-hydroxypencyl)isocyanurate, 2.4 -bis(n-octylthio)-6-(4-hydroxy-3,5-t-)ethylanilino)-1,3,
54 rianne, tetrakis[methylene-3-(3,5-
/-t-butyl-4-hydroxyphenyl)propionate comethane, bis(3,5-t-butyl-4-hydroxyethyl quinhensylphosphonate)calcium, bis(3,5-di-t-butyl- ethyl 4-hydroquinhenylphosphonate) nickel, bis[3,3-bis(3-t-4-hydroquinphenyl)butyric anthocoglycol ester, N,N'-
bis[3,5-t-butyl-4-hydroxylephenyl)propionyl]hydrane), 2.2°-oxamidobis[ethyl-3-(3,5-so-t-butyl-4-
Hydroquinphenyl)propionate] 2.2゛-methylenebis(4-methyl-6-t-butylphenol)terephthalate, 1.3.54limethyl-2,4,6-tris(3,5-
monobutyl-4-hydroquinhensyl) Hensen,
3.9-bis[1,1-dimethyl-2~(β-(3-1
-butyl-4hydroxy-5-methylphenyl)propionyloxy)ethyl]-2,4,8,lO-tetraoxazolester[5,5] undecane, 2,2-bis[4-(2-(3,5- Sheet-t-butyl-
4-hydroxyhydrocinnamoyloxy))ethoxyphenyl]propane, β-(3,5-the-t-butyl-4-hydroquinphenyl)propionic acid alkyl ester.

Among them, the following compounds are preferably used.

Triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroquinphenyl)propionate] ■,6-hexanethiol bis[3-(3,5-di-
t-butyl-4-hydroxyphenyl)propionate]2,2-thiodiethylenebis[3-(3,5-di-t
-butyl-4-hydroquinphenyl)propionate]
N, N-hexamethylenebis(3,5-t-butyl 4-hydroxyhydrontimito), 3,5-t-butyl-4-hydroxyhenylphosphonate diethyl ester, 1.3.5 -) lis(2,6-methyl-3-hydroquine-41-butylhensyl)isocyanurate, 1.3
．． 5-Tris[(3,5-t-butyl-4-hydroxyphenyl)propionyloquinethyl]yanoa.

Anurate, Tris(4-t-butyl-2,6-trimethyl-3-hydroxyhenyl)isocyanurate, 2,4-bis(n-octylthio>-Pi-(4-hydroxy73.5-so-t- butylanilino)-1,3,5
-h rianne, tetrakis methylene-3i3.5-7
-t-butyl-4-hydroxyphenyl) propionate comethane, bis(3,5-not-butyl-4-hydroxyphenyl).

Calcium (ethyl phosphonate), Nickel bis(ethyl 3,5-t-butyl-4-hydroxyhensylphosphonate), Nickel bis[3,3-bis(3-1-4-hydroxyphenyl)butyric acid coglycol] Ester, N, N“-
bis[3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydran), 2,2'-oxamitobis[ethyl-3-(3,5-di-t-butyl-4-
Hydroxyphenyl)propionate] 2.2゛-methylenebis(4-methyl-6-1-butylphenol)terephthalate, 1.3.54limethyl-2,4,6-tris(3,5-
(t-butyl-4-hydroxybenzyl) Hensen,
3.9-bis[1,l-dimethyl-2-(β-(3-t
-butyl-4hydroxy-5-methylphenyl)propionyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5-oundecane, 2.2-bis[4-(2-(3,5- di-t-butyl-
4-hydroxyhydrocinnamoyloxy))ethoxyphenylcopropane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester.

The β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester is particularly preferably an alkyl ester having 18 or less carbon atoms.

Further, compounds particularly preferably used in the present invention are as follows.

Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, bis(3,5-di-t-butyl-4-hydroxypencylphosphonate ethyl)calcium, Bis(3,5-di-t-butyl-4-hydroxyhensyl ethylphosphonate)nickel, Bis[3,5-bis(4-hydroxy-3-1-butylphenyl)butyric acid coglycol ester, N , N'--bis[3,5-di-t-butyl-4-hydroquinphenyl)propionyl]hydrazine), 2.2
-Ogizamide bis[ethyl-3-(3,5-di-butyl-4-hydroxyphenyl)propionate] 2.2-methylenebis(4-methyl-et-butylphenol)terephthalate, 1.3.54limethyl-2, 4,6-tris(3,5-
di-t-butyl-4-hydroxyhensyl) Hensen, 3
．． 9-bis[1,1-dimethyl-2-(β-(3-1-
butyl-4hydroxy-5-methylphenyl)propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 1.3.5-tris[(3,5-di-t -butyl-4-
hydroxyphenyl)propionyloxyethyl]isocyanurate, 2,2-bis[4-(2-(3,5-di-t-butyl-
4-hydroxyhydrocinnamoyloxy))ethoxyphenyl]propane and the like.

These phenolic stabilizers may be used alone or in combination.

In the present invention, the above-mentioned phenolic stabilizer (
A) is usually 0.01 parts by weight per 100 parts by weight of the crosslinked polymer.
It is used in an amount of ~10 parts by weight, preferably 0.05-5 parts by weight.

In the present invention, when the phenolic stabilizer (A) is used in the above-mentioned blending ratio, thermoplastic elastomers can be produced which have excellent heat resistance, are economical, and do not deteriorate resin properties such as tensile strength. A composition is obtained.

Organic thioether stabilizer (B) In the present invention, in addition to the above polymer particles and phenol stabilizer (A), an organic thioether stabilizer (B) can be used.

As the organic thioether stabilizer, conventionally known stabilizers can be used without particular limitation, or specifically, the following compounds can be used.

Polyhydric alcohols of dialkylthiodipropionates such as dilauryl-cimyristyl-distearyl and alkylthiopropionic acids such as butyl-octyl-lauryl-stearyl (e.g. glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl) isocyanurate) (for example, pentaerythritol tetralauryl thioprobionate).

More specifically, dilaurylthiodipionate,
Simyristyl thiodipropionate, stearyl thiodipropionate, laurylstearyl thiodipropionate, cystearyl thiodibutyrate.

These organic thioether stabilizers may be used alone or in combination.

In the present invention, the organic thioether stabilizer (B) as described above is usually used in an amount of 0.00 parts by weight per 100 parts by weight of the crosslinked polymer.
0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

In the present invention, when the organic thioether stabilizer (B) is used in the above-mentioned blending ratio, it has excellent heat resistance, is economical, and has thermoplastic properties that do not deteriorate the properties of the resin, including tensile strength. An elastomer composition is obtained.

Organic phosphite stabilizer (C) In the present invention, the above-mentioned polymer particles, phenol stabilizer (A) and organic thioether stabilizer (B) are used.
), an organic phosphite stabilizer (C) can be used.

As the organic phosphite stabilizer, conventionally known stabilizers may be used without particular limitation, and specifically, the following compounds may be used.

Trioctyl phosphite, l-lilauryl phosphite, tridecyl phosphite, octyldiphenyl phosphite, tris(2,4-t-butylphenyl)
Phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, stearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5- 1-Butyl-4-hydroxyphenyl)butane phosphite, tetra(C12-C1
51-combined alkyl)-4,4°-isopropylidenephenylphosphite, tetra(tridecyl)-4,
4-butylidene(3-methyl-et-butylphenol) diphosphite, tris(3,5-di-t-
butyl-4-hydroxyphenyl) phosphite, tris(mono/cy mixed nonylphenyl) phosphite, hydrogenated-4,4-isopropylidene diphenol polyphosphite, bis(octylphenyl) bis[4,4-butylidene bis] (3-methyl-11i-t-butylphenol)] bow, 6-hexanethiol cyphosphite, phenyl 4,4°-isopropylidene diphenol pentaerythritol diphosphite, tris[4,4 isopropylidene bis(2 -t-butylphenol)] phosphite, phenyl diisodecyl phosphite, di(
(nonylphenyl) pentaerythritoltone phosphite, tris(1,3-stearoyl oxine isoprobyl) phosphite, 4.4°-isopropylidene bis(2-1-butylphenol) cy(nonylphenyl)
Phosphite, 9.10-cyhydro-9-oxa-9
-oxa-10-phosphaphenanthrene-10-oxide.

Further, as the bis(dialkylphenyl)pentaerythritol diphosphite ester, a spiro type represented by the following formula (1) or a cage type represented by the formula (2) are also used. Usually mixtures of both isomers are most often used for economic reasons arising from the process of preparing such phosphite esters.

Preferably, RR2 is an alkyl group having 1 to 9 carbon atoms, particularly a branched alkyl group, especially a t-butyl group, and the substitution position in the phenyl group is most preferably 2, 4, or 8 positions. Suitable phosphite esters include bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-
4-methylphenyl) pentaerythritol diphosphite, and also phosphonites with a structure in which carbon and phosphorus are directly bonded, such as tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphite. Compounds such as phosphonites may also be mentioned.

These organic phosphite stabilizers may be used alone or in combination.

In the present invention, the organic phosphite stabilizer (C) as described above is usually used at 0% per 100 parts by weight of the crosslinked polymer.
．． 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

In the present invention, when the organic phosphite stabilizer (C) is used in the above-mentioned blending ratio, it has excellent heat resistance, is economical, and does not impair the properties of the resin, such as tensile strength and elongation. A thermoplastic elastomer composition is obtained.

Hindered amine stabilizer (D) In the present invention, in addition to the above polymer particles, phenol stabilizer (A), organic thioether stabilizer (B), and organic phosphite stabilizer (C), A hindered amine stabilizer (D) can be used.

As the hindered amine stabilizer, conventionally known compounds having a structure in which all the hydrogens bonded to carbons at the 2- and 6-positions of piperidine are substituted with methyl groups may be used without particular limitation, or specific Typically, the following compounds are used.

(1) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) Methyl succinate-1-(2-hydroquinethyl)-4-hydroquine-2,2,6,8 -tetramethylpiperidine polycondensate, (3) polyC[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-)riazin-2-4-ynylco[(2,26 , 6-tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperinyl)imino]], (4) Tetrakis(2,2,8,6-tetramethyl -4
-piperinyl)-1,2,3,4-butanetetracarpoxylate, (5) 2.2.6.6-tetramethyl-4-pipericinylhenzoate, (6) bis-(1,2, (7) bis-(N-methyl-2,2, 6,6-tetramethyl-4piperidinyl) sebacate, (8) 1,1°-(1,2-nitaneshiyl)bis(3
, 3,5,5-tetramethylpiperazinone), (9) (Mixto2.2.6.6-tetramethyl-4
-piperidyl/tridenyl)-1,2,3,4-butanetetracarboxylate, (10) (Mixto 1.2.2,6.6-pentamethyl-4piperidyl/tridecyl)-1,2,3,4
-butanetetracarboxylate, (11) Mixed (2,2,6,6-tetramethyl-4-piperidyl/β,β,β゛,β“-tetramethyl-3-9[2,4,8, 10-Tetraoxaspiro (5
, 5) Undecane] diethyl l-1,2,3,4-butanetetracarboxylate, (12) Mixto + 1.2.2,6.6-pentamethyl-4piperidyl/β, β, β°, β “-tetramethyl-3-9[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl l-1,2,3,4-
Butane tetracarboxylate, (13) N,N-bis(3-aminopropyl)ethylenediamine-2-4-bis[N·-butyl N-(1,2
,2,6,6-bentamethyl-4-piperacyl)aminoco-6-chloro-1,3,5-triazine condensate, (14) poly[[6-N-morpholyl-1,3,5-triazine 2-4 -silco[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(
2,2,13,6-tetramethyl-4-piperidyl)iminococo, (15) N,N-bis(2,2,6,6-
condensate of tetramethyl-4-piperidyl)hexamethylenecyamine and 1,2-dibromoethane, (1[i) [N-(2,2,6,6-tetramethyl-
4-piperial)-2-methyl-2-(2,2,6,6
-tetramethyl-4-piperidyl)iminocobropionamide.

Among them, the above (1) (2) (3) (4)
(8) (10), (1,1), (14), (15)
Compounds are preferably used.

These hindered amine stabilizers may be used alone or in combination.

In the present invention, the hindered amine stabilizer (D) as described above is generally used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on parts by weight of the crosslinked polymer [OC]. used.

In the present invention, when the hindered amine stabilizer (D) is used in the above-mentioned blending ratio, it has excellent heat resistance and weather resistance, is economical, and can be heated without impairing the properties of the resin, such as tensile elongation. A plastic elastomer composition is obtained.

Higher fatty acid metal salt (E) In the present invention, the above-mentioned polymer particles, a phenolic stabilizer (A), an organic thioether stabilizer (B),
In addition to the organic phosphite stabilizer (C) and the hindered amine stabilizer (D), a higher fatty acid metal salt (E) can be used.

Examples of metal salts of higher fatty acids include magnesium salts and calcium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, capric acid, arachinic acid, palmitic acid, hehenic acid, 12-hydroxystearic acid, ricinoleic acid, and montanic acid. Salts, alkaline earth metal salts such as barium salts, alkali metal salts such as cadmium salts, zinc salts, lead salts, sodium salts, potassium salts, and notium salts are used. Specifically, the following compounds are used.

Magnesium stearate, Magnesium laurate,
Magnesium palmitate, carunium stearate,
Calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium arachinate, barium hehenate, zinc stearate, zinc oleate, zinc laurate, stearate, sodium stearate, palmitic acid Sodium, hexathorium laurate, potassium stearate, potassium laurate, calcium 12-hydroxystearate, calcium montanate.

These metal salts of higher fatty acids may be used alone or in combination.

In the present invention, higher fatty acid metal salts (E
) is usually 0.01 to 100 parts by weight of the crosslinked polymer.
It is used in an amount of 10 parts by weight, preferably (L), 45 to 5 parts by weight.

In the present invention, when higher fatty acid metal salt (E) is used in the above-mentioned blending ratio, residual chlorine in the polymer derived from the catalyst is sufficiently absorbed, does not cause resin deterioration, and heat resistance is improved. The result is a thermoplastic elastomer composition that is both economical and has excellent performance and does not impair the properties of the resin, such as tensile elongation.

Since the higher fatty acid metal salts described above have effects as lubricants and antirust agents, the thermoplastic elastomer composition according to the present invention has excellent moldability and is effective in preventing rust in molding machines and the like.

In the present invention, the above components (A) (B) (C
) In addition to (D) and (E), for example, heat stabilizers, weather stabilizers, parts, dyes, lubricants, antistatic agents, etc.
Compounding agents that are normally added and mixed with polyolefins can be added within a range that does not impair the purpose of the present invention.

In order to produce the thermoplastic elastomer composition in the present invention, a mixture containing, for example, the above-mentioned non-crosslinked polymer particles, a crosslinking agent, and a phenolic stabilizer (A), or in addition to these components, may be used. and one or more selected from the group consisting of organic thioether stabilizers (B), organic phosphite stabilizers (C), hindered amine stabilizers (D) and higher fatty acid metal salts (E). A mixture containing a stabilizer may be melt-kneaded to effect partial or complete crosslinking.

The above-mentioned crosslinking agent is about 0% per 100 parts by weight of the polymer particles.
．． It is used in an amount of 0.01 to 2 parts by weight, preferably 0.03 to 1.0 parts by weight, more preferably 0.05 to 0.5 parts by weight.

As the kneading device used in the above-mentioned melt blending, an open type device such as a mixing roll, or a closed type device such as a Banbury Mixer 1 extruder, a kneader, or a continuous mixer can be used. Among such kneading devices, an extruder is particularly preferably used.

The kneading is preferably carried out in a non-release type device, and preferably in an atmosphere of inert scum, such as nitrogen or carbon dioxide scum. The temperature is usually 150 to 280°C, preferably 170 to 240°C, and the kneading time is usually 1 to 20°C.
minutes, preferably 1 to 10 minutes.

Further, in the present invention, the thermoplastic elastomer composition is
For example, a mixture containing the above gas-phase crosslinked polymer particles and a phenolic stabilizer (A), or in addition to these components, an organic thioether stabilizer (B) and an organic phosphite stabilizer (C). ) Hindered amine stabilizer (D
It can also be produced by melt-kneading a mixture containing one or more stabilizers selected from the group consisting of ) and higher fatty acid metal salts (E).

Furthermore, in the present invention, the gas-phase crosslinked polymer particles as described above are first melted, and then the phenolic stabilizer (A) or the phenolic stabilizer (A) is added to the melt.
), an organic thioether stabilizer (B), an organic phosphite stabilizer (C), a hindered amine stabilizer (D)
A thermoplastic elastomer composition can also be produced by adding and kneading one or more stabilizers selected from the group consisting of and higher fatty acid metal salts (E).

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

The crosstalk is preferably carried out in a non-release type device, and preferably in an atmosphere of an inert gas such as nitrogen or carbon dioxide scum. The temperature is usually 150 to 280°C, preferably 170 to 240°C, and the crosstalk time is usually 1 to 2
0 minutes, preferably 1 to 10 minutes.

Effects of the Invention According to the present invention, it has excellent tensile strength characteristics, flexibility, elasticity, impact resistance at low temperatures, surface smoothness, and paintability, as well as excellent thermal stability during molding, long-term thermal stability, and weather resistance. An excellent thermoplastic elastomer composition is obtained. In particular, thermoplastic elastomer compositions containing hindered amine stabilizers have excellent weather resistance.

The thermoplastic elastomer composition according to the present invention can be molded using molding equipment used for ordinary thermoplastic polymers, and is suitable for extrusion molding, calendar molding, and especially injection molding.

Such thermoplastic elastomer compositions can be used for body panels, bumper parts, site shields, automobile parts such as steering link wheels, footwear such as shoe soles and sandals, electric wire coverings, electrical parts such as connector cap plaques, golf club clips, Baseball hat clip, swimming fins,
Leisure goods such as underwater glasses, waterproof sheets, water-stopping materials, joint materials, architectural window frames, architectural gaskets, civil engineering and building material parts such as decorative rigid board covering materials, gaskets, waterproof cloth,
Used for carden hose and held horses.

[Examples] Hereinafter, the present invention will be explained by examples, but the present invention is not limited to these examples.

[Adjustment of catalyst component [A]] A high-speed stirring device (Special Kika I pear type) with an internal volume of 2 g was heated to sufficient N.
After 2 substitutions, 700 ml of refined kerosene, +lF Sales M
g Cf), 24.2 g of ethanol, and 3 g of Emazol 320 (trade name, manufactured by Kao Atlas ■, Sorbitan Stearate) were added, and the system was heated while stirring.
The mixture was stirred at 120° C. and 800 rpm for 30 minutes. Under high-speed stirring, using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2Ω glass flask (equipped with a stirrer) filled with 1 g of refined kerosene cooled to -10°C.

The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

After 7.5 g of the carrier was suspended in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added, and the temperature of the suture removal was raised to 120°C. After stirring and mixing at 120°C for 2 hours, the solid part was collected by filtration, and the solid part was collected again at 150 m
1 was suspended in titanium tetrachloride, and stirred and mixed again at 130° C. for 2 hours.

Furthermore, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to remove the solid catalyst component (
A) was obtained. The ingredients are 2.2% by weight of titanium,
Chlorine 63 weight 0o, Makne, Ram 20 weight NIL 9Ω
% isobutyl phthalate 55 weight-〇.

Met. The average particle size is 64 μm, and the particle size distribution is (+: Also.

[Preliminary polymerization] The catalyst component [A] was subjected to the following preliminary polymerization.

After charging 200 ml of purified hexane into a 40 CI ml glass reactor purged with nitrogen, 20 mmol of triethylaluminum, 4 mmol of diphenylene methquine 7 run, and the Ti catalyst component [A] were added in terms of titanium atoms. After charging 2 mmol, propylene was fed at a rate of 5.9 NΩ/hour for 1 hour (ji: feeding, Ti catalyst component [
A]1. 2.8 g of propylene was polymerized per g. The humidity was maintained at 20°C and 2°C during the polymerization. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

[Polymerization] 2.0 kg of propylene and 19N liter of hydrogen were added to a 20 g polymerization vessel at room temperature, then heated to H temperature, and prepolymerized at 50°C with 15 mmol of triethylaluminum, 15 mmol of dicyclohexyldimethoxine, and catalyst component [A]. 0.05 mmol of the treated material was added in terms of titanium atoms, and the temperature inside the polymerization vessel was maintained at 70°C. Thirty minutes after the temperature reached 70°C, the vent bulk was opened and propylene was vented until the inside of the polymerization vessel reached normal pressure to carry out homopolymerization of propylene. After purging, copolymerization was carried out subsequently.

That is, ethylene is 48ONΩ/hour, propylene is 72ONΩ/hour.
0 rl/hour, and hydrogen was supplied to the polymerization reactor at a rate of 12 Nρ/hour. The opening degree of the vent of the polymerization vessel was adjusted so that the pressure inside the polymerization vessel was 10 kg/crl·G.

The temperature during copolymerization was kept at 70°C. Copolymerization time is 150
Copolymerization was carried out for minutes.

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

Production of copolymers (2) and (3) In the production of copolymer (1), the prepolymerization conditions were changed as shown below, and the copolymerization conditions were as shown in Table 1. In the same manner as producing copolymer (1),
Copolymers (2) to C3)i were produced.

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

[Preliminary Polymerization The cocatalyst component [A] was subjected to the following prepolymerization. 400 ml of purified hexane in a 1 g glass reactor purged with nitrogen
After charging, 1.1.32 mmol of triethylaluminum, 0.27E of cyclohexylmethyl methoxysilane,
After charging O, 132 mmol in terms of titanium atoms, of the above-mentioned 1゛1 catalyst component [A], propylene gas and ethylene gas were charged at 8.4 NΩ/hour and 1.5 NΩ/hour, respectively. ON
100Ω into the liquid phase of the polymerization vessel while mixing at a rate of Ω7/hour.
Supplied for minutes. Furthermore, the humidity was maintained at 20° C. and 20° C. during the prepolymerization. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

As a result of the analysis, approximately 92 g of polymer was present on the used Ti catalyst component [A]Ig in the prepolymerized solid catalyst, while in the separated filtrate, the used Ti catalyst component [A1
There was an equivalent of 6.2 g of solvent soluble polymer per gram.

(The following is a blank space) Table Example 1 100 parts by weight of the copolymer powder obtained as described above and 0.2 parts by weight of 1,3-bis(tert~butylperoquine isopropyl)benzene were added to 20 parts by weight of divinylhene. , 3 parts by weight and a solution dissolved and dispersed in 5 parts by weight of paraffinic process oil were mixed using a tumbler blender, and the solution was uniformly adhered to the powder surface of copolymer (1).

The powder of the above copolymer (1) has an average particle size of 2200
μm, the apparent density is 0.45/ml, and 1
The number of particles passing through the 50 mesh was 0.1% by weight, and the falling time was 8.3 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.5.

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

100 parts by weight of the obtained pellets, 0.2 parts by weight of tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and bis(2,
The physical properties and moldability of a thermoplastic elastomer composition obtained by extruding 0.2 parts by weight of 2,L6-tetramethyl-4-piperidine) sebacate at 210°C using an extruder were evaluated as follows.

First, the pellets were injection molded using the following equipment and conditions to produce a square plate with a thickness of 3 +++n, and the moldability was evaluated. Further, test pieces were cut from the square plates thus obtained, and their tensile properties, initial bending modulus, and Izot impact strength were measured.

Molding conditions Molding machine: Dynamelter (manufactured by Nagi Seisakusho) Molding temperature: 2
00℃ Injection pressure crab - next time 1300 kg/cJ secondary pressure
Next time 00 kg/c/ Injection speed: Maximum molding speed, 90 seconds/1 cycle Gate: Direct Kate (Land length 10 + nn, Medium 10 order, Depth 3 + nm) Formability judgment criteria 1: Those with a significant number of flow marks 2 3. Flow marks are slightly visible on the entire surface of the molded product. 4. Flow marks are slightly visible on the entire surface of the molded product. 5. Flow marks are barely visible on the opposite side of the cage. 5. Flow marks are not visible at all. Physical property evaluation tensile properties: 1,0096 tensile stress (Mloo, kg/.d)
Tensile strength at break (T, kg/c4) Elongation at break (EB, 96) Measured in accordance with JIS K-6301.

Initial bending modulus (FM, kg/c) AST~I
Measured according to D790.

Izod impact strength (IZOD kg-cm/
cm) Measured according to ASTM D 256.

(With notches) Appearance evaluation The coating of the square plate obtained under the above molding conditions and the coating sharpness were evaluated as follows.

1. Painting conditions and procedures ■) Paint the surface of the square plate 1.1. 1-Lychloroethane steam cleaning (20 seconds) and degreasing.

2) After applying Brimer UniStole P-401<F-Tsukiishura Kagaku Kogyo ■), dry at room temperature.

3) After applying paint R-271 (manufactured by Nippon B Chemical), baking was performed at 100°C for 30 minutes.

2. Evaluation of paint film clarity Automotive technology (Journal of the 5oci
ety of Aut.

motive Engineers or Japan
) 4 (P. G D (
Portable Gloss 1) istinctn
Ess of Image) values were measured.

The results are shown in Table 2.

Example 2 In Example 1, the powder of copolymer (1) obtained by mixing in a tumble blender and two types of stabilizers were mixed, and then heated by extruding at 210°C in a nitrogen atmosphere with an extruder. The same procedure as in Example 1 was carried out except that the plastic elastomer composition was changed.

The results are shown in Table 2. Example 3 The procedure was carried out in the same manner as in Example 1, except that copolymer (2) was used instead of copolymer (1), and Table 2
I got the result.

The powder of the above copolymer (2) has a V uniform particle size of 21
(] Oμm, and the apparent density is 0.43/ml
]50 The particles passing through the mesh have a weight of 0196
The falling time was 9.3 seconds.

Moreover, the geometric standard deviation of this polymer particle was 1.5.

Example 4 The same procedure as Example 1 was carried out except that copolymer (3) was used instead of copolymer (1).

The powder of the above copolymer (3) has an average particle size of 2000
μm, the apparent density was 0.4 (JJJg/ml), the particles passing through the 150 mesh were 0.2% by weight, and the falling time was 10.3 seconds. The geometric standard deviation of the particles is 1.6.

The results are shown in Table 2.

Example 5 The same procedure as in Example 1 was carried out except that bis(2,2,6,6-tetramethyl-4-piperidine) sebacate was not used.

The results are shown in Table 2.

Examples 6 to 8 1 equipped with a stirring blade having a helical double ribbon
3 kg of the polymer particles obtained as described above were placed in a 5 g stainless steel autoclave, and the inside of the system was completely purged with nitrogen. Then, without stirring the polymer particles, a crosslinking mixture having a compounding ratio as shown in Table 3 was added dropwise to the polymer particles at room temperature for 10 minutes, and the mixture was further stirred for 30 minutes. impregnated 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 inside the yarn was lowered to 80° C., and the yarn was dried under reduced pressure.

100 parts by weight of the obtained thermoplastic elastomer, 30.2 parts by weight of tetrakis C methylene-3-(3,5-di-t-butyl-4hydroquinphenyl)propionate and bis(2,2,6,6-tetra A mixture of 0.2 parts by weight of methyl-4-piperidine) sebacate was heated at 210°C in an extruder.
The thermoplastic elastomer composition obtained by extrusion was evaluated in the same manner as in Example 1.

The results are shown in Table 3.

table BPO/Hensil Beroxide VB Divinylhensen

Claims (1)

[Claims] 1) Crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part in the presence of a crosslinking agent,
and melt-kneading to obtain a thermoplastic elastomer composition containing a crosslinked polymer and a phenolic stabilizer (A). 2) A crosslinked polymer obtained by crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part and a phenolic stabilizer (A) are melt-kneaded to form a crosslinked polymer. The method for producing a thermoplastic elastomer composition according to claim 1, characterized in that a thermoplastic elastomer composition containing the phenolic stabilizer (A) is obtained. 3) Non-crosslinked polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are melt-kneaded in the presence of a crosslinking agent and a phenolic stabilizer (A) to form a crosslinked polymer. 2. The method for producing a thermoplastic elastomer composition according to claim 1, which comprises obtaining a thermoplastic elastomer composition containing a phenolic stabilizer (A) and a phenolic stabilizer (A). 4) Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are heated to the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer in the presence of at least a crosslinking agent. The gas-phase crosslinked polymer particles obtained by contacting the particles at a temperature lower than the higher of the two are melt-kneaded in the presence of the phenolic stabilizer (A) to combine the crosslinked polymer and the phenolic stabilizer (A). The method for producing a thermoplastic elastomer composition according to claim 1, characterized in that a thermoplastic elastomer composition containing A) is obtained. 5) Crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part in the presence of a crosslinking agent,
The crosslinked polymer, the phenolic stabilizer (A), the organic thioether stabilizer (B), and the organic phosphite stabilizer (
C), one or two selected from the group consisting of hindered amine stabilizers (D) and higher fatty acid metal salts (E)
1. A method for producing a thermoplastic elastomer composition, comprising obtaining a thermoplastic elastomer composition containing one or more stabilizers. 6) A crosslinked polymer obtained by crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a phenolic stabilizer (A), and an organic thioether stabilizer (B) , an organic phosphite stabilizer (C), a hindered amine stabilizer (D), and one or more stabilizers selected from the group consisting of higher fatty acid metal salts (E) are melt-kneaded to form a thermoplastic material. 6. The method for producing a thermoplastic elastomer composition according to claim 5, which comprises obtaining an elastomer composition. 7) Non-crosslinked polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are mixed with a crosslinking agent, a phenolic stabilizer (A), and an organic thioether stabilizer (B). , an organic phosphite stabilizer (C), a hindered amine stabilizer (D) and a higher fatty acid metal salt (E). , a crosslinked polymer, a phenolic stabilizer (A), an organic thioether stabilizer (B), an organic phosphite stabilizer (C)
, a hindered amine stabilizer (D), and one or more stabilizers selected from the group consisting of higher fatty acid metal salts (E). A method for producing a thermoplastic elastomer composition according to item 5. 8) Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are heated to the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer in the presence of at least a crosslinking agent. The gas-phase crosslinked polymer particles obtained by contacting the particles at a temperature lower than the higher of the following are combined with a phenol stabilizer (A), an organic thioether stabilizer (B), and an organic phosphite stabilizer ( C), a hindered amine stabilizer (D) and a higher fatty acid metal salt (E) are melt-kneaded in the presence of one or more stabilizers selected from the group consisting of a crosslinked polymer and a phenol-based stabilizer. Stabilizer (A), organic thioether stabilizer (B), and organic phosphite stabilizer (C)
, a hindered amine stabilizer (D), and one or more stabilizers selected from the group consisting of higher fatty acid metal salts (E). A method for producing a thermoplastic elastomer composition according to item 5.