JPS5815547A - Ethylenic copolymer composition - Google Patents

Abstract

PURPOSE:To provide an ethylenic copolymer Compsn. excellent in resistance to environmental stress crack, impact at low temp. and chemicals and useful for production of hollow molding products, consisting of at least two ethyleneic copolymers obtained by copolymerization of ethylene and alpha-olefin in the presence of a specified organo aluminum catalyst. CONSTITUTION:Two types of copolymers A and B are prepared by using a solid catalyst component containing Mg, halogen and Ti and an organoaluminum compd. A is an ethylene/propylene/butene-1 copolymer having a high load melt index of 0.03-10g/10min and a density of 0.890-0.935g/cm<3> and B is a copolymer of ethylene and 1-12C alpha-olefin having an olefin content of at least 20mol%, a melt index of 10-5,000g/10min and a density of 0.890-0.940g/cm<3>. The titled compsn. consists of 80-20pts.wt. A and 20-80pts.wt. B and has a melt index of 0.02-30g/10min and a density of 0.890-0.935.

Description

[Detailed description of the invention] Purpose of the invention The present invention relates to ethylene-based copolymer compositions.

More specifically, by copolymerizing ethylene and α-olefin using a catalyst system obtained from (A) a solid catalyst component containing at least a magnesium atom, a halogen atom, and a titanium atom, and (B) an organoaluminum compound. A composition comprising at least two kinds of ethylene-based copolymers obtained, comprising: (1) a high-hard melt index of at least -(weight) of 0.03 to 10 g;
/10 minutes and the density is 0890 to 0.93597
a copolymer of ethylene and propylene and/or butene-1 which is cc and (2) at least one has a melt index of 10 to 5ooog/:+o minutes,
The α-
The copolymer is a copolymer of ethylene and the α-olefin in which the comonomer contained in the copolymer contains at least 20 moles of α-olefin having 5 to 12 carbon atoms. The present invention relates to a characteristic ethylene copolymer composition, and its purpose is to provide an ethylene copolymer composition that is superior in moldability and environmental stress cracking resistance.

BACKGROUND OF THE INVENTION Generally, the density is low (0,890 to 0.93 s, 9
/crn3) Copolymers of ethylene and α-olefins are used in a wide variety of fields because they have excellent environmental stress cracking resistance, low-temperature impact resistance, gloss and surface of molded products, and chemical resistance. However, when this copolymer with a narrow molecular weight distribution is molded under conditions of high injection speed of an extruder, the resulting molded product does not exhibit irregular surfaces, and therefore can be used for example in films, bottles, sheets, cables, etc. K, which is extruded to produce products such as pipes, is not desirable.

Furthermore, when a copolymer of ethylene and α4 olefin is molded into a film, bottle, sheet, cable, etc., it is necessary to have excellent tear strength.

Therefore, it is necessary to use a copolymer with a high molecular weight as K. When a molded article as described above is formed using a polymer having a high molecular weight, if the molecular weight distribution is narrow, the tear strength is excellent, but the moldability is not satisfactory. Furthermore, the surface of the molded product becomes irregular (shrink skin, streaks, avatars, etc. appear on the surface).

For these reasons, ethylene is homopolymerized or ethylene and α-olefin are copolymerized using a catalyst system obtained from titanium trichloride or its eutectic and an organoaluminum compound, resulting in a product with a wide molecular weight distribution and a high molecular weight. Many ethylene polymers have been proposed that not only have good moldability but also have excellent mechanical properties as described above. However, when ethylene polymers are produced using the above-mentioned catalyst system, the polymerization activity is low, so unless the catalyst residue is removed, this catalyst residue will not only cause rusting of equipment such as molding machines. , causing deterioration and discoloration of the molded product. For this reason, in order to remove the catalyst residue remaining on the polymer after polymerization, a device is required that removes the catalyst residue using a treating agent.

In recent years, catalyst systems obtained from solid catalyst components containing magnesium atoms, halogen atoms, and titanium atoms and organoaluminum compounds are highly active olefin polymerization catalysts, making it possible to remove catalyst residues after polymerization. It is also known that it can be simplified or omitted.

It has been reported that when ethylene is homopolymerized or ethylene and α-olefin are copolymerized using the above catalyst system, the molecular weight distribution is narrow, and many efforts are generally being made to widen the molecular weight distribution. However, the molecular weight distribution of the obtained ethylene polymer is not necessarily wide enough, and the moldability is not good, so it is difficult to say that it is satisfactory for molding into bottles, films, sheets, cables, pipes, etc.

l Structure of the Invention Based on the above, the present inventor has made various searches to obtain an ethylene polymer composition that does not have these problems, and has found that <A) At least magnesium atoms, halogen atoms, and titanium atoms are A composition comprising at least two types of ethylene-based copolymers obtained by copolymerizing ethylene and α-olefin using a catalyst system obtained from a solid component containing and (B) an organoaluminum compound, (1) At least one [High Lord Mel 1]
...index (hereinafter referred to as HLMIJ) is 0.0
Copolymer of ethylene and propylene and/or butene-1 [hereinafter referred to as "copolymer" 80 to 2
0 parts by weight and (2) "melt index" (hereinafter referred to as 1M, I, j) is 10 to 5000 g/]0 minutes, and the density is 08
90 to 0.940, +77 cm, and an α-olefin having at most 12 carbon atoms is used as a comonomer, and an α-olefin having 5 to 12 carbon atoms is used in the comonomer contained in the copolymer. content of at least 20
A copolymer of molti ethylene and the α-olefin [hereinafter referred to as "copolymer (■)"] M, I, characterized by 20 to 80 parts by weight, at 0.02 to 30 g/10 minutes. Yes, and the density is 0.890-0.935177cm
We have discovered that by obtaining an ethylene copolymer composition that solves all of these problems, it is possible to obtain an ethylene copolymer composition that has
We have arrived at the present invention.

Nephew Effects of the Invention As described above, each copolymer I-T LMI or M used in the production of the composition of the present invention.

Because the density and the amount and type of comonomer α-olefin used in the copolymer are all special, the resulting copolymer composition has excellent environmental stress resistance that these ethylene-based polymers have. It not only maintains crack resistance, low-temperature impact resistance, and chemical resistance, but also exhibits the following characteristics (effects).

(1) When molding the copolymer composition, moldability is good. Therefore, even when the molding temperature is low, the molding pressure does not increase. As a result, the cooling time becomes shorter and the molding cycle can be shortened.

(2) Roughness of the surface of the molded product (occurrence of rough skin, streaks, avatars, etc.) and melt fractures are unlikely to occur even when molded at high molding speeds.

(3) The molded product has good gloss.

(4) Furthermore, the environmental stress cracking resistance (hereinafter referred to as “ES”) of the molded product is
CR) is also good.

DETAILED DESCRIPTION OF THE INVENTION (A) Solid catalyst component The solid catalyst component used to produce the copolymer used in the present invention contains magnesium atoms, halogen atoms, and titanium atoms. The solid catalyst component is obtained by treating a magnesium-containing compound with a trivalent and/or tetravalent titanium compound. In this treatment, only the magnesium compound and the titanium compound may be treated once, but the magnesium compound and the electron-donating organic compound may be treated in advance, and the resulting treated product and the titanium compound may be treated. . Further, the magnesium compound, the titanium compound, and the electron donating compound may be treated (they may be treated simultaneously or separately). Furthermore, the magnesium-based compound and the electron-donating organic compound may be treated in advance, and the resulting treated product may be treated with the titanium-based compound and the electron-donating organic compound.

In addition, when processing by any one of the above-mentioned processing methods, it may be treated together with an alkyl metal compound described below, or it may be further treated with an alkyl metal compound before or after the treatment.

(1) Magnesium-based compounds Preferred magnesium-based compounds used to produce the solid component include magnesium-based compounds represented by the following formulas [Formula 11 and (It)], as well as magnesium oxide and water. Examples include magnesium oxide.

Mg(OR')rnX2Lm(I)(1
) and (11), m is o, i or 2, and n is 1 or 2. R1 and R2 are hydrogen atoms or aliphatic hydrocarbon groups having at most 16 carbon atoms, alicyclic It is a hydrocarbon group selected from the group consisting of hydrocarbon and aromatic hydrocarbon groups, and X and X2 are halogen atoms. In formula (T) and formula (II), R1
and R2 is preferably a hydrogen atom or an argyl group having at most 12 carbon atoms, and a phenyl group, and Xl and X2 are preferably chlorine, bromine, and iodine atoms, with chlorine and bromine atoms being particularly preferred. .

Among the magnesium compounds represented by formula (1), representative examples of preferred compounds include magnesium chloride, magnesium bromide, magnesium ethylate, magnesium ethylate, and hydroxymagnesium chloride. ! Among the magnesium compounds represented by the formula (■), representative examples of suitable compounds include butyl ethylmagnesium, dibutylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, phenylmagnesium chloride, ethylmagnesium bromide, butyl Magnesium bromide and (
11) Examples include phenylmagnesium bromide.

(2) Titanium compound 1. The titanium compound used to produce the solid catalyst component is a compound containing trivalent and/or tetravalent titanium. Typical examples thereof include tetravalent titanium compounds represented by formula (1), titanium metal tetrachloride (for example, metallic titanium, metallic aluminum), hydrogen, or trivalent titanium obtained by reduction using an organoaluminum compound. Examples include eutectics of titanium chloride and titanium trichloride.

Ti(OR3)t! Bar 7? (II) (In the formula 1111, l is 0 or engineering to 4, and R3 is from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having at most 12 carbon atoms. In the formula (II), R3 is preferably an alkyl group having at most 6 carbon atoms, and X3 is preferably a chlorine atom or a bromine atom, particularly preferably a chlorine atom.

(Among the tetravalent titanium compounds represented by the formula IIIj,
(12) Representative examples of suitable ones include titanium tetrachloride, methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, dimethoxytitanium dichloride, jetoxytitanium dichloride, triethoxytitanium trichloride, tetraethoxy and tetra One example is butoxytitanium.

(3) In producing the solid catalyst components such as electron-donating organic compounds, "electron-donating organic compounds, inorganic compounds, and alkyl metal compounds" (
Although these compounds (hereinafter referred to as "electron-donating organic compounds, etc.") are not necessarily required, polymerization activity etc. can be improved by using some or all of these compounds at any stage of the treatment method described below. be able to.

The electron-donating organic compound is an organic compound having at least one polar group, and is generally called a Lewis base. The electron-donating organic compound is well known as a modifier for polymerization activity, crystallinity, etc. for obtaining an olefin polymerization catalyst.

Examples include nitrites.

Furthermore, alkyl metal compounds are group Ia of the periodic table,
At least one metal from the group Hb group and
5) (which may contain any one of an alkoxy group, a halogen atom, and a hydrogen atom).

(4) Processing method The solid catalyst component can be prepared by mechanically co-pulverizing the above-mentioned magnesium compound and titanium compound or these and an electron-donating organic compound (hereinafter referred to as "co-pulverizing method"), in an inert solvent, or It can be produced by a method of contacting in the absence of an inert cocoon medium (when the treated material is liquid) (hereinafter referred to as the "contact method") or a method of combining these methods. If three or more of the above-mentioned compounds are used, all of them may be produced using one of the following two methods, but some of the above-mentioned compounds may be treated with one of the methods to produce the same product. may be processed by a method or other method.

To carry out the co-pulverization method, a commonly used method of co-pulverizing a magnesium-based compound and a titanium-based compound, or these and an electrodynamic compound to produce a solid catalyst component for olefin polymerization may be applied. . In the co-grinding method, it is necessary to reduce the material to be ground at least until it can be used. In addition, it is sufficient to co-pulverize the materials until they are almost uniform. Co-milling time is generally 5 minutes to 24 hours. Furthermore, the process is carried out in the presence of moisture and under an atmosphere of inert gas.

Further, the contact method is a method in which the reaction is carried out in an inert solvent containing no water and in the complete absence of an inert solvent. The contact temperature is between room temperature (20° C.) and 250″C, which can be achieved by treatment in an inert gas for 5 minutes to 24 hours.

The treated product obtained by the contact method is washed with an inert solvent until almost no treated product (titanium-based compound, etc.) is found in the washing solution.

The treated product thus purified can be purified by removing the inert solvent by methods such as drying under reduced pressure.

When an electron-donating organic compound is used for treatment by either the co-pulverization method or the contact method, the ratio of the electron-donating organic compound to 1 mole of the magnesium compound is usually at most 50 moles. . Moreover, the ratio of the magnesium-based compound and the titanium-based compound may be within the following range.

The content of titanium atoms in the solid component obtained as described above is generally 0.01 to 30% by weight.

Further, the content of magnesium atoms is 0.1 to 30% by weight, and the content of herogen atoms is at most 90% by weight.

(n) Organoaluminum compound Among the organoaluminum compounds used in the production of the copolymer of ethylene and α-olefin of the present invention, the general formulas of typical ones are the following formula (OV), ) expression].

Az RRR(IV) RRhe-o-ht: RR(VI A /' R,,,X+,5
In the square equation, equation (V) and equation (2), R4, R
5 and R may be the same or different, and are an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms;
Although it is a halogen atom or a hydrogen atom, at least one of them is a hydrocarbon group, and RSR, R, and R may be the same or different types and are the hydrocarbon groups. R
” is the above-mentioned hydrocarbon group, and X is a herogen atom.

Among the organoaluminum compounds shown in measurements, representative ones include trialkylaluminum such as triethylaluminum, tripropylaluminum, tributylaluminum, l-su5xylaluminum and trioctylaluminilla, and diethylaluminum octide. and alkyl aluminum hydrides such as diisobutyl aluminum hydride, diethylaluminum chloride, and diethylaluminium bromide.

Further, among the organoaluminum compounds represented by the formula (V), representative examples include alkyldialumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.

Further, among the organoaluminum compounds indicated by (capital), ethylaluminum sesquichloride is a typical example.

In producing the ethylene-α-olefin copolymer used in the present invention, the solid catalyst component and the organoaluminum compound, or a reaction product or mixture of these and an electron-donating organic compound, etc. are separately placed in a reactor (polymerization vessel). However, two or all of them may be mixed in advance, or they may be diluted in advance with an inert solvent used as a solvent in the polymerization described later.

(C) Production of copolymer (1) and copolymer (It) (
1) Amount of solid catalyst component and organic aluminum compound used In producing the copolymer (■) and copolymer (11) of ethylene and α-olefin used in the present invention, the copolymer (■) and copolymer (11) used in the present invention are obtained as described above. There are no restrictions on the amount of the solid catalyst component and the organoaluminum compound used, but the inert solvent or α-olefin used in the polymerization (when the inert solvent is not used and is used as a substitute for it) 11! per 1 mg to 1 g of solid catalyst component and 0
Use proportions of organoaluminum compound of 1 to 10 mmol can be used. Further, the amount of the organoaluminum compound used is generally in the range of 1 to 1000 mol per 1 atom of titanium metal included in the solid catalyst component.

(2) α-olefin The α-olefin used to produce the copolymer (I) and copolymer (It) of ethylene and α-olefin used in the present invention has a double bond at the terminal. It is a hydrocarbon having at most 12 carbon atoms. Representative examples include propylene, butene-1,4
-Methylpentene-1, Hegysene-1 and Octene-
1 is given.

(3) Other copolymerization conditions Copolymerization may be carried out by dissolving ethylene and α-olefin in an inert solvent, or the copolymerization may be carried out in α-olefin instead of using an inert solvent. Good too. In this case, if necessary, a molecular weight regulator (generally hydrogen) may be present.

The polymerization temperature is generally from -10'C to 300°C, and practically from room temperature (25°C) to 270°C.

In addition, as for the type of polymerization solvent and the ratio of ethylene and α-olefin used, conditions used in the production of general ethylene polymers may be applied.

Furthermore, the configuration of the polymerization reactor, the method of controlling polymerization, the method of post-treatment, the proportion of monomer (α-olefin of ethylene) and the proportion of organoaluminum compound to the inert organic solvent used in the polymerization, and the proportion of the inert organic solvent Regarding the type of catalyst, there are no limitations inherent to this catalyst system, and all known methods can be applied.

(D+ Copolymer (1) Ethylene, propylene and/or
Alternatively, in order to produce copolymer (I) by copolymerizing with butene-1, the copolymerization should be carried out in the presence of at least 10 weight units of propylene and/or butene-1 relative to ethylene in the reaction system. Bye.

Additionally, hydrogen is commonly used to control the molecular weight of the copolymer.

HLM of the copolymer obtained in this copolymer (I)
I (according to JIS K-6760, temperature is 190
°C and a load of 21.6 kg) is 0.0
3 to 10 g/10 minutes, particularly preferably 03 to 50 g/10 minutes. Also, the density is 0890~0,935 j)
/cc.

If the HLMI value of the copolymer (I) is less than 0.03 g/10 min, it becomes substantially impossible to mix with the copolymer (■) described later, which causes deterioration of the physical properties of the composition obtained by the present invention. . Also, if the HLMI value is greater than 10 g/10 min, the molecular weight distribution cannot be broadened enough to be effective in improving the moldability of the final product. Furthermore, the density of the copolymer is 0.935! If it exceeds 97 cc, environmental stress cracking resistance decreases, and transparency and low-temperature impact strength decrease, which is not preferable. In addition, copolymers with a density lower than 089 ofl/cc tend to adhere to each other and are difficult to handle.

(E) Copolymer (I) Copolymer (Copolymer (I) can be produced under almost the same conditions as Copolymer (I) except for the production method and comonomer.

This copolymer (α as a comonomer contained in Ill)
- The copolymerization ratio of the α-olefin having 5 to 12 carbon atoms in the olefin is at least 20 molar ratio, preferably 25 molar ratio or more.

The density of this copolymer (It) is 0890 to 94o,
9/Cm3 and 0.900-o94ag/cn
? is preferable, and 0.900 to 0.935 l 7c
m is preferred. Also, Mj, (JIS K-6
According to 760, the temperature is 190℃ and the load is 2.1
6 kg) is 10 to 500 (1/710 min, preferably 10 to 3000 g/10 min, particularly preferably 10 to 1000.7/IO min. Copolymer (■) HT, MT and M, I,
The ratio (Hr, M r 7M, I, ) is generally from 20 to 45.

If the density of this copolymer (n) is higher than 0940 g/cc, the final product will have less flexibility and will have poor environmental stress cracking resistance. Furthermore, it results in a decrease in transparency and low-temperature impact strength. On the other hand, if the density is 0,84) Oj)
If it is lower than /cc, the final product (molded product) will tend to be sticky and its commercial value will drop significantly.

Furthermore, if M, I, and rK of the copolymer are lower than 10,9/10 min, the molecular weight distribution cannot be effectively broadened to improve the moldability of the composition of the present invention. . On the other hand, when M, (■) exceeds 500 Gg and 710 minutes, the final product tends to become sticky. This phenomenon occurs because the density of the copolymer (■) decreases, and M,
, becomes more pronounced as , becomes higher, so M, 1. is 5000g
/ It is not desirable to exceed 10 minutes.

In the production of copolymer (1) and copolymer (II) described below, the α-olefin, catalyst system, and production method used for copolymerization may be the same or different.

(F) It can be obtained by melt-kneading at least the copolymer (■) and the copolymer (loss) of the composition.

Melt mixing can be accomplished by mixing using melt mixing machines such as open rolls, Niegoo mixers, Banbury mixers, and extruders commonly used in the field of ethylene polymers. Melt-kneading 1- In advance, these copolymers are tri-blended using a dry blender such as a Henschel mixer to create a mixture, and this mixture is melt-kneaded to obtain a more uniform composition. I can do it.

The density of the composition of the present invention obtained as described above is 08
90 to 0.935 fl/an. Further, M and T are usually 0.02 to 3o, 9/+o minutes. Furthermore, T (T, M I 7M, T,
is between 50 and 300. The proportion of the copolymer (11) in the composition of the present invention is 20 to 80% by weight, particularly preferably 25 to 75% by weight.The proportion of the copolymer (■) in the composition of the present invention If it is out of the range of 20 to 80 weight coefficients, the molecular weight distribution of the final copolymer will not be effectively broadened.

The catalyst system used in the production of the copolymer (1) and the copolymer (II) of the present invention has the following characteristics compared to a catalyst system consisting of a transition metal compound (unsupported) and an organoaluminium compound:
Its polymerization activity is high. Therefore, it is not necessary to remove the catalyst residue remaining in each copolymer, but depending on the intended use of the composition, the catalyst residue may be removed by a simple method used in this field.

The catalyst system used in the production of these copolymers is desirably highly active to the extent that the step of removing catalyst residues can be substantially omitted. Particularly desirable are catalyst systems which allow the amount of titanium oxide (Tho, . . . ) remaining in the copolymer to be at most 500 ppm.

Further, it is preferable that the molecular weight distribution of the copolymer (n) is not too broad, and if the scale of molecular weight distribution is expressed as HLMI/M, ■, HLM I 7M, 1. The value of is at most 45
A catalyst system is desirable. This is due to the stickiness of the composition obtained by the present invention (this causes a bleed phenomenon in the case of a film, and causes odor, etc. in the case of a bottle).
is due to the ultra-low molecular weight portion contained in the copolymer side. If the value is at most 45, the final product will have good physical properties. Therefore, when producing high M, I, the performance of the catalyst system used is
MI/M, 1. It is necessary to select one that falls within the above range.

As mentioned above, the copolymer composition obtained by the present invention not only has good moldability, but also has excellent environmental stress resistance, gloss, low-temperature impact resistance, transparency, etc. Therefore, it can be molded into a film shape, sheet shape, pipe shape, container shape, etc. using molding methods such as extrusion molding and blow molding that are practiced in the field of ethylene polymers.

The composition of the present invention obtained by the above-described molding method can be used in various fields, and typical applications include bottles, films, sheets, pipes, and cables.

EXAMPLES EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be explained in more detail with reference to Examples below.

In addition, in the examples and comparative examples, the density is JIS
Measured according to K-6760.

Each compound used in the production of each solid component and solid catalyst component and the production of the ethylene polymer used in each Example and Comparative Example (for example, inert solvent, ethylene, α-olefin, titanium compound, magnesium (compounds, cyclic organic compounds, ether compounds, solid components, organoaluminum compounds) were used after substantially removing water in advance. The production and copolymerization of Mapco, the solid component, and the solid catalyst component were carried out substantially in the absence of water and under a nitrogen atmosphere.

[Production of each solid component and solid catalyst component] 20.0 g of anhydrous magnesium chloride (obtained by heating and drying commercially available anhydrous magnesium chloride in a nitrogen stream at about 500° C. for 15 hours) and 1. 0 & titanium tetrachloride in a vibrating ball mill container (stainless steel,
A porcelain ball mill with a cylindrical shape and an internal volume of 111 mm and a diameter of 10 mm was placed in a container filled with 50% of its apparent volume. This has an amplitude of 6
Installed on a vibrating ball mill with a frequency of 30 Hz,
Co-pulverization was carried out for 8 hours, and a homogeneous co-pulverized product [titanium atom content: 425% by weight, magnesium atom content, IjL
210% by weight, chlorine atom content 746% by weight, hereinafter referred to as "solid component (1)"] was obtained.

Of this solid component (150g is 500ml!
After adding 1.0 ornl of toluene to the flask and suspending it, add 15ml of pyridine (as a cyclic organic compound) at room temperature (approximately 25°C) with thorough stirring.
was added dropwise over 2 hours. After dropping, turn the treatment system to 80°.
C. and stirred at this temperature for 2 hours. Then, the treatment system was cooled to almost room temperature, and the temperature was 12.5 +++
/l of diethylaluminum hydride (as an alkyl metal compound) in toluene solution (concentration 10 mol/l)
was added dropwise over 1 hour. After dropping, the treatment system was heated to 60℃.
℃ and stirred at this temperature for 2 hours.

Then, the liquid containing the product was cooled to room temperature, and the product was
- After thorough washing with hexane (until almost no titanium atoms were observed in the washing solution), drying was performed under reduced pressure at a temperature of 60° C. for 3 hours. As a result, a solid substance [hereinafter referred to as "solid catalyst component (A)"] was obtained.

Co-pulverization was carried out under exactly the same conditions as for solid component (1), except that the amount of titanium tetrachloride used in producing solid component (1) was changed by 7.0 gK, and a uniform co-pulverized product was obtained. [Titanium atom content: 6.58% by weight, magnesium atom content: 18.7% by weight, chlorine atom content: 74.7% by weight, hereinafter referred to as "solid component (2)"] was obtained.

Of this solid component (2), take 15.0.9 and 50
100m/! of n-heptane was added and suspended, and a solution of 20.6 m (! of triethylaluminum (as an alkyl metal compound) in n-hexane (concentration: 1 mol/l) was added over 2 hours with sufficient stirring at room temperature. After dropping, the treatment system was heated to 60°C and stirred at this temperature for 2 hours.Then, the treatment system was cooled to approximately room temperature, and a 200m7!
-Hebutane was added and stirred thoroughly. Then, this treatment system was allowed to stand still, and about 200 ml of supernatant was removed. A solid substance was obtained by repeating this operation four times. A solution of isoamyl ether (as an ether compound) in n-hebutane (concentration 1 mol/I) was added to this solid at 20.6 mA.
and stirred for 2 hours at room temperature. Next, this treated solution was thoroughly washed with n-heptane, and then dried under reduced pressure at a temperature of 60°C for 3 hours to obtain a solid substance (hereinafter referred to as "solid catalyst component (B)"). Ta.

Examples 1 to 6, Comparative Examples 1 to 3 [Production of (A) Copolymer (1)] The solid catalyst component (A+ or (B)) obtained in the following manner was placed in an autoclave of 1001 as the main catalyst. Add 10. (17) triethylaluminum (as a co-catalyst, organoaluminum compound) to each of them in the amounts shown in Table 1, and add 30 kl as an inert solvent.
of isobutane was charged. Then, each autoclave was closed and the internal temperature was raised to 70°C. Hydrogen was added to each autoclave, and the partial pressure of ethylene was increased to 10 kJ/
It was press-fitted until it reached Cm2 (gauge pressure). Furthermore, at the start of polymerization, α-olefin (the type is shown in Table 1) was injected as a comonomer. Ethylene and α-olefin were copolymerized while injecting ethylene to maintain the respective ethylene partial pressures, and an ethylene copolymer (11), whose HL M IF and density are shown in Table 1, was produced.

Each ethylene copolymer was dried for 3 hours under dry nitrogen fluidization at a temperature of 60°C. H of the obtained copolymer (I)
L M I and density are shown in Table 1.

[(B) Copolymer (loss production)]

In (A), the solid catalyst component (A) or (B) used in producing copolymer (1) was used in the amounts shown in Table 2, and the type of α-olefin was changed as a comonomer. Copolymerization of ethylene and α-olefin was carried out under the same conditions as in (A) except for the following conditions.

After the copolymerization was completed, drying was performed in the same manner as in (A). M, T, and density of the obtained copolymer are shown in Table 2.

Table 2 also shows the proportion of α-olefin species present in the comonomer of the copolymer (measured using C-NMR).

Copolymer (I) and copolymer (II) obtained as above were mixed in the amounts shown in Table 3 in a twin-screw extruder (manufactured by Kobe Steel, trade name: 2FC) set at 210°C.
M) was used to conduct one-arm melt crossing.

The resulting composition M, 11, HL M I 7M, I,
and density are shown in Table 3.

In each of the compositions obtained as described above, 0.02% by weight of 2,6-di-tert-butyl-p-cresol and 0.3% by weight of calcium were added as stabilizers. Pellets were prepared by adding stearate and kneading at 200'C using an extruder with an inner diameter of 40 mm.

Next, blow molding machine [Product name: Braco S■, inner diameter
45 bleached, L/D 22], a 300 cc round bottle was blow-molded. (However, blow molding was not possible in Comparative Example 3). The molding conditions are as follows: Resin temperature: 205℃ Nozzle mantle: 9MM goo 14 blades Gescrew rotation speed: 40 rotations (34) Mold cooling temperature: 20℃ Cooling time
15 seconds extrusion amount 8
．． 21 k! Nitrogen was injected into each of the round bottles obtained over 1.7 hours so that the internal pressure was 0.35 kg/cm2 ('f-pressure) K'17:r. These bottles were heated to 70°C in an aqueous solution of nonionic surfactant (concentration 10.
0% by weight), and the ESCR was measured. The results obtained are shown in Table 3. In addition, roughness on the surface of each round bottle obtained by the above-mentioned blow molding was visually observed.

The results are shown in Table 3, and the state of rough skin is shown as follows.

[Skin condition]

◎: Very good ○: Good △: Poor ×: Very bad (ESCR) 0: No cracks even after 100 hours △: 10 to 10
From the second example and comparative example, when the composition obtained by the present invention is blow-molded, the resultant blow-molded product (
For example, not only is the ESCR force of the bottle (bottle) very good, but also its surface is extremely rough, so it is clear that it is promising for use in hollow molded products in the future.

Patent applicant: Showa Denko Co., Ltd. Agent: Patent attorney Sei Kikuchi (38), 341-(37)

Claims (1)

[Claims] Ethylene and α-olefin are copolymerized using a catalyst system obtained from (A) a solid catalyst component containing at least a magnesium atom, a halogen atom, and a titanium atom, and (B) an organoaluminum compound. A composition comprising at least two types of ethylene-based copolymers obtained by Copolymer of ethylene and propylene and/or butene-1 having a diameter of .890 to 0.93597 cm 8
(2) at least one melt index is 10 to 20 parts by weight;
5000 g/l 0 minutes, and the density is 0890-0.
9 a Ojj 7 cm3, and using an α-olefin having at most 12 carbon atoms as a comonomer, the content of α-olefin having 5 to 12 carbon atoms in the comonomer contained in the copolymer is at least 20 to 80 parts by weight of a copolymer of ethylene and the α-olefin having a melt index of 002
〜30g71.0min, and the density is 0.890~0
．． An ethylene copolymer composition having a weight of 935 g/cm .