JP2001139635A - Ethylene-α-olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene-based polymer obtained by a gas phase polymerization method in the presence of a catalyst, having a small amount of a cold xylene-soluble portion (CXS component) and hardly causing problems such as blocking when processed into a film or sheet. Provided is an α-olefin copolymer. A (A) melt flow rate (MFR) obtained by a gas phase polymerization method in the presence of a catalyst: 0.3 to 5.0.
g / 10 minutes (B) Melt flow rate ratio (MFRR): 20 or more (C) Density (d): 0.910 to 0.930 g / cm ³ (D) Cold xylene soluble part (CXS) (% by weight) Is a range represented by the formula (1): 1.5 × 10 ⁻⁴ × d ⁻¹²⁵ × MFR ^0.5 + 0.3 ≧ CXS An ethylene-α-olefin copolymer represented by the formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ethylene-α-olefin copolymer obtained by a gas phase polymerization method in the presence of a catalyst. More specifically, the cold xylene soluble part (C
XS) relates to an ethylene-α-olefin copolymer having a low content.

[0002]

2. Description of the Related Art In recent years, characteristics such as easiness of handling of a packaging material using a plastic film have been evaluated, and demand for a plastic film using an ethylene resin or the like has been growing. The characteristics of the film used for the packaging material include the ease of handling of the film and the bag made of the film, and the fact that the opening of the bag is easy to open when filling the contents, especially at the time of automatic filling. It is required to have excellent blocking properties, slip properties, and the like.

[0003] As an ethylene resin used for such a film, an ethylene-α-olefin copolymer is suitably used. For example, Japanese Patent Application Laid-Open No. 52-125590
Japanese Patent Application Publication No. JP-A-2005-64131 discloses a method for producing an ethylene-α-olefin copolymer by a high-pressure ionic polymerization method in the presence of a catalyst. However, the ethylene-α-olefin copolymer obtained by the high-pressure ion polymerization method may contain a volatile component that causes smoke and gas during molding due to a process problem.

Therefore, it has been reported that an ethylene-α-olefin copolymer produced by a gas phase polymerization method is used instead of an ethylene-α-olefin copolymer produced by a high pressure ionic polymerization method. . The ethylene-α-olefin copolymer obtained by a gas phase polymerization method in which polymerization proceeds substantially in the absence of a solvent has a low content of volatile components causing smoke and gas generation during molding. There are advantages.

For example, Japanese Patent Application Laid-Open No. 54-154488 discloses a method for producing an ethylene-α-olefin copolymer produced by a gas phase polymerization method and an ethylene-α-olefin copolymer produced by the method. Is disclosed. However, the ethylene-α-olefin copolymer has a cold xylene-soluble part (CXS component) that causes blocking and the like.
Was included.

Japanese Patent Application Laid-Open No. 5-155938 discloses a method for reducing the hexane extract present in an ethylene-α-olefin copolymer produced by a gas phase polymerization method, and a method for reducing the amount of ethylene produced by the method. An α-olefin copolymer is disclosed. However, even with this method, there were many cold xylene soluble parts (CXS components).

[0007] As described above, ethylene-α-olefin copolymers generally produced by a gas phase polymerization method have many cold xylene-soluble parts (CXS components) which cause blocking and the like. It has been desired to reduce and improve the cold xylene soluble part (CXS component) in the copolymer.

Under the circumstances described above, the content of volatile components is small, there is no problem such as generation of smoke or gas during molding, and the cold xylene soluble part (CXS component) is small.
A material that does not easily cause problems such as blocking when processed into a film or sheet has been desired.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a film or sheet obtained by a gas phase polymerization method using a Ziegler-Natta catalyst, which has a small amount of cold xylene-soluble portion (CXS component). An object of the present invention is to provide an ethylene-α-olefin copolymer in which problems such as blocking are less likely to occur.

[0010]

SUMMARY OF THE INVENTION The present inventors have determined melt flow rate (MFR), density and cold xylene solubles (C
It has been found that an ethylene-α-olefin copolymer obtained by a gas phase polymerization method in which the XS component) satisfies a specific relationship achieves the object of the present invention, and has completed the present invention.

That is, the present invention provides (A) a melt flow rate (MFR) of 0.3 to 5.0 obtained by a gas phase polymerization method in the presence of a catalyst.
g / 10 minutes (B) Melt flow rate ratio (MFRR): 20 or more (C) Density (d): 0.910 to 0.930 g / cm ³ (D) Cold xylene soluble part (CXS) (% by weight) Is a range represented by the formula (1) 1.5 × 10 ⁻⁴ × d ⁻¹²⁵ × MFR ^0.5 + 0.3 ≧ CXS The formula (1) relates to an ethylene-α-olefin copolymer.

The present invention also relates to a process for producing a polymer in the presence of a catalyst.
(A) Melt flow rate (MFR) obtained by the method: 0.5 to 3.0
g / 10 minutes (B) Melt flow rate ratio (MFRR): 21 or more (C) Density (d): 0.915 to 0.930 g / cm^Three (D) Cold xylene soluble part (CXS) (% by weight) is the formula
Range shown in (1) 1.5 × 10^-Four× d^-125× MFR^0.5+ 0.3 ≧ CXS Equation (1) (E) Total melting measured by differential scanning calorimeter (DSC)
Ratio of heat of fusion of 110 ° C. or less to heat of fusion (HL11
0) is the range shown in the equation (2). −68858 × d^Two+ 124830 × d-56505 ≧ HL110 Formula (2) (F) An ethylene-α-olefin copolymer having a composition distribution variation coefficient Cx ≦ 0.85
is there. Hereinafter, the present invention will be described in detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The gas-phase polymerization method in the presence of a catalyst according to the present invention is a method for producing a polymer by proceeding polymerization in a solid phase and in a gas phase without a solvent substantially. There are no particular restrictions. Known reactors such as a vertical reactor and a horizontal reactor can be used, and they may or may not have a stirrer, or a plurality of them may be used. The manufacturing method may be a continuous type or a batch type. The polymerization pressure may be any value within the range of normal pressure to 40 kg / m ² , and the polymerization temperature may be any value within the range of 55 to 95 ° C.

The catalyst used in the present invention comprises ethylene and α
-It is a solid catalyst for olefin polymerization capable of copolymerizing olefin. Examples of the catalyst include catalyst systems described in Japanese Patent Application Nos. Hei 10-59846, Hei 10-59848, Hei 11-0665433, and the like.

A specific solid catalyst for olefin polymerization used in the present invention is a solid catalyst component (I) containing magnesium, halogen, titanium and an electron donor.

The magnesium contained in the solid catalyst component (I) is a magnesium atom of Group 2 element of the periodic table,
Titanium is a titanium atom of Group 4 element of the periodic table.

The halogen contained in the solid catalyst component (I) is a halogen belonging to Group 17 of the periodic table.
It is a chlorine atom, a bromine atom, an iodine atom or the like, and preferably a chlorine atom.

The electron donor contained in the solid catalyst component (I) is an organic compound containing at least one of an oxygen atom, a sulfur atom, a nitrogen atom and / or a phosphorus atom, for example, amines, sulfoxides, Examples thereof include ethers and esters, and are preferably ethers or esters.

Examples of the ethers include dialkyl ethers, such as diethyl ether, dibutyl ether, and tetrahydrofuran. Preferably, they are dibutyl ether and tetrahydrofuran.

Examples of the esters include saturated aliphatic carboxylic esters, unsaturated aliphatic carboxylic esters, alicyclic carboxylic esters, and aromatic carboxylic esters. For example, ethyl acetate, ethyl acrylate, ethyl methacrylate, butyl benzoate, dibutyl succinate, dibutyl malonate, dibutyl maleate, dibutyl itaconate, di-n-butyl phthalate, diisobutyl phthalate, di-2 phthalate -Ethylhexyl, di-n-octyl phthalate and the like are preferable, and di-2-ethylhexyl phthalate and di-n-octyl phthalate are preferable.

As the solid catalyst component (I), preferably,
A contact product obtained by contacting a solid catalyst component precursor containing magnesium, titanium and a hydrocarbyloxy group with a halogen compound of a Group 14 element and an electron donor; Are brought into contact with each other.

As a precursor of a solid catalyst component containing magnesium, titanium and a hydrocarbyloxy group, preferably, in the presence of an organosilicon compound having a Si—O bond, a compound of the general formula Ti (OR ¹ ) _a X _{4- a} (wherein, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and a represents a number satisfying 0 <a ≦ 4). Is a solid product containing a trivalent titanium atom obtained by reduction with

Examples of the organosilicon compound having a Si—O bond include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, with tetrabutoxysilane being preferred.

General formula Ti (OR ¹ ) _a X _4-a (wherein, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a satisfies 0 <a ≦ 4. As the hydrocarbon group (R ¹ ) of the titanium compound represented by the following formula:
Examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group, and a butyl group is preferable.

The halogen atom (X) of the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a includes a chlorine atom,
Examples thereof include a bromine atom and an iodine atom, and a chlorine atom is preferable. A is 1, 2, 3, or 4, and preferably 4.

Examples of the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a include, but are not limited to, butoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxychlorotitanium, and tetrabutoxytitanium. It is titanium tetrabutoxy.

Examples of the organic magnesium include a Grignard compound having an Mg-carbon bond. For example, methylchloromagnesium, ethylchloromagnesium, propylchloromagnesium, butylchloromagnesium and the like can be mentioned, and butylchloromagnesium is preferable.

Examples of the halogen compound of the Group 14 element to be brought into contact with the solid catalyst precursor include a halogen compound of a carbon atom or a silicon atom, and are preferably of the general formula SiR
(Wherein, R ² is a hydrocarbon group having 1 to 20 carbon atoms, X is .b represents a halogen atom is a number satisfying _{^{0 <b ≦ 4) 2 4}} -b X b is represented by Is a halogen compound of a silicon atom.

The number in the general formula SiR ² _4-b X b (wherein, R ² has carbon atoms of 1 to 20 hydrocarbon group, X is satisfying the .b is 0 <b ≦ 4 represents a halogen atom Represents a hydrocarbon group (R ² ) of the silicon compound represented by, for example, a methyl group, an ethyl group, a propyl group and a butyl group, and is preferably a butyl group.

[0030] As the halogen atom of the general formula SiR ² _4-b X _b in the silicon compound represented by (X) is chlorine atom, a bromine atom, an iodine atom and the like, preferably a chlorine atom. In addition, b includes 1, 2, 3, and 4, and is preferably 3 or 4.

The silicon compound represented by the general formula SiR ² _{4-b Xb} includes, for example, butyltrichlorosilane, dibutyldichlorosilane, trichlorobutylsilane and tetrachlorosilane, and is preferably tetrachlorosilane.

Examples of the electron donor to be brought into contact with the solid catalyst precursor include those described above.

The contact product obtained by contacting the solid catalyst component precursor with a halogen compound of Group 14 element and an electron donor is further contacted with a contact product obtained by contacting with a contact compound obtained by contacting a halogen compound of Group 14 element with an electron donor. Examples thereof include a bromine atom and an iodine atom, and a chlorine atom is preferable.

Examples of the compound having a Ti-halogen bond include tetrachlorotitanium, trichlorobutoxytitanium, dichlorodibutoxytitanium, chlorotributoxytitanium and the like, with tetrachlorotitanium being preferred.

The ethylene-α-olefin copolymer of the present invention is formed on the solid catalyst component (I) by contacting the solid catalyst component (I) and the organoaluminum with ethylene and α-olefin.

In the gas phase polymerization method in which substantially no solvent is present, the steps of recovering and purifying the solvent can be omitted, and when forming and processing a film using the obtained ethylene-α-olefin copolymer, fuming, The content of a volatile component causing gas generation can be reduced.

The ethylene-α-olefin copolymer of the present invention is a copolymer of ethylene and one or more α-olefins having 3 to 12 carbon atoms. Examples of the α-olefin include propylene, butene-1, pentene-
1,4-methyl-1-pentene, hexene-1, octene-1, decene-1 and the like, preferably propylene, butene-1, hexene-1, octene-1;
More preferably, they are butene-1 and hexene-1.

The ethylene-α-olefin copolymer of the present invention includes, for example, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methyl-
1-pentene copolymer, ethylene-hexene-1 copolymer, ethylene-octene-1 copolymer, etc., and preferably ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene -1 copolymer,
Ethylene-octene-1 copolymer, more preferably ethylene-butene-1 copolymer, ethylene-hexene-1
It is a copolymer.

The α-olefin content of the ethylene-α-olefin copolymer of the present invention is preferably 0.5 to 3
0 mol%, particularly preferably 1.0 to 20 mol%.

The melt flow rate (MFR) of the ethylene-α-olefin copolymer of the present invention is from 0.3 to 5.0.
g / 10 min, preferably 0.5 to 3.0 g / 10 min.
Min, particularly preferably 0.7 to 2.5 g / 10 min.

Melt flow rate (MFR) is 0.3 g
If it is less than / 10 minutes, when it is applied to a film, the extrusion load during the film forming process becomes excessively large, and problems such as generation of melt fracture may easily occur.
If the time exceeds 10 minutes, the mechanical properties of the film may be impaired, or the film-forming stability may be insufficient.

[0042] The melt flow rate ratio (MFRR) of the ethylene-α-olefin copolymer of the present invention is 20 or more, preferably 21 or more.

When the melt flow rate ratio (MFRR) is 20
If it is less than 5, when applied to a film, the extrusion load at the time of film forming processing becomes excessive, and problems such as occurrence of melt fracture may easily occur.

The density of the ethylene -α- olefin copolymer of the present invention is a 0.910~0.930g / cm ^3, preferably 0.915~0.930g / cm ^3, particularly preferably 0.918 is a ~0.927g / cm ^3.

[0045] In the density is less than 0.910 g / cm ^3, such as insufficient blocking resistance deteriorates and stiffness occur as a result of applying to the film, may handling properties of the film is deteriorated, 0.930 g / cm ³ If the ratio exceeds, the gloss and transparency of the film may be insufficient.

The cold xylene soluble part (CXS) (% by weight) of the ethylene-α-olefin copolymer of the present invention has a range of 1.5 × 10 ⁻⁴ × d ⁻¹²⁵ × MFR represented by the formula (1). ^0.5 + 0.3 ≧ CXS Formula (1), preferably 1.5 × 10 ⁻⁴ × d ⁻¹²⁵ × MFR ^0.5 ≧ CXS Formula (3)

The cold xylene soluble part (CXS) is determined by the formula (1)
If the upper limit is exceeded, the film may have insufficient blocking resistance and slipperiness. Note that the lower limit is 0 or more.

The ratio of the heat of fusion of 110 ° C. or less (HL11) to the total heat of fusion of the ethylene-α-olefin copolymer of the present invention measured by a differential scanning calorimeter (DSC).
0) is preferably in the range represented by the formula (2). −68858 × d ² + 124830 × d−56505 ≧ HL110 Equation (2)

When the HL110 exceeds the expression (2), when applied to a film, the film may be inferior in stiffness, rigidity and blocking resistance. In addition, 110 with respect to the total heat of fusion measured by the differential scanning calorimeter (DSC).
The rate of heat of fusion below ℃ (HL110) is ethylene-α
-Indicates the rigidity of the olefin copolymer;
It can be obtained from measurement. The smaller this value is, the higher the rigidity of the ethylene-α-olefin copolymer is.

The composition distribution variation coefficient Cx is defined as ethylene-α-
It shows a measure of the composition distribution of an olefin copolymer and can be determined by the following equation. Cx = σ / SCB _ave σ: Standard deviation of composition distribution SCB _ave : Average value of the number of short-chain branches per 1000 carbon atoms The smaller this value is, the narrower the composition distribution is.

The composition distribution variation coefficient Cx of the ethylene-α-olefin copolymer of the present invention is preferably 0.85 or less, more preferably 0.83 or less. When the composition distribution variation coefficient Cx exceeds 0.85, when the composition is applied to a film, the strength of the film may be reduced, and the blocking resistance and the transparency may be poor.

[0052]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Sample preparation (melt flow rate (MF
R), Melt flow rate ratio (MFRR) and sample for density measurement) The sample for melt flow rate (MFR), melt flow rate ratio (MFRR) and density measurement was previously extruded at 170 to 250 ° C using an extruder. The sample was prepared by melt extrusion.

The evaluation was performed according to the following method. (1) Smoke evaluation A T-die was attached to a φ30 mm extruder manufactured by Union Co., Ltd., and the temperature of each heater was set to 290 ° C. Each resin is extruded from the extruder at a screw rotation speed of 100 rpm,
Smoke generated in one minute was collected, and the amount of generated smoke was measured using a digital dust meter MODEL3411 manufactured by Kanomax Japan Co., Ltd. The value obtained by averaging the results obtained by repeating this process five times was defined as the smoke emission amount, and was expressed in units of CMP (1 CMP).
= 0.01 mg / m ³ , where φ0.3 μm in terms of stearic acid particles). A smaller value indicates a smaller amount of smoke.

(2) Melt flow rate (MFR) A method specified in JIS K 6760 was used. The test was performed at a load of 2.16 kg and a temperature of 190 ° C.

(3) Melt flow rate ratio (MFRR) According to a method specified in JIS K 6760. The value obtained by dividing the MFR value obtained at a load of 2.16 kg and a temperature of 190 ° C. by the MFR value obtained at a load of 21.6 kg and a temperature of 190 ° C. was determined as a melt flow rate (MFRR).

(4) Density (d) According to the method specified in JIS K 6760.

(5) Cold Xylene Soluble Part (CXS) Code of federal regula in the United States
ions, Foodand Drugs Admin
The method specified in §175.1520 of the instruction was followed.

(6) Ratio of heat of fusion of 110 ° C. or less to total heat of fusion measured by differential scanning calorimeter (DSC) (HL110): 110 ° C. or less of total heat of fusion measured by differential scanning calorimeter (DSC) Heat of fusion ratio (HL110)
Is a differential scanning calorimeter DSC-7 type device manufactured by Perkin Elmer Co., Ltd., and about 5 mg of a sample is packed in an aluminum pan and heated to 150 ° C. at 100 ° C./min.
At 5 ° C / min to 40 ° C.
After holding at 0 ° C. for 5 minutes, the temperature was raised to 150 ° C. at 5 ° C./min, and the melting curve was measured. The point at which the melting curve returned to the high-temperature base line and the point at 40 ° C. in the melting curve were connected with a straight line. The heat of fusion is determined from the total area of the portion surrounded by this straight line and the melting curve, the total area is divided into two at 110 ° C., and the area ratio of the portion at 110 ° C. or less to the total area is calculated as the heat of fusion at HL 110 ).

(7) Composition distribution variation coefficient Cx Measured using a multifunctional LC manufactured by Tosoh Corporation. The ethylene-α-olefin copolymer used for the measurement was heated to a predetermined temperature of 145.
Dissolve (concentration: 0.2 g / 20 ml) in ortho-dichlorobenzene (ODCB) solvent heated to 0 ° C., put into a column filled with sea sand in a column oven, and raise the temperature of the oven at a rate of 40 ° C./60 minutes. Cool down to 125 ° C.
The temperature was lowered from ℃ to -15 ° C over 14 hours. Subsequently, the temperature was raised at a rate of 10 ° C./60 minutes, raised to 125 ° C., and the relative concentration and branching degree of the copolymer flowing out during that time were measured by FT-IR connected to a column. Data is 1
Seven points were taken at equal intervals between 0 ° C. The temperature was raised to the final temperature while obtaining the relative concentration of the copolymer flowing out at each set temperature and the degree of branching (SCB) per 1000 main chain carbons. However, the relationship between each elution temperature and the degree of branching is
Equation (4) was followed regardless of the type of comonomer. Also,
No elution was performed at the temperature where SCB was negative. SCB = −0.7322 × elution temperature (° C.) + 70.68 Formula (4) A composition distribution curve is obtained from the obtained relative concentration and branching degree, and from this curve, the average short-chain branching degree per 1000 carbons (S
CBave) and the standard deviation (σ) of the composition distribution were obtained to obtain a composition distribution variation coefficient Cx representing the width of the distribution. Average short-chain branching degree (SCBave) = ΣN (i) · W (i) Equation (5) N (i): short-chain branching degree at i-th data sampling point W (i): at i-th data sampling point Relative concentration, ie, ΣW (i) = 1 Standard deviation of composition distribution (σ) = {Σ (N (i) -SCBave) ² · W (i)} ^0.5 Equation (6)

(8) Blocking After the formed film was conditioned at 23 ± 2 ° C. and 50 ± 5% RH for 24 hours or more, the two formed films were laminated.
After bonding for 7 days in an oven adjusted to 40 ° C. under a load of 800 g / cm ² , using a Mackenzie-type single fiber tensile tester modified type blocking measurement device manufactured by Shimadzu Corporation, test piece size 10 cm × 22 cm, peeling Area 50c
The test pieces were fixed to upper and lower clamps under the conditions of m ² and a peeling load speed of 20 g / min, and the load when the two films were completely peeled was recorded while rotating the driving motor to move the peeling load. This load is g / 50 cm ²
The unit was expressed as an index of blocking. The smaller this value is, the better the blocking resistance is.

Example 1 (1) Synthesis of Solid Catalyst Component (I) After replacing a 200 L SUS reaction tank equipped with a stirrer with nitrogen, 80 L of hexane, 20.6 kg of tetraethoxysilane, and tetrabutoxy 2.2 kg of titanium was charged to 5 ° C. Next, 50 L of butylmagnesium chloride (2.1 mol / L of dibutyl ether solvent) was added dropwise with stirring over 4 hours while maintaining the temperature at 5 ° C.
After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour and further at 20 ° C. for 1 hour, and then filtered and washed three times with 70 L of toluene, then 63 L of toluene and phenyltrichlorosilane.
4 kg, 9.5 kg of diisobutyl phthalate, and 1
The reaction was performed at 05 ° C for 2 hours. Then, after filtration and washing three times with 90 L of toluene, 63 L of toluene was added, the temperature was raised to 70 ° C., and 13.0 kg of TiCl ₄ was added.
The reaction was performed at 105 ° C. for 2 hours. Then, solid-liquid separation,
Washing was performed 6 times with 95 L of toluene at 95 ° C., and twice with 90 L of hexane at room temperature, and dried to obtain 15.2 kg of a solid catalyst component (I) having excellent powder properties. The obtained solid product contained 1.17 wt% of Ti.

(2) Preliminary polymerization of solid catalyst component After replacing the autoclave with an internal volume of 210 L with stirring with nitrogen, the solid catalyst component obtained in the above (1) was replaced with 1.515.
kg, 98.4 L butane, triethylaluminum3.
2337 moles were charged. Then set the temperature to 40 ° C,
Hydrogen was added until the total pressure became 0.928 MPa, and ethylene was further added at a rate of 2.44 g / g solid catalyst component · hr / g solid catalyst component / hr. After completion of the reaction, butane was flushed to obtain 28.55 kg of a prepolymerized catalyst.

(3) Polymerization Using the above prepolymerized catalyst, random copolymerization of ethylene and butene-1 was carried out using a continuous fluidized-bed gas-phase polymerization facility. After raising the temperature of the polymerization vessel to 90 ° C., 80 kg of polyethylene powder previously dried under reduced pressure was charged as a dispersant, and then the ethylene / butene-1 / hydrogen molar ratio was 63/27/1.
The mixed gas adjusted to be 0 under a pressure of 2 MPa,
It was circulated in the polymerization tank so as to have a flow rate of 0.34 m / sec. When the molar ratio of ethylene / butene-1 / hydrogen deviated from the set value, the molar ratio was adjusted by adding. Then 46.7 mmol of triethylaluminum /
hr, the preliminary polymerization catalyst was charged into the tank at a flow rate of 0.73 g / hr, and fluidized-bed gas-phase copolymerization of ethylene / butene-1 was continuously performed for 24 hours. The obtained polymer had good particle properties and hardly any adhesion to the polymer wall.
The amount of polymer produced per catalyst (polymerization activity) was 2810
It was 0 g polymer / g solid catalyst component. Table 2 shows the physical properties of the obtained ethylene-butene-1 copolymer.

Next, 1000 ppm of calcium stearate and n-type were added to the obtained ethylene-butene-1 copolymer.
Octadecyl-3- (4'-hydroxy-3,5'-di-t-butylphenyl) propionate 1000 pp
m, tetrakis (2,4 di-tert-butylphenyl) 4,4'biphenylenediphosphonite 800p
After adding pm, the product was manufactured using a 20 mmφ extruder manufactured by Tanabe Plastics Co., Ltd., a die 25 mmφ, and a lip 2.0 mm inflation molding machine under the conditions of a processing temperature of 180 to 190 ° C., an extrusion rate of 1.2 kg / hr and a blow ratio of 1.8. The film was formed into a film having a thickness of 20 μm, and the blocking value was measured. The results are shown in Table 2.

Examples 2 to 7 Using a prepolymerized catalyst obtained using the same solid catalyst component (I) as in Example 1, except for the conditions shown in Table 1, the same gas phase weight as in Example 1 was used. An ethylene-butene-1 copolymer was produced by a synthetic method, and a film was obtained in the same manner as in Example 1. Table 2 shows their physical properties and blocking values.

Comparative Examples 1 to 5 Ethylene obtained by gas phase polymerization shown as a comparative example
The butene-1 copolymer is shown below. Comparative Example 1: Sumikasen-LC manufactured by Sumitomo Chemical Co., Ltd.
A1010 Comparative Example 2: Sumikasen-LF manufactured by Sumitomo Chemical Co., Ltd.
S150A Comparative Example 3: Sumikasen-LF manufactured by Sumitomo Chemical Co., Ltd.
S140A Comparative Example 4: Sumikasen-LF manufactured by Sumitomo Chemical Co., Ltd.
S150C Comparative Example 5: Sumikasen-LF manufactured by Sumitomo Chemical Co., Ltd.
S240A Using these ethylene-butene-1 copolymers, a film was obtained in the same manner as in Example 1. Table 2 shows their physical properties and blocking values.

Examples 1 and 2 having the same MFR and the same density
When Comparative Examples 1 and 2 are compared, Examples 1 and 2 have a smaller amount of cold xylene-soluble portion (CXS), a smaller coefficient of variation in composition distribution (Cx), and a smaller blocking value. That is, it can be seen that the examples are excellent in blocking resistance of the ethylene-butene-1 copolymer when formed into a film.

Comparing Example 4 with Comparative Example 3, Example 5 and Comparative Example 4, and Example 7 and Comparative Example 5 in which the values of the MFR and the density are almost the same, the Example shows that the cold xylene-soluble portion is (C
XS), the composition distribution variation coefficient (Cx) is small,
Also, the blocking value is small. That is, it can be seen that the examples are excellent in blocking resistance of the ethylene-butene-1 copolymer when formed into a film.

From the comparison of the ratio of the heat of fusion at 110 ° C. or less (HL110) to the total heat of fusion measured by a differential scanning calorimeter (DSC) and the calculated value of equation (2 ′), Examples 1 to 7 and Comparative Examples It can be seen that 1 to 5 satisfy the formula (2). On the other hand, Examples 1 to 7 satisfy the formula (1) from comparison between the cold xylene soluble part (CXS) and the calculated value of the formula (1 ′). However, it can be seen that Comparative Examples 1 to 5 are not satisfied.

Example 8, Comparative Example 6 Evaluation of the amount of volatile components (smoke) The ethylene-butene-1 copolymer obtained by the gas phase polymerization method of Example 8 (the ethylene-butene-1 used in Example 7)
Comparison of the amount of volatile components (smoke emission) between the ethylene-butene-1 copolymer (Sumikasen-L CL2060 manufactured by Sumitomo Chemical Co., Ltd.) obtained by the high-pressure ionic polymerization method of Comparative Example 6 and the ethylene-butene-1 copolymer obtained in Comparative Example 6. Was performed. This sample was evaluated by adding 0.05 parts by weight of hydrotalcite which is unlikely to become a volatile component (smoke) as a neutralizing agent.
Table 3 shows the physical properties and the results of the smoke emission evaluation. The ethylene-butene-1 copolymer obtained by the gas-phase polymerization method of Example 8 (the same as the ethylene-butene-1 copolymer used in Example 7) was obtained by the high-pressure ionic polymerization method of Comparative Example 6. Compared to the obtained ethylene-butene-1 copolymer, the amount of volatile components (smoke emission) during molding was small, indicating that the handling during molding was excellent.

From the comparison of the ratio of the heat of fusion at 110 ° C. or less (HL110) to the total heat of fusion measured by a differential scanning calorimeter (DSC) and the calculated value of the equation (2 ′), Example 8 shows the equation (2). It can be seen that Comparative Example 6 was not satisfied. That is, when the film of Example 8 was formed into a film, the film had good stiffness and rigidity, and good blocking resistance.
Indicates that the film has insufficient stiffness and rigidity, and blocking resistance.

[0073]

[Table 1] Polymerization conditions

[0074]

[Table 2] * 1: Formula (1 ′) = 1.5 × 10 ⁻⁴ × d ^{− 125} × MFR ^0.5 +
0.3 * 2: formula (2 ') = - 68858 × d 2 + 124830 × d
-56505

[0075]

[Table 3]

[0076]

As described above, according to the present invention, the content of volatile components is low and the content of cold xylene solubles (CXS) is low.
Can provide an ethylene-α-olefin copolymer having a small amount of, and a low content of cold xylene-soluble matter (CXS), so that it is possible to provide a good film having particularly excellent properties such as blocking resistance. In addition, the film can be optimally used as a packaging material for foods, fibers, pharmaceuticals, fertilizers, miscellaneous goods, industrial supplies, etc., and as an agricultural coating and an architectural coating, by taking advantage of its excellent properties.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J011 MA15 MA16 MA19 MB01 MB03 4J028 AA02A AB02A AC04A AC05A AC06A BA01B BA02A BB00A BB01B BC06A BC13A BC15B CA20A CB27A CB30A CB43A CB44A CB47A EB08 CB47A CB92 4J100 AA02P AA03Q AA04Q AA07Q AA16Q AA17Q AA19Q AA21Q CA04 DA11 DA22 DA40 DA43 FA09 FA22 JA58

Claims (2)

[Claims] (1) A melt flow rate (MFR) obtained by a gas phase polymerization method in the presence of a catalyst: 0.3 to 5.0.
g / 10 minutes (B) Melt flow rate ratio (MFRR): 20 or more (C) Density (d): 0.910 to 0.930 g / cm ³ (D) Cold xylene soluble part (CXS) (% by weight) Is a range represented by the formula (1): 1.5 × 10 ⁻⁴ × d ⁻¹²⁵ × MFR ^0.5 + 0.3 ≧ CXS Formula (1) 2. The ethylene-α-olefin copolymer according to claim 1, wherein (E) is added to (A) to (D), and (E) 110 to the total heat of fusion measured by a differential scanning calorimeter (DSC). C. or below (HL11
0) satisfies the following equation (2): −68858 × d ² + 124830 × d−56505 ≧ HL110 Equation (2) (F) Composition distribution variation coefficient Cx ≦ 0.85. Ethylene described
α-olefin copolymer.