JP2005105036A - Olefinic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefinic resin composition which has excellent extrusion moldability and can give films having excellent transparency, heat retainability and strength. <P>SOLUTION: This olefinic resin composition is characterized by comprising (A) 70 to 99.9 wt. % of an ethylene-α-olefin copolymer characterized by having a Q value of ≥3 calculated from a chain length distribution obtained by a GPC measurement, having a melt flow rate (MFR) and a 190°C melt tension (MT: unit is cN) which satisfy the following expression: 2×MFR<SP>-0.59</SP><MT<20×MFR<SP>-0.59</SP>(1), and having an intrinsic viscosity ([η]; unit is dL/g) and the above-mentioned MFR which satisfy the following expression: 1.02×MFR<SP>-0.094</SP><[η]<1.50×MFR<SP>-0.156</SP>(2), and (B) 30 to 0.1 wt. % of an inorganic compound salt comprising a cation containing a divalent metal and an anion containing silicon, phosphorus and boron. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an olefin resin composition excellent in extrusion processability, and relates to an olefin resin composition capable of producing a film excellent in transparency, heat retention and strength.

  In recent years, the demand for resins used outdoors, such as automobile materials, building materials, and agricultural materials, has increased dramatically. For example, as an agricultural material, the film for agriculture used for covering of facilities, such as a house and a tunnel, is mentioned. As agricultural films, polyolefin resin films such as polyvinyl chloride films and polyolefin resin films (for example, polyethylene films and ethylene / vinyl acetate copolymer films) have been widely used. Recently, polyolefin resin films, which are lightweight and hardly generate toxic gases during incineration, have been widely used for gardening. In addition, in order to express good crop growth in facility horticulture, the performance required for these agricultural films includes transparency for good sunlight transmission in the daytime and a house that prevents temperature drop especially at night. It is important to achieve both heat retention and keep the temperature inside the facility high. In addition, strength that can guarantee these performances over a long period of time, that is, impact resistance strength and friction resistance strength in the case of a film is extremely important.

As a resin composition used to produce a film with improved heat retention, transparency, impact resistance, and scratch resistance, an ethylene-based resin specified by temperature rise elution fractionation and gel permeation chromatography characteristics A film made of an ethylene resin composition with an inorganic compound containing a specific atom is disclosed. (For example, see Patent Document 1)

Japanese Patent Laid-Open No. 10-72539

However, the film obtained from the above resin composition does not satisfy all of heat retention, transparency, impact resistance, and scratch resistance. In addition, the ethylene resin composition has various problems such as poor processability, that is, high extrusion torque, low melt tension, poor extrusion processability, and easy appearance deterioration called melt fracture. have.

The present invention provides an olefin resin composition capable of producing a film excellent in extrusion processability and excellent in transparency, heat retention and strength.

That is, the present invention is an ethylene-α-olefin copolymer comprising a component (A): a structural unit derived from ethylene and a structural unit derived from an α-olefin having 4 to 20 carbon atoms, and gel permeation The Q value calculated from the chain length distribution obtained by chromatographic measurement is 3 or more, the melt flow rate (MFR; the unit is g / 10 minutes) and the melt tension at 190 ° C. (MT; the unit is cN). And the intrinsic viscosity ([η]; the unit is dl / g) and the MFR satisfy the relationship of the following formula (2): 70 to 99.9% by weight of an ethylene-α-olefin copolymer
2 x MFR ^-0.59 <MT <20 x MFR ^-0.59 Formula (1)
1.02 × MFR ^−0.094 <[η] <1.50 × MFR ^−0.156 Formula (2)
Component (B): Inorganic compound represented by the following formula (A), (I) or (U) 30 to 0.1% by weight
An olefin-based resin composition comprising:
_{^{[{Mg y5 M 2+ y6}}} 1-β Al β (OH) 2] β + · [A n- zβ / n · fH 2 O] β- ( A)
(Wherein M ²⁺ is, Zn, ^{.A n-} is showing a divalent metal ion of at least one of Ca and Ni .Beta showing a n-valent anion, y5, y6 and b satisfy the following conditions.)
0 ≦ β <0.5, y5 + y6 = 1, y5 ≦ 1, y6 <1, 0 ≦ f <2.
[{Mg _y1 M ²⁺ _y2 } _1-x Al _x (OH) ₂ ] ^{x +} · [(A) _z1 · (B) _z2 · bH ₂ O] ^x− (A)
( ^Wherein M ²⁺ represents one or more divalent metal ions selected from Zn, Ca, and Ni. A represents at least one of silicon-based, phosphorus-based, and boron-based oxygenate ions. B represents at least one anion other than A, and x, y1, y2, z1, z2, and b satisfy the following conditions.)
0 <x ≦ 0.5, y1 + y2 = 1, y1 ≦ 1, y2 <1, 0 <z1, 0 ≦ z2, 0 ≦ b <2.
[{Li _y3 G ²⁺ _y4 } Al ₂ (OH) ₆ ] ^{α +} · [(C) _z3 · (D) _z4 · dH ₂ O] ^α− (U)
(In the formula, G ²⁺ represents one or more divalent metal ions selected from Mg, Zn, Ca, and Ni. C represents at least one of silicon-based, phosphorus-based, and boron-based multimeric oxygenate ions. D represents at least one anion other than C, and α, y3, y4, z3, z4, and d satisfy the following conditions.)
α = y3 + 2y4, 0 <y3 ≦ 1, 0 ≦ y4 ≦ 1, 0.5 ≦ (y3 + y4) ≦ 1, 0 <z3, 0 ≦ z4, 0 ≦ d <5

The olefin resin composition of the present invention has excellent extrusion processability, and the film obtained by molding the olefin resin composition has transparency, heat retention, punching impact resistance, friction resistance, etc. It has excellent strength and is suitably used as an agricultural film.

The ethylene-α-olefin copolymer used for the component (A) forming the olefin resin composition of the present invention is derived from a structural unit derived from ethylene and an α-olefin having 4 to 20 carbon atoms. It is an ethylene-α-olefin copolymer containing structural units.

The structural unit derived from ethylene is a unit derived from ethylene as a monomer and contained in the ethylene-α-olefin copolymer.

The structural unit derived from an α-olefin having 4 to 20 carbon atoms is a unit derived from an α-olefin having 4 to 20 carbon atoms as a monomer and contained in an ethylene-α-olefin copolymer. is there. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like. More preferable examples include 4-methyl-1-pentene and 1-hexene.

The α-olefin having 4 to 20 carbon atoms may be a combination of two or more. For example, 1-butene and 4-methyl-1-pentene, 1-butene and 1-hexene, 1-butene and 1-butene Examples include octene, 1-butene and 1-decene. More preferably, 1-butene and 4-methyl-1-pentene, 1-butene and 1-hexene are mentioned.

Content of the structural unit induced | guided | derived from ethylene is 50 to 99 weight% with respect to the total weight (100 weight%) of an ethylene-alpha-olefin copolymer. Content of the structural unit induced | guided | derived from a C4-C20 alpha olefin is 1-50 weight% with respect to the total weight (100 weight%) of an ethylene-alpha-olefin copolymer.

The ethylene-α-olefin copolymer in the present invention is not limited to the structural unit derived from ethylene and the structural unit derived from an α-olefin having 4 to 20 carbon atoms. A structural unit derived from another monomer other than olefin may be contained. Examples of other monomers include conjugated dienes (for example, butadiene and isoprene), non-conjugated dienes (for example, 1,4-pentadiene), acrylic acid, acrylic acid esters (for example, methyl acrylate and ethyl acrylate), and methacrylic acid. , Methacrylate esters (for example, methyl methacrylate and ethyl methacrylate), vinyl acetate and the like.

The ethylene-α-olefin copolymer in the present invention is preferably a copolymer of ethylene and an α-olefin having 5 to 10 carbon atoms, or ethylene, 1-butene and an α-olefin having 5 to 10 carbon atoms. It is a copolymer, more preferably a copolymer of ethylene and an α-olefin having 6 to 10 carbon atoms, or a copolymer of ethylene, 1-butene and an α-olefin having 6 to 10 carbon atoms. .

The ethylene-α-olefin copolymer in the present invention has a melt flow rate (MFR; the unit is g / 10 minutes) and a melt tension at 190 ° C. (MT; the unit is cN) represented by the following formula ( It satisfies the relationship 1).
2 x MFR ^-0.59 <MT <20 x MFR ^-0.59 Formula (1)

It is known that an ethylene-α-olefin copolymer generally has an increased MFR and fluidity, that is, a melt viscosity is lowered and a melt tension is lowered. The ethylene-α-olefin copolymer of the present invention is considered to have a polymer structure such as a long-chain branch, and has an appropriate range of melt tension higher than that of a normal ethylene-α-olefin copolymer, In order to satisfy the relationship of formula (1), the extrusion processability is excellent. When the melt tension is too low and the relationship of 2 × MFR ^−0.59 <MT is not satisfied in the formula (1), the extrusion processability may be deteriorated, and the melt tension is too high, in the formula (1). When MT <20 × MFR ^−0.59 is not satisfied, high-speed take-up processing may be difficult.

As a relational expression satisfied by the ethylene-α-olefin copolymer in the present invention,
2.2 × MFR ^-0.59 <MT <15 × MFR ^-0.59
And more preferably
2.5 × MFR ^-0.59 <MT <10 × MFR ^-0.59
It is.

The melt flow rate (MFR; unit is g / 10 minutes) in the above formula (1) is a load of 21.18 N (2.16 Kg) at 190 ° C. according to the method defined in JIS K7210-1995. It is a measured value.

The melt tension (MT; unit is cN) in the above formula (1) is 190 ° C. and extrusion rate is 5.5 mm / min using a melt tension tester sold by Toyo Seiki Seisakusho. When a molten resin strand is extruded from an orifice having a diameter of 2.09 mmφ and a length of 8 mm with a piston, and the strand is wound up at a rotational speed of 40 rpm / min using a roller having a diameter of 50 mm, the strand This is the tension value just before the break.

In the ethylene-α-olefin copolymer in the present invention, the intrinsic viscosity ([η]; the unit is dl / g) and the MFR satisfy the relationship of the following formula (2).
1.02 × MFR ^−0.094 <[η] <1.50 × MFR ^−0.156 Formula (2)

It is known that an ethylene-α-olefin copolymer generally has an increased MFR and an increase in fluidity, that is, a decrease in melt viscosity and a decrease in intrinsic viscosity. The ethylene-α-olefin copolymer of the present invention is considered to have a polymer structure such as a long chain branch, and has an intrinsic viscosity in a suitable range lower than that of a normal ethylene-α-olefin copolymer. Since the ethylene-α-olefin copolymer of the invention satisfies the relationship of the above formula (2), the extrusion torque is low and the extrusion processability is excellent. If the intrinsic viscosity ([η]) is too low and the relationship of 1.02 × MFR ^−0.094 <[η] is not satisfied in the formula (2), the impact strength may be reduced, and the intrinsic viscosity ([η ]) Is too high, and in equation (2), ^if the relationship [η] <1.50 × MFR ^−0.156 is not satisfied, the extrusion torque may be high and the extrusion processability may be poor.

As a relational expression satisfied by the ethylene-α-olefin copolymer in the present invention,
1.05 × MFR ^−0.094 <[η] <1.47 × MFR ^−0.156
And more preferably
1.08 × MFR ^−0.094 <[η] <1.42 × MFR ^−0.156
It is.

The intrinsic viscosity ([η]; the unit is dl / g) in the above formula (2) is obtained by adding ethylene-α-olefin to 100 ml of tetralin containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor. After preparing a sample solution by dissolving 100 mg of the copolymer at 135 ° C., and determining the relative viscosity (ηrel) at 135 ° C. calculated from the falling time of the sample solution and the blank solution using an Ubbelohde viscometer Is calculated from the following equation. The blank solution is tetralin containing only 5% by weight of BHT as a thermal deterioration preventing agent.
[Η] = 23.3 × log (ηrel)

The melt flow rate (MFR; unit is g / 10 minutes) in the above formula (2) is the same as the melt flow rate (MFR) used in the above formula (1).

The ethylene-α-olefin copolymer in the present invention is the most log normal distribution curve obtained by dividing the chain length distribution curve obtained by gel permeation chromatography measurement into at least two log normal distribution curves. It is preferable that the chain length A at the peak position of the lognormal distribution curve corresponding to the component having a high molecular weight and the MFR satisfy the relationship of the following formula (3).
3.30 <logA <−0.0815 × log (MFR) +4.05 Formula (3)

By satisfy | filling the relationship of said Formula (3), the ethylene-alpha-olefin copolymer in this invention is low in extrusion torque, is excellent in extrusion molding processability, and is excellent in the external appearance of extrusion molded articles, such as a film. When the chain length A is too low and the relationship of 3.30 <logA is not satisfied in the formula (3), the melt tension may be lowered and the extrusion processability may be deteriorated, and the chain length A is too high. In the formula (3), when the relationship of logA <−0.0318 × Ln (MFR) +3.935 is not satisfied, the extrusion torque is high and the extrusion processability may be inferior. The appearance of the product may deteriorate.

As a relational expression satisfied by the ethylene-α-olefin copolymer in the present invention, more preferably,
3.30 <logA <−0.0815 × log (MFR) +4.03
And more preferably
3.30 <logA <−0.0815 × log (MFR) +4.02
It is.

The chain length distribution curve can be obtained by gel permeation chromatography measurement under the following conditions.
(1) Apparatus: Waters 150C manufactured by Water
(2) Separation column: TOSOH TSKgelGMH-HT
(3) Measurement temperature: 145 ° C
(4) Carrier: orthodichlorobenzene (5) Flow rate: 1.0 mL / min (6) Injection volume: 500 μL

The chain length distribution curve is divided as follows.
First, a chain length distribution curve in which a weight ratio dW / d (logAw) (y value) is plotted against logAw (x value) that is the logarithm of chain length Aw is measured by gel permeation chromatography measurement. The number of plot data is usually at least 300 or more so as to form a continuous distribution curve. Next, four lognormal distribution curves (xy) having a standard deviation of 0.30 and an arbitrary average value (usually corresponding to the chain length A of the peak position) with respect to the above x value. Curve) is added at an arbitrary ratio to create a composite curve. Further, the average value and the ratio are obtained so that the deviation sum of squares of the y value with respect to the same x value of the actually measured chain length distribution curve and the combined curve becomes a minimum value. The minimum value of the deviation sum of squares is usually 0.5% or less with respect to the deviation sum of squares when the ratios of the peaks are all zero. The logarithm corresponding to the component having the highest molecular weight among the lognormal distribution curves obtained by dividing the logarithmic normal distribution curve into four lognormal distribution curves when the average value and the ratio giving the minimum value of the deviation sum of squares are obtained. Log A is calculated from the chain length A at the peak position of the normal distribution curve. The ratio of the peak of the lognormal distribution curve corresponding to the highest molecular weight component is usually 10% or more.

It is known that an ethylene-α-olefin copolymer generally has an increased MFR and fluidity, that is, a melt viscosity is lowered and a relaxation time is lowered. The ethylene-α-olefin copolymer in the present invention is considered to have a polymer structure such as a long chain branch, and has an appropriate range of relaxation time longer than that of a normal ethylene-α-olefin copolymer. It is preferable that the characteristic relaxation time at ℃ (τ; the unit is sec) and the MFR satisfy the relationship of the following formula (4).
2 <τ <8.1 × MFR− ^0.746 formula (4)

By satisfy | filling the relationship of said Formula (4), the ethylene-alpha-olefin copolymer in this invention is low in extrusion torque, is excellent in extrusion moldability, and is excellent in the external appearance of extrusion molded articles, such as a film. When the characteristic relaxation time (τ) is too low and the relationship of 2 <τ is not satisfied in the formula (4), the melt tension may be lowered and the extrusion processability may be deteriorated. ) Is too high and the relationship of τ <8.1 × MFR ^−0.746 is not satisfied in the formula (4), the extrusion torque is high and the extrusion processability may be inferior. The appearance of the extruded product may be deteriorated.

As a relational expression satisfied by the ethylene-α-olefin copolymer in the present invention, more preferably,
2 <τ <7.9 × MFR ^−0.746
And more preferably
2 <τ <7.8 × MFR ^−0.746
It is.

The characteristic relaxation time (τ) at 190 ° C. is dynamic viscoelasticity data at each temperature T (K) measured under the following conditions using Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics as a viscoelasticity measuring device. Is shifted based on the temperature-time superposition principle, and the dynamic viscosity (η; unit is Pa · sec) at 190 ° C. depends on the shear rate (ω: unit is rad / sec). Is a numerical value calculated when the master curve is approximated by the following cross equation after obtaining the master curve.

Measurement conditions of dynamic viscoelasticity data at each temperature T (K) (1) Geometry: Parallel plate, diameter 25 mm, plate interval: 1.5-2 mm
(2) Strain: 5%
(3) Shear rate: 0.1 to 100 rad / sec
(4) Temperature: 190, 170, 150, 130 ° C
In addition, an appropriate amount (for example, 1000 ppm or more) of an antioxidant such as Irganox 1076 is blended in advance in the sample, and all measurements are performed under nitrogen.

Cross approximate expression η = η0 / [1+ (τ × ω) ⁿ ]
(Η0 and n are constants determined for each ethylene-α-olefin copolymer used for measurement, similarly to the characteristic relaxation time τ.)
In addition, Rheometrics Rhios V. is used as a calculation software for creating a master curve and cross-type approximation. Use 4.4.4.

The melt flow rate (MFR) of the ethylene-α-olefin copolymer in the present invention is usually 0.1 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, more preferably 0. 0.1 to 10 g / 10 minutes, and more preferably 0.1 to 5 g / 10 minutes.

The ethylene-α-olefin copolymer in the present invention has a Q value calculated from a chain length distribution obtained by gel permeation chromatography measurement of 3 or more, preferably 3.5 to 25, more preferably 4 to 4. 20, more preferably 7.5-17. The Q value is preferably the above value from the viewpoints of extrusion torque, extrusion processability, smoke suppression during extrusion process, and fluidity. The Q value is a value representing the molecular weight distribution of the ethylene-α-olefin copolymer. From the chain length distribution obtained by gel permeation chromatography measurement, the polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn ) And Mw divided by Mn (Mw / Mn).

The density of the ethylene-α-olefin copolymer in the present invention is usually 890 to 950 kg / m ³ , and is a value measured according to a method defined in JIS K6760-1981. The density is preferably 900 to 930 kg / m ³ , more preferably 905 to 925 kg / m ² from the viewpoint of the balance between the rigidity and impact strength of the film obtained from the ethylene-α-olefin copolymer of the present invention. m is ^3.

The ethylene-α-olefin copolymer in the present invention is considered to have a polymer structure such as a long-chain branch, and has a higher flow activation energy than a normal ethylene-α-olefin copolymer. The flow activation energy (Ea; unit is kJ / mol) of the ethylene-α-olefin copolymer in the present invention is preferably greater than 40 kJ / mol from the viewpoint of fluidity. More preferably, it is 45 kJ / mol or more, More preferably, it is 50 kJ / mol or more.

The flow activation energy (Ea) is measured under the same conditions as when the characteristic relaxation time (τ) is calculated using a Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics as a viscoelasticity measuring device. When dynamic viscoelasticity data at each temperature T (K) is shifted based on the temperature-time superposition principle, it is a numerical value calculated from the Arrhenius equation of the following shift factor (aT), It is an indicator of

Arrhenius type equation of shift factor (aT) log (a _T ) = Ea / R (1 / T−1 / T ₀ )
(R is a gas constant and T ₀ is a reference temperature (463 K).)
The calculation software includes Rheometrics Rhios V. The Ea value when the correlation coefficient r2 obtained when performing linear approximation in Arrhenius type plot log (aT)-(1 / T) using 4.4.4 is The activation energy of the flow of the ethylene-α-olefin copolymer in

The ethylene-α-olefin copolymer in the present invention is considered to have a polymer structure such as a long-chain branch, and has a higher melt flow rate ratio than a normal ethylene-α-olefin copolymer. The melt flow rate ratio (MFRR) of the ethylene-α-olefin copolymer of the present invention is usually preferably 60 or more from the viewpoint of fluidity. An ethylene-α-olefin copolymer having a melt flow rate ratio (MFRR) of 60 or more has low extrusion torque and excellent extrusion processability.

The melt flow rate ratio (MFRR) is a value obtained by measuring a melt flow rate value measured at 190 ° C. under a load of 211.82 N (21.60 kg) according to a method defined in JIS K7210-1995 with a load of 21.18 N (2 .16 kg) divided by the melt flow rate value. In addition, the polymer which mix | blended 1000 ppm of antioxidant previously was used for said melt flow rate measurement.

As the melting point (unit is ° C.) of the ethylene-α-olefin copolymer in the present invention, when the density is 927 kg / m ³ or less, at least two melting points are usually present from the viewpoint of heat resistance. The maximum melting point (Tmax) is 115 ° C. or higher, preferably 118 ° C. or higher. Even when there is only one melting point and the melting point is below 115 ° C., there is a melting component at 118 ° C. or higher.

The above melting point is a differential scanning calorimeter DSC-7 manufactured by PerkinElmer, and 8 to 12 mg of sample is packed in an aluminum pan and held at 150 ° C. for 2 minutes, and then up to 40 ° C. at 5 ° C./min. The melting peak temperature observed when the temperature is lowered and held at 40 ° C. for 2 minutes and then raised to 150 ° C. at 5 ° C./min. Among them, the temperature at the highest melting peak position is defined as the maximum melting point Tmax.

The ethylene-α-olefin copolymer in the present invention can be produced by copolymerizing ethylene and an α-olefin under hydrogen conditions using the following metallocene olefin polymerization catalyst.
The metallocene-based olefin polymerization catalyst used in the production of the ethylene-α-olefin copolymer in the present invention is a catalyst obtained by contacting a co-catalyst carrier, a crosslinked bisindenyl zirconium complex and an organoaluminum compound, The cocatalyst support is a support obtained by contacting diethylzinc, fluorinated phenol, water, silica, and trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH).

The amount of diethyl zinc, fluorinated phenol, and water used is not particularly limited, but when the molar ratio of the amount of each compound used is diethyl zinc: fluorinated phenol: water = 1: p: q, p and It is preferable that q substantially satisfies the following formula (3).
| 2-p-2q | ≦ 1 (3)
P in the formula (3) is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Yes, most preferably a number from 0.30 to 1.00.

The amount of silica to be used with respect to diethylzinc is the number of moles of zinc atoms contained in 1 g of the particles obtained by adding zinc atoms derived from diethylzinc contained in particles obtained by contact of diethylzinc and silica. Thus, the amount is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol. Therefore, the amount may be appropriately determined so as to be within this range. The amount of trimethyldisilazane to be used with respect to silica is preferably an amount of 0.1 mmol or more of trimethyldisilazane per 1 g of silica, and more preferably 0.5 to 20 mmol.

The cross-linked bisindenylzirconium complex is preferably racemic-ethylenebis (1-indenyl) zirconium dichloride or racemic-ethylenebis (1-indenyl) zirconium diphenoxide.
The organoaluminum compound is preferably triisobutylaluminum or trinormaloctylaluminum.

The amount of the crosslinked bisindenylzirconium complex used is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol with respect to 1 g of the promoter support. The amount of the organoaluminum compound used is preferably 1 to 2000 in terms of the ratio of the number of moles of aluminum atoms in the organoaluminum compound to the number of moles of zirconium atoms in the crosslinked bisindenylzirconium complex (Al / Zr). .

The polymerization method is preferably a polymerization method involving the formation of ethylene-α-olefin copolymer particles, such as gas phase polymerization, slurry polymerization, and bulk polymerization, and preferably gas phase polymerization.

As a method of supplying each component of the metallocene-based olefin polymerization catalyst used for the production of the ethylene-α-olefin copolymer in the present invention to the reaction vessel, usually an inert gas such as nitrogen or argon, hydrogen, ethylene, etc. And a method of supplying in a water-free state, and a method of supplying each component in a solution or slurry after dissolving or diluting each component in a solvent. Each component of the catalyst may be supplied individually, or arbitrary components may be supplied in contact in advance in an arbitrary order.
Moreover, it is preferable to carry out prepolymerization before carrying out the main polymerization and to use the prepolymerized catalyst component that has been prepolymerized as a catalyst component or catalyst for the main polymerization.

The polymerization temperature is usually below the temperature at which the copolymer melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C.
Further, hydrogen may be added as a molecular weight regulator for the purpose of regulating the melt fluidity of the copolymer. An inert gas may coexist in the mixed gas.

In addition, the ethylene-α-olefin copolymer in the present invention preferably has a structure in which polymer structures such as long-chain branches are considered to be extremely intertwined from the viewpoint of further improving the extrusion processability, It has a higher flow activation energy than an ethylene-α-olefin copolymer having a polymer structure such as a normal long chain branch. The activation energy (Ea; unit is kJ / mol) of the flow of the ethylene-α-olefin copolymer in the present invention is preferably 60 kJ / mol or more. More preferably, it is 63 kJ / mol or more, More preferably, it is 66 kJ / mol or more. When Ea is less than 60 kJ / mol, the melt tension is hardly increased at low temperatures, and sufficient moldability may not be obtained. Ea is preferably 100 kJ / mol or less, more preferably 90 kJ / mol or less. When Ea exceeds 100 kJ / mol, the melt viscosity is too low at a high temperature, so that sufficient processability cannot be obtained, and the surface of an extruded product such as a film may be rough, and the appearance may be significantly impaired. .

Furthermore, in the ethylene-α-olefin copolymer in the present invention, it is preferable that the swell ratio (SR) and the above [η] satisfy the relationship of the following formula (5) from the viewpoint of further improving the extrusion processability. .
When [η] <1.20, −0.91 × [η] +2.262 <SR <2 Formula (5)
When [η] ≧ 1.20, 1.17 <SR <2

It has been found that an ethylene-α-olefin copolymer having a polymer structure such as a normal long chain branch generally has an increased swell ratio (SR) as [η] decreases. The ethylene-α-olefin copolymer in the present invention preferably has a structure in which polymer structures such as long chain branches are considered to be intertwined very closely, and has a polymer structure such as normal long chain branches. By having SR in a suitable range higher than that of the ethylene-α-olefin copolymer and satisfying the relationship of the above formula (5), the extrusion torque is low and the stability at the time of extrusion molding is excellent. When SR is low and Formula (5) is not satisfied, extrusion torque is high and extrusion processability may be inferior. When SR exceeds 2, the surface of an extruded product such as a film is rough, and the appearance is remarkably impaired. May be.

The ethylene-α-olefin copolymer in the present invention preferably satisfies the following formula.
When [η] <1.23, −0.91 × [η] +2.289 <SR <1.9
When [η] ≧ 1.23, 1.17 <SR <1.9
Moreover,
In the case of [η] <1.30, −0.91 × [η] +2.353 <SR <1.8
When [η] ≧ 1.30, 1.17 <SR <1.8
It is preferable to satisfy.

The swell ratio (SR) in the above formula (5) was obtained by cooling in air after extrusion into a strand with a load of 21.18 N (2.16 Kg) at 190 ° C. when measuring the MFR. For the solid strand, the diameter D (unit is mm) at one point in the range of 1 to 6 mm from the tip, and the value divided by the orifice diameter 2.095 mm (D ₀ ) (D / D ₀ ). The diameter D was obtained as an average value of three strand samples.

The method for producing an ethylene-α-olefin copolymer in the present invention having such a structure that the polymer structure such as long chain branching is considered to be intertwined very closely, using the metallocene olefin polymerization catalyst, In this method, ethylene and α-olefin are copolymerized under hydrogen conditions and then kneaded by the following continuous extrusion granulation method. For example, by continuously forming a strand using an extruder equipped with an extension flow kneading (EFM) die as developed by Utracki et al. (US Pat. No. 5,451,106), and continuously cutting the strand. It is a method of manufacturing in pellet form. The other is a method in which a strand is continuously formed using an extruder having a bi-directional screw with a gear pump, and the strand is continuously cut to produce a pellet. In the latter, it is preferable that there is a staying part between the screw part and the die.

The olefin resin composition of the present invention contains 30 to 0.1% by weight of an inorganic compound represented by the following formula (A), (I) or (U) as a component (B). The film obtained by using the olefin resin composition containing the component (B) in a predetermined amount is excellent in balance between transparency and heat retention.
Component (B): Inorganic compound represented by the following formula (A), (I) or (U) 30 to 0.1% by weight
An olefin-based resin composition comprising:
^{_{[{Mg y5 M 2+ y6}}} 1-β Al β (OH) 2] β + · [A n- zβ / n · fH 2 O] β- ( A)
(Wherein M ²⁺ is, Zn, ^{.A n-} is showing a divalent metal ion of at least one of Ca and Ni .Beta showing a n-valent anion, y5, y6 and b satisfy the following conditions.)
0 ≦ β <0.5, y5 + y6 = 1, y5 ≦ 1, y6 <1, 0 ≦ f <2.
Examples of the anionic species A ^n-, e.g. ^{_{Cl -, Br -, I -}} , NO 3 -, ClO -, H 2 PO 4 -, HBO 3 2-, SO 4 2-, CO 3 2-, SiO 3 2 ^-, _HPO ⁴ 2-, include inorganic acids and organic acids such as _PO ^{4 3-.} In particular, CO ₃ ²⁻ is preferably used from the viewpoint of transparency.

[{Mg _y1 M ²⁺ _y2 } _1-x Al _x (OH) ₂ ] ^{x +} · [(A) _z1 · (B) _z2 · bH ₂ O] ^x− (A)
( ^Wherein M ²⁺ represents one or more divalent metal ions selected from Zn, Ca, and Ni. A represents at least one of silicon-based, phosphorus-based, and boron-based oxygenate ions. B represents at least one anion other than A, and x, y1, y2, z1, z2, and b satisfy the following conditions.)
0 <x ≦ 0.5, y1 + y2 = 1, y1 ≦ 1, y2 <1, 0 <z1, 0 ≦ z2, 0 ≦ b <2.
Examples of the anion of A include, for example, silicon-based SiO ₃ ²⁻ , Si ₂ O ₅ ²⁻ , Si ₃ O ₇ ²⁻ , Si ₄ O ₉ ²⁻ , (HSiO ₃ ) ⁻ , (HSi ₂ O ₅₎ ^-, such as ^{_{(Si n O 2n + 1)}} 2- or _{(HSi n O 2n + 1)} - ( which n is represented by an integer of 1 or more) such as is,
As the ^{_{phosphorus-based, PO 4 3-, (HPO 4}} ) 2-, (H 2 PO 4) -, P 2 O 7 4-, P 3 O 10 5-, P 3 O 9 3-, P 4 ^{_{O 12 4-, P 6 O 18}} P n O 3n n- or such _{^{6- [(PO 3) n]}} n- (n is an integer of 3 or more) those represented by like _{or, (H 2 P} 2 O ₇ ) ^2- like a phosphorus-based oxygenate ion with some H groups added,
Further, the boron system includes BO ₃ ³⁻ , (HBO ₃ ) ²⁻ , (H ₂ BO ₃ ) ⁻ , [B ₃ O ₃ (OH) ₄ ] ⁻ , [B ₅ O ₆ (OH) ₄ ] ⁻ or Monomeric oxygen acid ions such as [B ₄ O ₅ (OH) ₄ ] ² and multimeric oxygen acid ions may be mentioned.
In particular, multimeric oxygen acid ions are preferable from the viewpoint of improving heat retention, and silicon-based multimeric oxygen acid ions are particularly preferable.

[{Li _y3 G ²⁺ _y4 } Al ₂ (OH) ₆ ] ^{α +} · [(C) _z3 · (D) _z4 · dH ₂ O] ^α− (U)
(In the formula, G ²⁺ represents one or more divalent metal ions selected from Mg, Zn, Ca, and Ni. C represents at least one of silicon-based, phosphorus-based, and boron-based multimeric oxygenate ions. D represents at least one anion other than C, and α, y3, y4, z3, z4, and d satisfy the following conditions.)
α = y3 + 2y4, 0 <y3 ≦ 1, 0 ≦ y4 ≦ 1, 0.5 ≦ (y3 + y4) ≦ 1, 0 <z3, 0 ≦ z4, 0 ≦ d <5
Examples of the anion of A include, for example, silicon-based SiO ₃ ²⁻ , Si ₂ O ₅ ²⁻ , Si ₃ O ₇ ²⁻ , Si ₄ O ₉ ²⁻ , (HSiO ₃ ) ⁻ , (HSi ₂ O ₅₎ ^-, such as ^{_{(Si n O 2n + 1)}} 2- or _{(HSi n O 2n + 1)} - ( which n is represented by an integer of 1 or more) such as is,
As the ^{_{phosphorus-based, PO 4 3-, (HPO 4}} ) 2-, (H 2 PO 4) -, P 2 O 7 4-, P 3 O 10 5-, P 3 O 9 3-, P 4 ^{_{O 12 4-, P 6 O 18}} P n O 3n n- or such _{^{6- [(PO 3) n]}} n- (n is an integer of 3 or more) those represented by like _{or, (H 2 P} 2 O ₇ ) ^2- like a phosphorus-based oxygenate ion with some H groups added,
Further, the boron system includes BO ₃ ³⁻ , (HBO ₃ ) ²⁻ , (H ₂ BO ₃ ) ⁻ , [B ₃ O ₃ (OH) ₄ ] ⁻ , [B ₅ O ₆ (OH) ₄ ] ⁻ or Monomeric oxygen acid ions such as [B ₄ O ₅ (OH) ₄ ] ² and multimeric oxygen acid ions may be mentioned.
In particular, multimeric oxygen acid ions are preferable from the viewpoint of improving heat retention, and silicon-based multimeric oxygen acid ions are particularly preferable.

The olefin resin composition of the present invention may contain one or more inorganic compounds represented by the above (a), (b) or (c). When a plurality of inorganic compounds represented by (a), (b) or (c) are contained, the total is 30 to 0.1% by weight. From the viewpoint of transparency and heat retention, the component (B) is preferably a compound represented by (I) or (U).

You may make the olefin resin composition of this invention contain a well-known additive as needed. Examples of the additive include an antioxidant, a light stabilizer, an ultraviolet absorber, an antifoggant, an antifogging agent, a lubricant, an antiblocking agent, an antistatic agent, a pigment, and an inorganic filler.

Examples of the antioxidant include phosphorus-based compounds containing trivalent phosphorus atoms such as so-called hindered phenol compounds such as 2,6-dialkylphenol derivatives and 2-alkylphenol derivatives, phosphite compounds, and phosphonite compounds. An ester compound is mentioned.
These antioxidants may be used alone or in combination of two or more. In particular, from the viewpoint of stabilizing the hue, it is preferable to use a hindered phenol compound and a phosphorus ester compound in combination.
Moreover, content of antioxidant is suitably selected according to the intended use, for example, when using as an agricultural film, 0.01 to 1 weight% is preferable and 0.03 to 0.5 weight% is preferable. More preferred.

Examples of the light stabilizer include a hindered amine compound having a structure described in JP-A-8-73667, and specific examples thereof include the trade names Tinuvin 622-LD, Kimasorb 944-LD (above Ciba Specialty). Chemicals), Hostabin N30, VP Sanduvor PR-31 (manufactured by Clariant, Inc.), Saiyasorb UV3529, Saiyasorb UV3346 (manufactured by Cytec). Furthermore, sterically hindered amine ether compounds having the structure described in JP-A-11-315067 can be mentioned, and specifically, trade name Tinuvin NOR371 (manufactured by Ciba Specialty Chemicals) can be mentioned. The content of the light stabilizer is appropriately selected according to the intended use. For example, when used as an agricultural film, it is preferably 0.01 to 3% by weight, more preferably 0.05 to 2% by weight, 0.1 to 1 weight% is especially preferable.

Examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, benzoate UV absorbers, and cyanoacrylate UV absorbers. These can be used alone or in combination of two or more. You may use together.
The content of the ultraviolet absorber is appropriately selected according to the intended use. For example, when used as an agricultural film, 0.01 to 3% by weight is preferable from the viewpoint of weather resistance imparting effect and blooming suppression. 0.03 to 2% by weight is more preferable.

Examples of the anti-fogging agent include fluorine compounds having a perfluoroalkyl group, ω-hydrofluoroalkyl group, etc. (especially fluorine-based surfactants), and silicon-based compounds having alkylsiloxane groups (particularly silicon-based surfactants). Etc. Specific examples of the fluorosurfactant include Unidyne DS-403, DS-406, DS-401 (trade name) manufactured by Daikin Industries, Ltd., and Surflon KC-40 (trade name) manufactured by Seimi Chemical Co., Ltd. Examples of the silicon-based surfactant include SH-3746 (trade name) manufactured by Toray Dow Corning Silicon Co., Ltd. These may be used alone or in combination of two or more. The content of the anti-fogging agent is appropriately selected according to the intended use. For example, when used as an agricultural material, it is preferably 0.01 to 3% by weight, more preferably 0.02 to 2% by weight, 0.05 to 1% by weight is particularly preferable.

The antifogging agent is not particularly limited as long as it is a surfactant, but a nonionic surfactant is preferably used from the viewpoint of compatibility with the resin and thermal stability. Specifically, sorbitan-based interfaces such as sorbitan monopalmitate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monomontanate, sorbitan monooleate, sorbitan fatty acid esters such as sorbitan dioleate, and alkylene oxide adducts thereof Activator, glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerin monostearate, tetraglycerin dimontanate, glycerin monooleate, diglycerin monooleate, diglycerin sesquioleate, tetraglycerin Monooleate, hexaglycerin monooleate, hexaglycerin trioleate, tetraglycerin trioleate, tetraglycerin monolaurate, hexaglyceride Glycerin surfactants such as glycerin fatty acid esters and alkylene oxide adducts thereof such as polyethylene monolaurate, polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate, alkylene oxide adducts of alkylphenols, Esters of sorbitan / glycerin condensate and organic acid, polyoxyethylene (2 mol) stearylamine, polyoxyethylene (4 mol) stearylamine, polyoxyethylene (2 mol) stearylamine monostearate, polyoxyethylene (4 Mol) Polyoxyethylene alkylamines such as laurylamine monostearate and fatty acid esters thereof. These may be used alone or in combination of two or more. The content of the antifogging agent is appropriately selected according to the intended use. For example, when used as an agricultural material, 0.1 to 4% by weight is preferable from the viewpoint of antifogging durability and blooming suppression, Is preferably 0.5 to 3% by weight.

Examples of the inorganic filler include lithium aluminum composite hydroxide represented by a structural formula different from the component (B) in the present invention. Specific examples of the lithium aluminum composite hydroxide include Li ₂ Al ₄ (OH) ₁₂ .CO ₃ .3H ₂ O (trade name Mizukarak manufactured by Mizusawa Chemical Industry Co., Ltd.). Furthermore, metal oxides such as magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, and titanium oxide; hydroxides such as lithium hydroxide, magnesium hydroxide, calcium hydroxide, and aluminum hydroxide; magnesium carbonate, calcium carbonate, etc. Carbonates of: sulfates such as potassium sulfate, magnesium sulfate, calcium sulfate, zinc sulfate, aluminum sulfate; lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate phosphate (for example, JP-A-8-67774) Disclosed phosphates such as H-type zirconium phosphate); silicates such as magnesium silicate, calcium silicate, aluminum silicate, titanium silicate; aluminates such as sodium aluminate, potassium aluminate, calcium aluminate; aluminum Sodium silicate, potassium aluminosilicate, aluminosilicates such as calcium aluminosilicate; kaolin, clay, clay minerals such as talc, and other composite oxides thereof.

The manufacturing method of the olefin resin composition of this invention is not specifically limited, For example, it manufactures with the following method. A predetermined amount of the inorganic compound constituting the component (B) and, if necessary, other additives are mixed into the ethylene-α-olefin copolymer constituting the component (A) in the present invention using a mixer. As the mixer, for example, an olefin-based resin composition is produced using a conventional apparatus such as a ribbon blender, a super mixer, a Banbury mixer, a single screw extruder, or a twin screw extruder.

The olefin resin composition of the present invention can be suitably used for extrusion molding, injection molding, blow molding and the like. In particular, the olefin resin composition of the present invention can be suitably used for agricultural films.

Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, the test method in an Example and a comparative example is as follows.
1) Measurement of melt flow rate (MFR) Melt flow rate (MFR; unit is g / 10 min.) Is a load of 21.18 N (2.P) at 190 ° C. according to the method defined in JIS K7210-1995. 16 kg).
2) Measurement of melt tension (MT) The melt tension (MT; unit is cN) is 190 ° C. with a piston at an extrusion speed of 5.5 mm / min using a melt tension tester manufactured by Toyo Seiki Seisakusho. When the molten resin strand is extruded from an orifice having a diameter of 2.09 mmφ and a length of 8 mm, and the strand is wound up at a rotational speed of 40 rpm / min using a roller having a diameter of 50 mm, the strand is cut. Indicates the previous tension value.
3) Measurement of intrinsic viscosity [η] Intrinsic viscosity ([η]; unit is dl / g) was measured by adding ethylene-α to 100 ml of tetralin containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor. -100 mg of an olefin copolymer was dissolved at 135 ° C to prepare a sample solution, and a relative viscosity (ηrel) at 135 ° C calculated from the falling time of the sample solution and the blank solution was obtained using an Ubbelohde viscometer. After that, it is calculated from the following formula. The blank solution is tetralin containing only 5% by weight of BHT as a thermal deterioration preventing agent.
[Η] = 23.3 × log (ηrel)
4) Measurement of molecular weight distribution (Q value) The Q value is calculated by calculating the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene from the chain length distribution obtained by gel permeation chromatography measurement. Is a value obtained by dividing Mn by Mn (Mw / Mn).
The chain length distribution curve can be obtained by gel permeation chromatography measurement under the following conditions.
(1) Apparatus: Waters 150C manufactured by Water
(2) Separation column: TOSOH TSKgelGMH-HT
(3) Measurement temperature: 145 ° C
(4) Carrier: orthodichlorobenzene (5) Flow rate: 1.0 mL / min (6) Injection volume: 500 μL
5) Extrusion processability (bubble stability during inflation molding)
The stability of extrusion processing was as follows. The stability of the bubble was observed when the film was formed by a three-layer blown film molding machine under the conditions of die diameter: 100 mmφ, processing temperature: 160 ° C., and BUR: 2.0. Judged.
○ Bubble is stable and fluctuation in film width is small × Bubble is unstable and fluctuation in film width is large 6) Transparency test (Haze)
Haze (%) was measured using a direct reading haze computer HGM-2DP; C light source (manufactured by Suga Test Instruments) in accordance with JIS K7105.
7) Thermal insulation measurement (radiation absorption rate at 23 ° C)
The radiation absorption rate at 23 ° C. is measured by the following method.
Using an infrared spectrophotometer (Fourier transform infrared spectrophotometer FTIR-8700 manufactured by Shimadzu Corporation), the infrared absorption spectrum (transmission method) of the multilayer film is measured at a temperature of 23 ° C. in the range of wave numbers 4000 to 400 cm ^−1. Then, a value of transmittance T (ν)% at wave number ν is obtained.
On the other hand, according to the equation (1) obtained from Planck's law, the black body radiation spectrum intensity e (ν) at a wave number ν at 23 ° C. is calculated. Here, the black body radiation spectrum intensity e (ν) multiplied by the transmittance T (ν) is the radiation transmission intensity f (ν) (formula (2)).
What integrated radiation transmission intensity f (ν) in the range of wave numbers 4000 to 400 cm ⁻¹ and integrated radiation transmission energy F and black body radiation spectrum intensity e (ν) in the range of wave numbers 4000 to 400 cm ^−1. Is defined as a black body radiation energy E as a radiation transmission index G = 100 × F / E. In the actual integration, the calculation is performed for each section by trapezoidal approximation and integrated by dividing the section into wavenumber intervals of 2 cm ⁻¹ .
e (ν) = (A / λ ⁵ ) / {exp (B / (λ × T)) ⁻¹ } (1)
A = 2πhC ² = 3.74 × 10 ⁻¹⁶ (W · m ² )
B = hC / k = 0.01439 (m · K)
T (K) is the absolute temperature. λ (cm) is the wavelength. (Wave number ν is the reciprocal of wavelength)
(H is Planck's constant, C is the speed of light, and k is Boltzmann's constant.)
f (ν) = e (ν) × T (ν) / 100 (2)
8) Punching impact resistance test Measurement was performed using a punching tester manufactured by Toyo Seiki Seisakusho. A test film is fixed to a sample stage, a pendulum is shaken, and an impact is applied to the sample. The energy (kg · cm) required for this through fracture was read from the scale plate and used as the punching impact strength.

9) A test film (width 60 cm, length 50 cm) was attached to a friction-resistant test pipe frame (19 mmφ galvanized steel pipe), and the test film was further pressed and fixed with a 9 mm width mica wire (manufactured by Ishimoto Maolan). At the site where the pipe / film / mica wire overlaps, the film is moved 10 times in the direction of the mica wire in the direction of the mica wire (the time required for one reciprocation is 5 seconds), and friction with the mica wire The degree of the holes and rubbing traces produced by the above was determined according to the following criteria, and the friction resistance was evaluated.
○ Scratch scars are hardly seen △ Scratch scratches are deep, but there are no tears.

<Synthesis of Resin A1 as Component (A)>
[Preparation of catalyst components]
(1) Silica treatment Silica heated at 300 ° C. under nitrogen flow in a nitrogen-substituted 3 liter four-necked flask (Sypolol 948 manufactured by Devison; average particle size = 61 μm; pore volume = 1.70 ml / g) Specific surface area = 291 m 2 / g) 0.2 kg was added, and then 1.2 liters of toluene was added while washing off the silica adhering to the wall of the flask. After cooling to 5 ° C., a mixed solution of 1,1,1,3,3,3-hexamethyldisilazane 84.4 ml (0.4 mmol) and toluene 115 ml was added dropwise over 25 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and then at 95 ° C. for 3 hours and filtered. Thereafter, the filter was washed four times with 1.2 liters of toluene at 95 ° C. Then, after adding 1.2 liters of toluene, it was left still overnight.

(2) Synthesis of co-catalyst carrier To the slurry obtained above, 0.550 liter (1.10 mol) of diethylzinc in hexane (2.00 mol / liter) was added and cooled to 5 ° C. A solution prepared by dissolving 105 g (0.570 mol) of pentafluorophenol in 173 ml of toluene was added dropwise thereto over 65 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour. Then, it heated at 40 degreeC and stirred for 1 hour. After the temperature was adjusted to 5 ° C. with an ice bath, 14.9 g (0.828 mol) of H 2 O was added dropwise over 90 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 40 ° C. for 2 hours. Then, it left still overnight at room temperature. Then, after stirring at 80 ° C. for 2 hours, the mixture is allowed to stand to settle the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion is seen, the upper slurry portion is removed, and then the remaining liquid After filtering the components with a filter, 1.7 liters of toluene was added and stirred at 95 ° C. for 2 hours. Thereafter, the mixture was stirred 4 times with 1.7 liters of toluene at 95 ° C. and 2 times with 1.7 liters of hexane at room temperature, and then allowed to stand to precipitate the solid component. When the interface with the slurry portion was seen, the upper slurry portion was removed, and then the remaining liquid component was filtered through a filter. Thereafter, the solid component was dried at room temperature under reduced pressure for 3 hours to obtain 0.39 kg of a promoter support.

[Preparation of prepolymerization catalyst]
80 liters of butane containing triisobutylaluminum at a concentration of 2.5 mmol / liter and 11 liters of 1-butene as hydrogen at normal temperature and pressure are charged in an autoclave with a stirrer having an internal volume of 210 liters that has been previously purged with nitrogen. Thereafter, the temperature of the autoclave was raised to 23 ° C. Further, ethylene was charged by 0.2 MPa at the gas phase pressure in the autoclave, and after the system was stabilized, 10 mmol of triisobutylaluminum, 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, and then the above promoter support 0.63 kg was charged to initiate polymerization. While raising the temperature to 45 ° C. and continuously supplying ethylene and hydrogen, preliminary polymerization was carried out at 50 ° C. for a total of 4 hours. After completion of the polymerization, a prepolymerized catalyst in which ethylene, butane, hydrogen gas and the like are purged and the remaining solid is vacuum-dried at room temperature, and 14 g of ethylene / 1-butene copolymer is prepolymerized per 1 g of the promoter support. Ingredients were obtained.

[Polymerization and granulation]
Using the prepolymerization catalyst component obtained above, copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 75 ° C., a total pressure of 2 MPa, a hydrogen molar ratio to ethylene of 0.5%, a 1-hexene molar ratio to ethylene of 1.1%, ethylene to maintain a constant gas composition during the polymerization, 1-hexene and hydrogen were continuously supplied. Ethylene / 1-hexene copolymerization with an average polymerization time of 4 hr and a production efficiency of 21 kg / hr so that the prepolymerized catalyst component and triisobutylaluminum are continuously supplied and the total powder weight of the fluidized bed is maintained at 80 kg. I got a powder. The ethylene / 1-hexene copolymer powder thus obtained was blended with 1000 ppm of calcium stearate and 1800 ppm of Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) using a LCM100 extruder manufactured by Kobe Steel, Ltd. An ethylene / 1-hexene copolymer (A1) was obtained by granulation under conditions of 350 kg / hr, screw rotation speed 450 rpm, gate opening 0 mm, suction pressure 0.2 MPa, and resin temperature 200-230 ° C.

<Synthesis of Resin A2 as Component (A)>
A prepolymerized catalyst component in which about 12 g of ethylene / 1-butene copolymer was prepolymerized per 1 g of the co-catalyst support obtained in the same manner as the synthesis of the A1 resin was used, and the molar ratio of hydrogen to ethylene was 0.6%. To 1.55%, and the molar ratio of 1-hexene to ethylene was controlled in the range of 0.8% to 1.8%. Hexene copolymerization was carried out, and in the same manner as in Example 1, granulation was carried out using an LCM100 extruder manufactured by Kobe Steel, Ltd. to obtain an ethylene / 1-hexene copolymer (A2).

<Manufacture of olefin resin composition>
After mixing for 5 minutes at 150 ° C. using a Banbury mixer with the formulation shown in Table 1, granulation was performed by a granulator to obtain an olefin-based resin composition for each layer (values in parentheses in the table) Indicates parts by weight with respect to 100 parts by weight of resin in each layer).

<Production of film>
Using a three-layer blown film molding machine under the conditions of die diameter: 100 mmφ, processing temperature: 160 ° C., and BUR: 2.0 so that the inner layer in Table 1 is the inner surface of the blown film tube (the outer layer is the outer surface of the blown tube) The film was formed. The thickness of each layer is as shown in Table 1.

The evaluation results of the obtained film are shown in Table 1. The films in Examples 1 and 2 were excellent in transparency, heat retention, punching impact resistance and friction resistance.

［略号一覧］
Ａ１：エチレン−１−ヘキセン共重合体（ＭＦＲ０．４ｇ／１０分、[η]１．１８、密度０．９１５ｇ／ｃｍ^３、ＭＴ５．５ｃＮ、Ｑ値６．１）
式（１）値：２×（０．４）^{−０．５９}＜５．５＜２０×（０．４）^{−０．５９}
式（２）値：１．０２×（０．４）^{−０．０９４}＜１．１８＜１．５０×（０．４）^{−０．１５６}
Ａ２：エチレン−１−ヘキセン共重合体（ＭＦＲ０．４ｇ／１０分、[η]１．１９、密度０．９０５ｇ／ｃｍ^３、ＭＴ６．２ｃＮ、Ｑ値５．９）
式（１）値：２×（０．４）^{−０．５９}＜６．２＜２０×（０．４）^{−０．５９}
式（２）値：１．０２×（０．４）^{−０．０９４}＜１．１９＜１．５０×（０．４）^{−０．１５６}
Ａ３：エチレン−１−ヘキセン共重合体（商品名：エボリューＳＰ２０４０ ＭＦＲ３．６ｇ／１０分、[η]１．２８、密度０．９１７ｇ／ｃｍ^３、ＭＴ０．４ｃＮ、Ｑ値２．５） 三井住友ポリオレフィン社製）
式（１）値：２×（３．６）^{−０．５９}＞０．４
式（２）値：１．２８＞１．５０×（３．６）^{−０．１５６}
Ａ４：エチレン−１−ヘキセン共重合体（商品名：エボリューＳＰ０５４０ ＭＦＲ４．１ｇ／１０分、[η]１．２４、密度０．９０２ｇ／ｃｍ^３、ＭＴ０．２ｃＮ、Ｑ値２．２） 三井住友ポリオレフィン社製）
式（１）値：２×（４．１）^{−０．５９}＞０．２
式（２）値：１．２４＞１．５０×（４．１）^{−０．１５６}
Ａ５：低密度ポリエチレン（商品名：スミカセンＦ２０８−１ ＭＦＲ１．６ｇ／１０分、密度０．９２１ｇ／ｃｍ^３、ＭＴ１２．１ｃＮ） 三井住友ポリオレフィン社製）
Ａ６：エチレン−酢酸ビニル共重合体（商品名：エバテートＨ２０２１ 酢酸ビニル含有量１５重量％ 住友化学工業社製）
Ａ７：エチレン−酢酸ビニル共重合体（商品名：エバテートＤ２０１１ 酢酸ビニル含有量５重量％ 住友化学工業社製）
Ｅ１：商品名：スミライザーＢＰ７６ 住友化学工業社製
Ｅ２：商品名：イルガフォスＰ１６８ チバ・スペシャルティ・ケミカルズ社製
Ｅ３：商品名：スミライザーＢＨＴ 住友化学工業社製
Ｅ４：商品名：イルガノックス１０１０ チバ・スペシャルティ・ケミカルズ社製
Ｆ１：ヒンダードアミン系化合物（商品名：キマソーブ９４４ＬＤ チバ・スペシャルティ・ケミカルズ社製）
Ｆ２：ヒンダードアミン系化合物（商品名：チヌビン６２２ＬＤ チバ・スペシャルティ・ケミカルズ社製）
Ｇ１：商品名：スミソーブ１３０ 住友化学工業社製
Ｈ１：ジグリセリンセスキオレエート
Ｈ２：モノグリセリンモノステアレート／ジグリセリンセスキステアレートの重量比＝３／７なる混合物
Ｊ３：リチウムアルミニウム複合水酸化物縮合ケイ酸塩（商品名：フジレイン 富士化学工業社製）
構造式：［ＬｉＡｌ_２（ＯＨ）_６］_２・［Ｓｉ_２Ｏ_５・ｄＨ₂Ｏ］、０≦ｄ＜５
Ｋ１：脂肪酸アミド化合物 エチレンビスオレイン酸アミド
Ｋ２：脂肪酸アミド化合物 エルカ酸アミド
Ｌ１：ソジウムカルシウムアルミノシリケート（商品名：シルトンＪＣ−３０ 水澤化学工業社製）

[List of abbreviations]
A1: Ethylene-1-hexene copolymer (MFR 0.4 g / 10 min, [η] 1.18, density 0.915 g / cm ³ , MT 5.5 cN, Q value 6.1)
Formula (1) Value: 2 × (0.4) ^−0.59 <5.5 <20 × (0.4) ^−0.59
Formula (2) Value: 1.02 × (0.4) ^−0.094 <1.18 <1.50 × (0.4) ^−0.156
A2: ethylene-1-hexene copolymer (MFR 0.4 g / 10 min, [η] 1.19, density 0.905 g / cm ³ , MT 6.2 cN, Q value 5.9)
Formula (1) Value: 2 × (0.4) ^−0.59 <6.2 <20 × (0.4) ^−0.59
Formula (2) Value: 1.02 × (0.4) ^−0.094 <1.19 <1.50 × (0.4) ^−0.156
A3: Ethylene-1-hexene copolymer (trade name: Evolue SP2040 MFR 3.6 g / 10 min, [η] 1.28, density 0.917 g / cm ³ , MT 0.4 cN, Q value 2.5) Sumitomo Mitsui (Made by polyolefin)
Formula (1) Value: 2 × (3.6) ^−0.59 > 0.4
Formula (2) Value: 1.28> 1.50 × (3.6) ^−0.156
A4: Ethylene-1-hexene copolymer (trade name: Evolue SP0540 MFR 4.1 g / 10 min, [η] 1.24, density 0.902 g / cm ³ , MT 0.2 cN, Q value 2.2) Sumitomo Mitsui (Made by polyolefin)
Formula (1) Value: 2 × (4.1) ^−0.59 > 0.2
Formula (2) Value: 1.24> 1.50 × (4.1) ^−0.156
A5: Low density polyethylene (trade name: Sumikasen F208-1 MFR 1.6 g / 10 min, density 0.921 g / cm ³ , MT 12.1 cN) manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.)
A6: Ethylene-vinyl acetate copolymer (trade name: Evertate H2021 vinyl acetate content 15% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
A7: Ethylene-vinyl acetate copolymer (trade name: Evertate D2011, vinyl acetate content 5% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
E1: Product name: Sumilizer BP76, manufactured by Sumitomo Chemical Co., Ltd. E2: Product name: Irgaphos P168, manufactured by Ciba Specialty Chemicals Co., Ltd. E3: Product name: Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd. E4: Product name: Irganox 1010, Ciba Specialty Chemicals F1: hindered amine compound (trade name: Kimasorb 944LD, manufactured by Ciba Specialty Chemicals)
F2: hindered amine compound (trade name: Tinuvin 622LD, manufactured by Ciba Specialty Chemicals)
G1: Trade name: Sumisorb 130 Sumitomo Chemical Co., Ltd. H1: Diglycerin sesquioleate H2: Mixture of monoglycerin monostearate / diglycerin sesquistearate = 3/7 J3: Lithium aluminum composite hydroxide condensation Silicate (trade name: Fujirain manufactured by Fuji Chemical Industry Co., Ltd.)
Structural formula: [LiAl ₂ (OH) ₆ ] _2. [Si ₂ O ₅ .dH ₂ O], 0 ≦ d <5
K1: Fatty acid amide compound Ethylene bisoleic acid amide K2: Fatty acid amide compound Erucic acid amide L1: Sodium calcium aluminosilicate (trade name: Shilton JC-30, manufactured by Mizusawa Chemical Co., Ltd.)

Claims (1)

Component (A): an ethylene-α-olefin copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 4 to 20 carbon atoms, obtained by gel permeation chromatography measurement The Q value calculated from the chain length distribution is 3 or more, and the melt flow rate (MFR; unit is g / 10 minutes) and the melt tension at 190 ° C. (MT; unit is cN). An ethylene-α-olefin satisfying the relationship of the following formula (1), wherein the intrinsic viscosity ([η]; the unit is dl / g) and the MFR satisfy the relationship of the following formula (2) 70-99.9% by weight of copolymer,
2 x MFR ^-0.59 <MT <20 x MFR ^-0.59 Formula (1)
1.02 × MFR ^−0.094 <[η] <1.50 × MFR ^−0.156 Formula (2)
Component (B): Inorganic compound represented by the following formula (A), (I) or (U) 30 to 0.1% by weight
An olefin-based resin composition comprising:
_{^{[{Mg y5 M 2+ y6}}} 1-β Al β (OH) 2] β + · [A n- zβ / n · fH 2 O] β- ( A)
(Wherein M ²⁺ is, Zn, ^{.A n-} is showing a divalent metal ion of at least one of Ca and Ni .Beta showing a n-valent anion, y5, y6 and b satisfy the following conditions.)
0 ≦ β <0.5, y5 + y6 = 1, y5 ≦ 1, y6 <1, 0 ≦ f <2.
[{Mg _y1 M ²⁺ _y2 } _1-x Al _x (OH) ₂ ] ^{x +} · [(A) _z1 · (B) _z2 · bH ₂ O] ^x− (A)
( ^Wherein M ²⁺ represents one or more divalent metal ions selected from Zn, Ca, and Ni. A represents at least one of silicon-based, phosphorus-based, and boron-based oxygenate ions. B represents at least one anion other than A, and x, y1, y2, z1, z2, and b satisfy the following conditions.)
0 <x ≦ 0.5, y1 + y2 = 1, y1 ≦ 1, y2 <1, 0 <z1, 0 ≦ z2, 0 ≦ b <2.
[{Li _y3 G ²⁺ _y4 } Al ₂ (OH) ₆ ] ^{α +} · [(C) _z3 · (D) _z4 · dH ₂ O] ^α− (U)
(In the formula, G ²⁺ represents one or more divalent metal ions selected from Mg, Zn, Ca, and Ni. C represents at least one of silicon-based, phosphorus-based, and boron-based multimeric oxygenate ions. D represents at least one anion other than C, and α, y3, y4, z3, z4, and d satisfy the following conditions.)
α = y3 + 2y4, 0 <y3 ≦ 1, 0 ≦ y4 ≦ 1, 0.5 ≦ (y3 + y4) ≦ 1, 0 <z3, 0 ≦ z4, 0 ≦ d <5