JP2012082412A - Foamed film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamed film which is good in rigidity and foamed state and excellent in surface appearance and heat insulation property.SOLUTION: The foamed film includes a polyethylene-based resin composition which has a density of 930-960 kg/m, a melt flow rate of 0.1-20 g/10 min at 190°C and at a load of 2.16 kg, and a die swell at 190°C of 1.30-2.00.

Description

  The present invention relates to a foam film. More specifically, the present invention relates to a foamed film having a good surface appearance and foamed state.

Foamed film has a beautiful luster, moderate flexibility and mechanical strength, and is conventionally suitable as a packaging film, a decorative film, a tape substrate, a woven fabric substrate, etc. Is used. Above all, it is suitable for wrapping gifts, gifts, memorabilia, and chilled frozen foods.
As a method for obtaining the foamed film, a method using a specific propylene-based resin composition as a shrink label to be attached to the body of a beverage container such as a glass bottle or a PET bottle (for example, see Patent Document 1), a specific physical property A shrink label foam film (for example, see Patent Document 2) and a method using a specific propylene-based resin composition that has been further improved (for example, see Patent Documents 3 to 5) are disclosed.
Both are foamed films made of propylene-based resin, but it is extremely difficult to obtain a highly foamed foamed film with good surface appearance and foamed state.
Therefore, in order to solve such a problem, examination of a foamed film using a polyethylene resin as a raw material has been attempted.
Among the polyethylene resins, low density polyethylene has a long chain branch having an appropriate length in its molecular chain, and therefore has a relatively high melt viscosity upon melting due to the entanglement of the molecular chains. Also, the change in crystallinity near the melting point is more gradual than other ethylene resins. For this reason, although it is necessary to adjust the temperature within a narrow temperature range near the melting point, low density polyethylene can be foamed relatively easily as compared with other polyethylene resins.

However, since a problem that the surface smoothness of the foamed film using low-density polyethylene as a raw material becomes extremely poor is mentioned, a method using linear low-density polyethylene (for example, see Patent Document 6) is disclosed.
However, even if the low-density polyethylene resin described here is used, the rigidity is low and the foamed state is good, but it is extremely difficult to obtain a foamed film with excellent surface appearance and design. It was unsuitable for high-grade packaging applications.
On the other hand, high-density polyethylene has a very low melt viscosity at the time of melting because there are few branches in the molecular chain, and also has a high crystallinity and a high crystallization speed. In order to obtain a viscosity, it is necessary to adjust the temperature range more narrowly. Therefore, it is very difficult to obtain a foamed film by foaming high-density polyethylene and having a good foamed state and excellent surface appearance and design. It was difficult.

Japanese Patent Laid-Open No. 2007-2058 JP 2007-84696 A JP 2009-179647 A JP 2009-263438 A JP 2009-299012 A JP 2003-268147 A

L.A.UTRACKI, translated by Toshio Nishi, "Polymer Alloy and Polymer Blend", Tokyo Chemical Doujin, 1st Edition, December 6, 1991, p. 75

Therefore, as a result of paying attention to die swell, which is one of the indices of melt elastic properties, it was possible to obtain a foamed film having a good foamed state.
The problem to be solved by the present invention is to provide a foamed film having good rigidity and foamed state and excellent surface appearance and heat insulating properties.

  As a result of intensive studies to solve the above problems, the present inventor preferably includes a linear polyethylene (α) and a high-pressure low-density polyethylene (β), and has a specific physical property. The present inventors have found that a foamed film comprising a product can be adapted to the solution of the above problems, and have come to make the present invention based on this finding.

That is, this invention relates to the foamed film which comprises the polyethylene-type resin composition which has a specific physical property.
[1]
Polyethylene resin composition having a density of 930 to 960 kg / m ³ , 190 ° C., a melt flow rate of 0.1 to 20 g / 10 min at a load of 2.16 kg, and a die swell of 1.30 to 2.00 at 190 ° C. A foamed film comprising:
[2]
The foamed film according to [1], wherein the polyethylene-based resin composition has strain-hardening properties in measurement of elongational viscosity and has a strain-hardening degree (λmax) of 2.0 to 30.
[3]
The polyethylene resin composition satisfies the following requirements 1) to 4): [1] or [2].
1) 90 to 40% by mass of linear polyethylene (α) and 10 to 60% by mass of high-pressure low-density polyethylene (β) are included.
2) The melting point peak of the endothermic curve obtained in the temperature rise measurement by the differential scanning calorimeter is one.
3) The melt tension ratio (MTR ₁ ) represented by the following formula [1] is 2.5 or more.
MTR ₁ = (MT ₁₆₀ ° C.) / (MT ₁₉₀ ° C.) [1]
(However, in the above formula [1], the subscript of MT is the measurement temperature of melt tension.)
4) The tensile elastic modulus is 400 MPa or more.
[4]
The linear polyethylene (α) satisfies the following requirements (α-1) to (α-4), and the high-pressure method low-density polyethylene (β) is represented by the following (β-1) to (β-3). The foamed film according to any one of [1] to [3], which satisfies the above requirement.
(Α-1) An ethylene homopolymer or a copolymer comprising a repeating unit derived from ethylene and a repeating unit derived from one or two or more α-olefins having 3 to 20 carbon atoms.
(Α-2) The density is 935 to 975 kg / m ³ .
(Α-3) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 20 g / 10 min.
((Alpha) -4) Mw / Mn calculated | required by the gel permeation chromatography method is 3-7.
(Mn is a number average molecular weight, Mw is a weight average molecular weight, and Mw / Mn is an index representing a molecular weight distribution.)
(Β-1) The density is 910 to 930 kg / m ³ .
(Β-2) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 10 g / 10 min.
(Β-3) Molecular weight distribution determined by gel permeation chromatograph: Mw / Mn is 8-24.
[5]
The linear polyethylene (α) comprises (a) a carrier material, (b) an organoaluminum, (c) a transition metal compound having a cyclic η-binding anion ligand, and (d) the cyclic η-binding anion arrangement. It is produced by polymerization using a metallocene-supported catalyst [I] prepared from an activator capable of reacting with a transition metal compound having a ligand to form a complex that exhibits catalytic activity, and a liquid promoter component [II]. The foam film according to any one of [1] to [4].
[6]
The foamed film according to any one of [1] to [5], wherein the high-pressure low-density polyethylene (β) satisfies the following requirement (β-4).
(Β-4) The melt tension ratio (MTR ₂ ) represented by the following formula [2] is 0.7 or more, and the relationship between the melt flow rate ratio (FRR) and the melt tension (MT) is [3] is satisfied.
MTR ₂ = (MT ₂₄₀ ° C.) / (MT ₁₉₀ ° C.) [2]
(MT ₁₉₀ ° C.) ≧ 0.65 (FRR) −20 [3]
(However, in the above formulas [2] and [3], the subscript of MT is the measurement temperature of melt tension, FRR is MFR at temperature = 190 ° C., load = 21.6 kg, temperature = 190 ° C., load = (The value divided by MFR at 2.16 kg.)
[7]
Apparent density is 180 g / L or more and 800 g / L or less, and thickness is 10-500 micrometers, The foamed film in any one of [1]-[6] characterized by the above-mentioned.
[8]
The method for producing a foamed film according to any one of [1] to [7], wherein the polyethylene-based resin composition is molded by an inflation molding method or a T-die molding method.

  The foamed film comprising the polyethylene resin composition of the present invention has good rigidity and foamed state, excellent surface appearance and heat insulation, and is suitable for packaging applications.

It is an example of the plot figure of the extensional viscosity of the polyethylene-type resin composition used in one Example of this invention.

  Hereinafter, the present invention will be specifically described.

Density of the polyethylene resin composition used in the present invention is a 930~960kg / ^{m 3,} preferably 940~960kg / ^{m 3,} more preferably from 945~960kg / ^{m 3.} The density of a polyethylene-type resin composition can be measured by the method as described in the below-mentioned Example. The density of a polyethylene-type resin composition can be adjusted with each density and compounding quantity of the linear polyethylene ((alpha)) and high pressure method low density polyethylene ((beta)) to be used.

If the density of the polyethylene resin composition is 930 kg / m ³ or more, the rigidity is excellent. If the density of a polyethylene-type resin composition is 960 kg / m < ³ > or less, the foamed film which can make it compatible with favorable buffer property while being excellent in rigidity can be obtained.

  The density of the polyethylene-based resin composition is preferably within the above range in that the foamed film has excellent rigidity and can achieve both good buffering properties.

The melt flow rate (hereinafter sometimes abbreviated as “MFR”) of the polyethylene-based resin composition used in the present invention is 0.1 to 20 g / 10 min at 190 ° C. and a load of 2.16 kg, preferably 2. It is 0-10 g / 10min, More preferably, it is 4.0-8.0g / 10min. The MFR of the polyethylene resin composition can be measured by the method described in Examples described later. The MFR of the polyethylene resin composition can be adjusted by the MFR and the blending amount of the linear polyethylene (α) and the high pressure method low density polyethylene (β) to be used.
When the MFR of the polyethylene-based resin composition is 0.1 g / 10 min or more and 20 g / 10 min or less, the foamed film is excellent in foam molding processability.
The polyethylene-based resin composition used in the present invention has a die swell at 190 ° C. of 1.30 to 2.00, preferably 1.40 to 1.90, more preferably 1.50 to 1.80. . When the die swell at 190 ° C. is in the range of 1.30 to 2.00, the foamed state is good and the surface appearance and heat insulation are excellent. This is because if the die swell at 190 ° C. of the polyethylene resin composition is too small, the foam stability at the time of foaming is lowered and foam breakage occurs, the foamed state is good, and the surface appearance and heat insulation are excellent. Can not get a foam film. Further, when the foam film is manufactured, the width of the foam film becomes narrower or is easily cut by necking when the foam film comes out of the annular die, and it becomes difficult to cope with the wide foam film. Further, if the die swell at 190 ° C. is too large, the shrinkage after the molding of the foamed film is large, and the stretchability is low, so that stable molding into a desired shape becomes difficult, so the above range is appropriate. .

  The die swell of the polyethylene-based resin composition used in the present invention can be set in the range of 1.30 to 2.00, for example, by adjusting the molecular weight distribution, molecular weight, density, and the like of the resin composition. The polyethylene-based resin composition preferably comprises linear polyethylene (α) and high-pressure method low-density polyethylene (β), but each die swell, melt tension, MFR, density, or both The die swell of the composition can be adjusted to a range of 1.30 to 2.00 by adjusting the ratio of the above characteristics and the amount of each compound.

The die swell of the polyethylene-based resin composition at 190 ° C. refers to that measured by the method described in JIS K7199: 1999 “Plastic-capillary rheometer and plastic flow characteristic test method using slit direometer”. In addition, the die swell in 190 degreeC of a polyethylene-type resin composition can be measured using the Toyo Seiki Seisakusho Capillograph. Specifically, a polyethylene resin composition to be a measurement sample is supplied into a capillograph cylinder and heated and melted to 190 ° C., and this heated and melted polyethylene resin composition is subjected to a capillary die (inner diameter: 2.095 mm, From a length of 8 mm and an inflow angle of 90 °, the piston is extruded in a string at a constant speed of 10 mm / min. And the diameter of this string-like thing is measured at 190 degreeC, and the die swell in 190 degreeC of a polyethylene-type resin composition is computed based on a following formula.
Die swell of polyethylene resin composition at 190 ° C. = string diameter (mm) / capillary die inner diameter (mm)

When the resin composition has a shape such as powder or pellet, it can be measured as it is by the above method, but when the resin composition is in the shape of a film, after performing operations such as cutting, The die swell can be measured by the above method.
The polyethylene resin composition used in the present invention preferably has a strain hardening property in the measurement of elongational viscosity.
Although melt tension is improved by increasing the molecular weight of the resin (decreasing the melt flow rate), conventional polyethylene resins do not exhibit strain hardening in uniaxial elongational flow, and both are regarded as the same. Can not. In foam molding, the process from the bubble growth stage until the bubbles are fixed by cooling is an elongation flow of the resin, and a sudden increase in viscosity accompanying deformation of the resin, a so-called strain hardening phenomenon is important. When bubbles grow, in the case of strain-hardening polyethylene resin, even if only a part of the bubble is deformed, the viscosity of that part rapidly increases with the deformation, and the surrounding area is stretched. A foam holding air bubbles independent of the film is obtained.
As for the polyethylene-type resin composition used by this invention, the strain hardening degree ((lambda) max) in the measurement of an extensional viscosity has preferable 2.0-30, More preferably, it is 5.0-25, More preferably, it is 10-20. When the degree of strain hardening (λmax) is in the range of 2.0 to 30, the foamed state is good and the surface appearance and heat insulation are excellent.
It is effective to use the strain hardening degree (λmax) obtained from the measurement of the extensional viscosity as one of the foaming indices of the resin, and the strain hardening degree (λmax) is an index representing the strength at the time of melting. Large values have the effect of improving melt tension. The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is generally affected by the amount of branching and the length of the branched chain. Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.
Here, as to the method for measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial extensional viscosity can be measured. For example, details of the measuring method and the measuring instrument are known in the art: Polymer. 42 (2001) 8663, and preferable measuring methods and measuring instruments include the following.
(Measuring method)
Equipment: ARES manufactured by TA Instruments
Jig: Ext. Viscosity Fixture (EVF) Elongation Viscosity Measurement Jig Measurement Temperature: 134 ° C
Strain rate: 0.5 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and thickness 0.7 mm is formed by press molding.
(Calculation method)
The elongational viscosity at a strain rate of 0.5 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongational viscosity ηE (Pa · second) on the vertical axis. On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line to obtain the maximum value (ηmax) of the extensional viscosity ηE, and the viscosity on the approximate straight line up to that time is ηlin. FIG. 1 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The polyethylene resin composition used in the present invention is preferably composed of linear polyethylene (α) and high-pressure low-density polyethylene (β). The blending ratio of the linear polyethylene (α) and the high pressure method low density polyethylene (β) is preferably 90 to 40% by mass of the linear polyethylene (α) and 10 to 60% by mass of the high pressure method low density polyethylene (β). More preferably, the linear polyethylene (α) is 85 to 55% by mass, and the high-pressure method low-density polyethylene (β) is 15 to 45% by mass. More preferably, the linear polyethylene (α) is 80 to 70% by mass, the high-pressure method. It is 20-30 mass% of low density polyethylene ((beta)).
When the blending ratio of the high-pressure method low density polyethylene (β) is 10% by mass or more and 60% by mass or less, it is easy to obtain a foamed film having good rigidity and foamed state and excellent surface appearance and heat insulation. Can do.
It is preferable that the melting point peak of the endothermic curve obtained in the temperature rise measurement by the differential scanning calorimeter of the polyethylene resin composition used in the present invention is one. Thus, it is presumed that the linear polyethylene (α) and the high-pressure method low-density polyethylene (β) can be made in a compatible state and the crystal state of both can be prevented from phase separation. For this reason, it is possible to obtain a foamed film having a good foamed state and excellent surface appearance and heat insulation.
The endothermic curve in the temperature rise measurement of the polyethylene resin composition can be obtained by the same method as the measurement method for linear polyethylene (α) described later. Usually, linear polyethylene (α) and high-pressure low-density polyethylene (β) have low compatibility, but by using linear polyethylene (α) with a narrow molecular weight distribution, a resin composition having a single melting point peak is obtained. Obtainable. By using linear polyethylene (α) having a narrow molecular weight distribution, the compatibility between the two is considered to be enhanced.
The melt tension ratio (hereinafter abbreviated as MTR ₁ ) of the polyethylene-based resin composition used in the present invention is represented by the following formula [1], and its value is 2.5 or more from the viewpoint of excellent foaming state. Preferably, it is 3.0 or more. On the other hand, the upper limit is preferably 5.0 or less, more preferably 4.0 or less, from the viewpoint of excellent foaming.
MTR ₁ = (MT ₁₆₀ ° C.) / (MT ₁₉₀ ° C.) [1]
(However, in the above formula [1], the subscript of MT is the measurement temperature of melt tension.)
Here, MTR ₁ of 2.5 or more indicates that the melt tension value of the resin composition is greatly different from the processing temperature, and the resin composition has a melt extrusion temperature of 190 ° C. at a high temperature. While the melt tension is low, the melt tension of the resin composition is very high at a low temperature of 160 ° C., which is close to the processing temperature of foam molding. Since the melt tension of the polyethylene resin composition is extremely high in a low temperature region close to the processing temperature of foam molding, a foamed film having a good foamed state and excellent surface appearance and heat insulating properties can be obtained. On the other hand, if MTR ₁ is 5.0 or less, it is possible to effectively suppress the phenomenon that the MTR ₁ value is too large, so that the bubble growth is slowed during foaming and the foaming state does not proceed. As described above, the polyethylene resin composition used in the present invention preferably has MTR ₁ in the above range from the viewpoint of foam molding processability that affects the buffering property.
As for the tensile elasticity modulus of the polyethylene-type resin composition which comprises this foamed film of this invention, 400 Mpa or more is preferable. When it is less than 400 MPa, a foam film having low rigidity is obtained. From the viewpoint of increasing the rigidity of the foam film, 500 MPa or more is more preferable, and 700 MPa or more is more preferable.
On the other hand, the upper limit is that if the tensile modulus is too high, the buffering properties are reduced, and the contents may be damaged when used as a packaging container or the like. Therefore, the tensile modulus is preferably 1500 MPa or less, and 1200 MPa or less. Is more preferable, and 1000 MPa or less is more preferable.
The tensile elastic modulus of the polyethylene resin composition was measured according to JIS K7161 (1994).

  The polyethylene-based resin composition preferably has a melt tension at 190 ° C. of at least 10 mN from the viewpoint of processing into a foam film. The range of the melt tension at 190 ° C. is more preferably 10 to 40 mN, still more preferably 20 to 30 mN. If it is 10 mN or more, the foaming state of a foamed film is favorable. The polyethylene-based resin composition containing linear polyethylene (α) having specific physical properties and high-pressure low-density polyethylene (β) preferably used in the present invention has a relatively low melt tension at a high temperature of 190 ° C. Nevertheless, it is surprisingly high at a low temperature of 160 ° C. In the low temperature range close to the processing temperature of foam molding processing, the melt tension of the polyethylene resin composition is high, so it is possible to obtain a foam film with a good foamed state and excellent surface appearance and heat insulation. it can.

The polyethylene-based resin composition having such characteristics includes a high-pressure low-density polyethylene having a narrow molecular weight distribution (Mw / Mn) and a linear polyethylene (α) having a narrow molecular weight distribution and a broad molecular weight distribution, and generally having more branched side chains. It can be obtained by blending (β). When a conventional general Ziegler catalyst type linear polyethylene and a high pressure method low density polyethylene are mixed, both are incompatible, and the crystal state of both phase separates. It is difficult to obtain a resin composition having a high melt tension ratio (MTR ₁ ).

On the other hand, since the polyethylene resin composition is a specific polyethylene resin composition having a melt tension ratio (MTR ₁ ) of 2.5 or more, the foamed state is good and the surface appearance and heat insulation are excellent. It has a feature that a foamed film can be obtained.

(Linear polyethylene (α))
The linear polyethylene (α) preferably used for the polyethylene resin composition is an ethylene homopolymer or a repeating unit derived from ethylene and a repeating unit derived from one or more α-olefins having 3 to 20 carbon atoms. A copolymer consisting of “Linear” polyethylene is a concept that excludes conventional high-pressure low-density polyethylene, and is a concept that includes any other polyethylene.

  Examples of the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. 1-octadecene, 1-eicocene, 3-methyl-1-butene, 4-methyl-1-pentene, 6-methyl-1-heptene and the like. As the α-olefin, 1-butene, 1-hexene and 1-octene are preferable because they are generally easily available, and 1-butene is preferable in consideration of the polymerization process.

  The copolymer may be a copolymer of ethylene and one kind of α-olefin, or may be a copolymer of ethylene and an α-olefin obtained by combining two or more kinds. The linear polyethylene (α) may be a copolymer obtained by dry blending or melt blending a copolymer of ethylene and α-olefin and a copolymer of ethylene and another α-olefin at an arbitrary ratio. Good.

The density of the linear polyethylene (α) used in the present embodiment is preferably 935 to 975 kg / m ³ . The density of the linear polyethylene (α) is more preferably 940 to 965 kg / m ³ , and still more preferably 945 to 960 kg / m ³ .

Density linear polyethylene (alpha) is 935 kg / m ³ or more, if 975 kg / m ³ or less, when used in foamed film, since it is possible to achieve both good cushioning is excellent in rigidity, It is preferable to be within the above range.
In the present embodiment, the density can be measured by the method described in the following examples. Moreover, the density of the linear polyethylene (α) in the resin composition can be measured by fractionating the linear polyethylene by a method such as a cross fractionation chromatography method (CFC method).

  The MFR of the linear polyethylene (α) used in the present embodiment is preferably 0.1 to 20 g / 10 min at 190 ° C. and a 2.16 kg load. MFR of linear polyethylene ((alpha)) becomes like this. More preferably, it is 1-15 g / 10min, More preferably, it is 5-10 g / 10min.

When the MFR of the linear polyethylene (α) is 0.1 g / 10 min or more and 20 g / 10 min or less, the foamed film has excellent foam molding processability.
In the present embodiment, MFR can be measured by the method described in the following examples. Moreover, MFR of linear polyethylene ((alpha)) in a resin composition can be calculated | required from the compounding ratio of MFR and linear polyethylene of a resin composition.

  In the gel permeation chromatography method, the molecular weight distribution (Mw / Mn) of the linear polyethylene (α) used in the present embodiment is preferably 3-7, more preferably 3-6. It is. In the case of linear polyethylene obtained using a Ziegler catalyst which is a general catalyst, the molecular weight distribution is at least about 8-9, but by using a specific catalyst described later, a linear polyethylene having a narrow molecular weight distribution. Can be obtained.

  If the molecular weight distribution of the linear polyethylene (α) is within the above range, due to the uniformity of the molecular weight, the good compatibility state and foaming state are good, and the surface appearance and heat insulation are excellent. A foam film can be obtained.

  In particular, if the molecular weight distribution of the linear polyethylene (α) is 7 or less, a conventional general Ziegler-Natta catalyst is used in a blend of the linear polyethylene (α) and the high pressure method low density polyethylene (β). Unlike the case of the polymerized ethylene homopolymer or the copolymer of ethylene and α-olefin, the linear polyethylene (α) and the high pressure method low density polyethylene (β) may be in a good compatible state. It is presumed that it is possible to suppress phase separation of both crystal states. For this reason, it is possible to obtain a foamed film having a good foamed state and excellent surface appearance and heat insulation.

  In the present embodiment, the molecular weight distribution can be determined by gel permeation chromatography, and more specifically can be measured by the method described in the following examples. In addition, the molecular weight distribution of the linear polyethylene (α) in the resin composition can be measured by a method such as a cross-fractionation chromatography method (CFC method).

The linear polyethylene (α) used in the present invention is preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin, and preferably has a molecular weight distribution (Mw / Mn) of 3 to 7. narrow. For this reason, it is guessed that the subject of the present invention is achieved when the molecular weight becomes uniform.
The crystallization temperature, which is the melting point peak of the endothermic curve and the peak of the exothermic curve of the linear polyethylene (α) used in the present invention, can be determined in the temperature rise measurement and the temperature fall measurement using a differential scanning calorimeter, respectively.
It is preferable that the melting point peak of the endothermic curve obtained in the temperature rising measurement of the linear polyethylene (α) with a differential scanning calorimeter is one. Thus, it is presumed that the linear polyethylene (α) and the high-pressure method low-density polyethylene (β) can be made in a compatible state and the crystal state of both can be prevented from phase separation. For this reason, it is possible to obtain a foamed film having a good foamed state and excellent surface appearance and heat insulation.
The differential scanning calorimeter can be measured using a differential scanning calorimeter (Perkin Elmer DSC-7 type apparatus) under the following conditions. 1) About 5 mg of a polymer sample is packed in an aluminum pan, heated to 200 ° C. at 200 ° C./min, and held at 200 ° C. for 5 minutes. 2) Next, the temperature is lowered from 200 ° C. to 50 ° C. at a temperature lowering rate of 10 ° C./min, and held for 5 minutes after the temperature lowering is completed. 3) Next, the temperature is increased from 50 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. From the exothermic curve observed in the process of 2), the maximum temperature at the exothermic peak position can be obtained as the crystallization temperature (° C.). Further, the maximum temperature at the melting peak position can be determined as the melting point peak (° C.) from the endothermic curve observed in the process of 3).

The production method of the linear polyethylene (α) can be produced by the method described below as a first preferred embodiment.
The linear polyethylene (α) obtained by this production method is characterized by a narrow Mw / Mn and molecular weight distribution obtained by gel permeation chromatography.
A preferred method for producing the linear polyethylene (α) is a method of producing a polyolefin by single-stage polymerization of an α-olefin, and the catalyst used for the polymerization is a solid catalyst [A] and an organometallic compound [ B], and the solid catalyst [A] is represented by an organic magnesium compound (a-1) that is soluble in an inert hydrocarbon solvent represented by the following general formula (1) and the following general formula (2): The carrier (A-1) prepared by the reaction with the chlorinating agent (a-2) is reacted with alcohol (A-2), and then an organometallic compound represented by the following general formula (3) ( A-3) is reacted, and then prepared by supporting a titanium compound (A-4) represented by the following general formula (4). The organometallic compound [B] is represented by the following general formula ( 5) and the following general formula (6) A polyolefin production method, which belongs to the group consisting of an organomagnesium compound that is soluble in an inert hydrocarbon solvent.
(M ¹ ) _α (Mg) _β (R ¹ ) _a (R ² ) _b (OR ³ ) _c- (1)
(In the formula, M ¹ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ , R ² and R ³ are each a carbon number. 2 or more and 20 or less, and α, β, a, b and c are real numbers satisfying the following relationship: 0 ≦ α, 0 <β, 0 ≦ a, 0 ≦ b, 0 <c, 0 <a + b, 0 <c / (α + β) ≦ 2, kα + 2β = a + b + c (where k is the valence of M ¹ ))
_{^{H d SiCl e R 4 (4-}} (d + e)) - (2)
(Wherein R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and d and e are numbers satisfying the following relationship: 1 ≦ d, 1 ≦ e, 2 ≦ d + e ≦ 4)
_{^{M 2 R 5 f Q (h}} -f) - (3)
(Wherein M ² is a metal atom belonging to Groups I to III of the Periodic Table, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Q is OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R. ¹¹ , SR ¹² and a group belonging to the group consisting of halogen, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms or hydrocarbon groups, and f is greater than 0 A real number and h is the valence of M ² )
_{^{Ti (OR 13) i X (}} 4-i) - (4)
(In the formula, i is a real number of 0 or more and 4 or less, R ¹³ is a hydrocarbon group of 1 to 20 carbon atoms, and X is a halogen atom.)
R ¹⁴ _(3-j) AlQ ′ _j − (5)
(Wherein R ¹⁴ is a hydrocarbon group having 1 to 12 carbon atoms, Q ′ is a group belonging to the group consisting of a hydrogen atom, a halogen atom, and OR ¹⁵ , and R ¹⁵ is a group having 1 to 20 carbon atoms. And j is a real number of 0 or more and 2 or less)
(M ³ ) _γ (Mg) _δ (R ¹⁵ ) _m (R ¹⁶ ) _n- (6)
(In the formula, M ³ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹⁵ and R ¹⁶ each have 2 to 20 carbon atoms. The following hydrocarbon groups, γ, δ, m, and n are real numbers that satisfy the following relationship: 0 ≦ γ, 0 <δ, 0 ≦ k, 0 ≦ m, pγ + 2δ = m + n (where p is M Valence of ³ ))

  Next, the solid catalyst [A] will be described.

An organic magnesium compound (a-1) in which the solid catalyst [A] is soluble in an inert hydrocarbon solvent represented by the following general formula (1) and a chlorinating agent represented by the following general formula (2) ( The carrier (A-1) prepared by the reaction with a-2) is reacted with alcohol (A-2), and then an organoaluminum compound (A-3) represented by the following general formula (3) It is prepared by reacting and then supporting a titanium compound (A-4) represented by the following general formula (4).
(M ¹ ) _α (Mg) _β (R ¹ ) _a (R ² ) _b (OR ³ ) _c- (1)
(In the formula, M ¹ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ , R ² and R ³ are each a carbon number. 2 or more and 20 or less, and α, β, a, b and c are real numbers satisfying the following relationship: 0 ≦ α, 0 <β, 0 ≦ a, 0 ≦ b, 0 <c, 0 <a + b, 0 <c / (α + β) ≦ 2, kα + 2β = a + b + c (where k is the valence of M ¹ ))
_{^{H d SiCl e R 4 (4-}} (d + e)) - (2)
(Wherein R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and d and e are numbers satisfying the following relationship: 1 ≦ d, 1 ≦ e, 2 ≦ d + e ≦ 4)
_{^{M 2 R 5 f Q (h}} -f) - (3)
(Wherein M ² is a metal atom belonging to Groups I to III of the Periodic Table, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Q is OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R. ¹¹ , SR ¹² and a group belonging to the group consisting of halogen, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms or hydrocarbon groups, and f is greater than 0 A real number and h is the valence of M ² )
_{^{Ti (OR 13) i X (}} 4-i) - (4)
(In the formula, i is a real number of 0 or more and 4 or less, R ¹³ is a hydrocarbon group of 1 to 20 carbon atoms, and X is a halogen atom.)

  Next, the inert hydrocarbon solvent will be described. The inert hydrocarbon solvent is an aliphatic hydrocarbon compound such as pentane, hexane or heptane, an aromatic hydrocarbon compound such as benzene or toluene, or an alicyclic hydrocarbon compound such as cyclohexane or methylcyclohexane. A hydrocarbon is preferred.

  Next, the organomagnesium compound that is soluble in the inert hydrocarbon solvent represented by the general formula (1) will be described. This organomagnesium compound is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds It is. The relational expression kα + 2β = a + b + c of the symbols α, β, a, b, c indicates the stoichiometry between the valence of the metal atom and the substituent.

In the general formula (1), the hydrocarbon group represented by R ¹ to R ² is an alkyl group, a cycloalkyl group or an aryl group, and examples thereof include methyl, ethyl, propyl, butyl, propyl, hexyl, octyl, Examples include decyl, cyclohexyl, and phenyl groups, and preferably R ¹ to R ² are alkyl groups. When α> 0, as the metal atom M ¹ , a metal element belonging to Groups I to III of the periodic table can be used, and examples thereof include lithium, sodium, potassium, beryllium, zinc, boron, and aluminum. However, aluminum, boron, beryllium, and zinc are particularly preferable.

The ratio β / α of magnesium to the metal atom M ¹ can be arbitrarily set, but is preferably in the range of 0.1 to 30, particularly 0.5 to 10. Further, when a certain organomagnesium compound in which α = 0 is used, for example, when R ¹ is 1-methylpropyl or the like, it is soluble in an inert hydrocarbon solvent, and such a compound is also used in the present invention. Gives favorable results. In the general formula (M ¹ ) _α (Mg) _β (R ¹ ) _a (R ² ) _b (OR ³ ) _c , R ¹ and R ² when α = 0 are the following three groups (1), It is recommended that it is any one group of (2) and (3).

(1) At least one of R ¹ and R ² is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably R ¹ and R ² are both 4 to 6 carbon atoms, At least one is a secondary or tertiary alkyl group.
(2) R ¹ and R ² are alkyl groups having different carbon atoms, preferably R ¹ is an alkyl group having 2 or 3 carbon atoms, and R ¹ is an alkyl having 4 or more carbon atoms. Be a group.
(3) At least one of R ¹ and R ² is a hydrocarbon group having 6 or more carbon atoms, preferably an alkyl group that becomes 12 or more when the number of carbon atoms contained in R ¹ and R ² is added. .

  These groups are specifically shown below. As the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (1), 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2-methylbutyl, 2-ethylpropyl, 2 , 2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group and the like are used, and 1-methylpropyl group is particularly preferable. Next, in (2), examples of the alkyl group having 2 or 3 carbon atoms include ethyl, 1-methylethyl, propyl and the like, and an ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include butyl, pentyl, hexyl, heptyl, octyl group and the like, and butyl and hexyl groups are particularly preferable.

  Furthermore, examples of the hydrocarbon group having 6 or more carbon atoms in (3) include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like. Among the hydrocarbon groups, an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable. In general, an increase in the number of carbon atoms contained in an alkyl group facilitates dissolution in an inert hydrocarbon solvent. However, the use of an unnecessarily long alkyl group is not preferred in terms of handling because the solution viscosity increases. The organomagnesium compound is used as an inert hydrocarbon solution, but it can be used as long as a trace amount of Lewis basic compounds such as ethers, esters, and amines are contained or remain in the solution.

Next, the alkoxy group (OR ³ ) will be described. The hydrocarbon group represented by R ³ is preferably an alkyl group or aryl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group or aryl group having 3 to 10 carbon atoms. Specifically, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2-ethylbutyl, 2-ethylpentyl, Examples include 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, nonyl, decyl, phenyl, naphthyl groups, and the like. Butyl, 1-methylpropyl, 2 -Methylpentyl and 2-ethylhexyl groups are particularly preferred.

These organomagnesium compounds include an organomagnesium compound belonging to the group consisting of the general formulas R ¹ MgX and R ¹ ₂ Mg (R ¹ is as defined above, X is a halogen), and the general formula M ¹ R ² _k And an organometallic compound belonging to the group consisting of M ¹ R ² _(k-1) H (M ¹ , R ² , k are as defined above) in an inert hydrocarbon solvent at room temperature to 150 ° C. An alkoxymagnesium compound having a hydrocarbon group represented by R ³ that is soluble in an alcohol having an hydrocarbon group represented by R ³ or an inert hydrocarbon solvent, if necessary, and the like. It is synthesized by the method of reacting.

  Among these, when reacting an organomagnesium compound soluble in an inert hydrocarbon solvent with an alcohol, the order of the reaction is such that the alcohol is added to the organomagnesium compound, or the organomagnesium compound is added to the alcohol. Any method can be used, or a method of adding both at the same time. In the present invention, the reaction ratio between the organomagnesium compound soluble in the inert hydrocarbon solvent and the alcohol is not particularly limited, but as a result of the reaction, the alkoxy group-containing organomagnesium compound in the resulting alkoxy group-containing organomagnesium compound contains all of the alkoxy groups. The range of the molar composition ratio c / (α + β) is 0 ≦ c / (α + β) ≦ 2, and 0 ≦ c / (α + β) <1 is particularly preferable.

Next, the chlorinating agent preferably used will be described.
The chlorinating agent preferably used when synthesizing (A-1) is represented by the following general formula (2), and at least one is a silicon chloride compound having a Si—H bond.
^{_{H d SiCl e R 4 (4-}} (d + e)) - (2)
(Wherein R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and d and e are numbers satisfying the following relationship: 1 ≦ d, 1 ≦ e, 2 ≦ d + e ≦ 4)
In the above formula (2), the hydrocarbon group represented by R ⁴ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. For example, methyl, ethyl, propyl, 1- Examples thereof include methylethyl, butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl group, etc., preferably an alkyl group having 1 to 10 carbon atoms, and 1 carbon atom such as methyl, ethyl, propyl, 1-methylethyl group, etc. An alkyl group of ˜3 is particularly preferred. D and e are 1 or more real numbers satisfying the relationship of 2 ≦ d + e ≦ 4, and it is particularly preferable that e is 2 or more.

These compounds include HSiCl ₃ , HSiCl ₂ CH ₃ , HSiCl ₂ C ₂ H ₅ , HSiCl ₂ C ₃ H ₇ , HSiCl ₂ (1-CH ₃ C ₂ H ₅ ), HSiCl ₂ C ₄ H ₉ , HSiCl _{2 C 6 H 5, HSiCl 2 (} 4-Cl-C 6 H 4), HSiCl 2 CH = CH 2, HSiCl 2 CH 2 C 6 H 5, HSiCl 2 (1-C 10 H 7), HSiCl 2 CH 2 CH = CH ₂ , H ₂ SiClCH ₃ , H ₂ SiClC ₂ H ₅ , HSiCl (CH ₃ ) ₂ , HSiCl (C ₂ H ₅ ) ₂ , HSiClCH ₃ (1-CH ₃ C ₂ H ₅ ), HSiClCH ₃ (C _{6 H 5), HSiCl (C 6} H 5) 2 and the like, selected from these compounds or these compounds two or more mixed Silicon chloride compounds are used consisting of an object. As the silicon chloride compound, trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, and ethyldichlorosilane are preferable, and trichlorosilane and monomethyldichlorosilane are particularly preferable.

  Next, the reaction between the organomagnesium compound and the chlorinating agent that are preferably used will be described. In the reaction of the organomagnesium compound and the chlorinating agent, the chlorinating agent is previously converted into a reaction solvent body, for example, a chlorinated hydrocarbon such as an inert hydrocarbon solvent, 1,2-dichloroethane, o-dichlorobenzene, dichloromethane, or the like. It is preferably used after being diluted with an ether-based medium such as diethyl ether or tetrahydrofuran, or a mixed medium thereof. In particular, in view of the performance of the catalyst, an inert hydrocarbon solvent is preferable. In this case, although there is no restriction | limiting in particular about the temperature of reaction, For progress of reaction, Preferably it implements above the boiling point of the silicon chloride compound used as a chlorinating agent, or 40 degreeC or more. Although there is no restriction | limiting in particular also in the reaction ratio of an organomagnesium compound and a silicon chloride compound, Usually, it is 0.01-100 mol of silicon chloride compounds with respect to 1 mol of organomagnesium compounds, Preferably, with respect to 1 mol of organomagnesium compounds, It is the range of 0.1-10 mol of silicon chloride compounds.

  Regarding the reaction method, a method of simultaneous addition in which an organomagnesium compound and a silicon chloride compound are simultaneously introduced into the reactor and a reaction is performed, and after the silicon chloride compound is charged in the reactor in advance, the organomagnesium compound is introduced into the reactor. There is a method, or a method of introducing an organomagnesium compound into the reactor in advance and then introducing a silicon chloride compound into the reactor, but after introducing the silicon chloride compound into the reactor in advance, the organomagnesium compound is introduced into the reactor The method of making it preferable is. The solid component obtained by the above reaction is preferably separated by filtration or decantation, and then sufficiently washed with an inert hydrocarbon solvent to remove unreacted products or by-products.

The reaction between the organomagnesium compound and the silicon chloride compound can also be performed in the presence of a solid. This solid may be either an inorganic solid or an organic solid, but it is preferable to use an inorganic solid. The following are mentioned as an inorganic solid.
(I) Inorganic oxide (ii) Inorganic carbonate, silicate, sulfate (iii) Inorganic hydroxide (iv) Inorganic halide (v) Double salt, solid solution or mixture of (i) to (iv)

Specific examples of the inorganic solid include silica, alumina, silica / alumina, hydrated alumina, magnesia, tria, titania, zirconia, calcium phosphate, barium sulfate, calcium sulfate, magnesium silicate, magnesium / calcium, aluminum silicate [(Mg / Ca ) O · Al ₂ O ₃ · 5SiO ₂ · nH ₂ O], potassium silicate · aluminum [K ₂ O · 3Al ₂ O ₃ · 6SiO ₂ · 2H ₂ O], magnesium iron silicate [(Mg · Fe) ₂ SiO ₄ ], Aluminum silicate [Al ₂ O ₃ · SiO ₂ ], calcium carbonate, magnesium chloride, magnesium iodide, and the like, and particularly preferred are silica, silica / alumina and magnesium chloride. The specific surface area of the inorganic solid is preferably 20 m ² / g or more, particularly preferably 90 m ² / g or more.

  Next, the alcohol (A-2) that is preferably used will be described. As the alcohol (A-2), a saturated or unsaturated alcohol having 1 to 20 carbon atoms is preferable. Such alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 1-pentanol, Examples include hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, phenol, cresol, and the like, and linear alcohols having 3 to 8 carbon atoms are particularly preferable. It is also possible to use a mixture of these alcohols.

  Although there is no restriction | limiting in particular in the usage-amount of alcohol (A-2), It is preferable that it is more than 0.05 and 10 or less by molar ratio with respect to the magnesium atom contained in a support | carrier (A-1), 0.1 or more 1 or less is more preferable, and 0.2 or more and 0.5 or less are more preferable. When the amount of alcohol (A-2) used is greater than 0.05 in terms of the molar ratio to the magnesium atom contained in the support (A-1), the Si-containing component contained in the catalyst support is efficiently removed. This is preferable because the catalytic properties are improved. Moreover, when the usage-amount of alcohol (A-2) is 10 or less by the molar ratio with respect to the magnesium atom contained in a support | carrier (A-1), an excess alcohol remains in a catalyst, and catalyst characteristics are obtained. This is preferable because the phenomenon of lowering can be suppressed. Furthermore, when the amount of alcohol (A-2) used is 0.2 or more and 0.5 or less in terms of a molar ratio to the magnesium atom contained in the carrier (A-1), the catalyst characteristics are improved. This is preferable because an appropriate amount of alcohol remaining in the catalyst remains in the catalyst. The reaction of the carrier (A-1) and the alcohol (A-2) can be carried out in the presence or absence of an inert hydrocarbon solvent. Although there is no restriction | limiting in particular in the temperature at the time of reaction, It is preferable to implement in 25 to 200 degreeC.

Next, the organometallic compound (A-3) that is preferably used will be described.
This organometallic compound (A-3) is represented by the following general formula (3).
^{_{M 2 R 5 f Q (h}} -f) - (3)
(Wherein M ² is a metal atom belonging to Groups I to III of the Periodic Table, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Q is OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R. ¹¹ , SR ¹² and a group belonging to the group consisting of halogen, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms or hydrocarbon groups, and f is greater than 0 A real number and h is the valence of M ² )

M ² is a metal atom belonging to Groups I to III of the Periodic Table, and examples thereof include lithium, sodium, potassium, beryllium, magnesium, boron, aluminum, and the like, and magnesium, boron, and aluminum are particularly preferable. The hydrocarbon group represented by R ⁵ is an alkyl group, a cycloalkyl group or an aryl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a cyclohexyl group and a phenyl group. Is an alkyl group.

Q represents a group belonging to the group consisting of OR ⁶ , OSiR ⁷ R ⁸ R ⁹ , NR ¹⁰ R ¹¹ , SR ¹² and halogen, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² Is a hydrogen atom or a hydrocarbon group, and Q is particularly preferably halogen.

  Examples of the organometallic compound (A-3) include methyllithium, butyllithium, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, butylmagnesium chloride, butyl Magnesium bromide, butylmagnesium iodide, dibutylmagnesium, dihexylmagnesium, triethylboron, trimethylaluminum, dimethylaluminum bromide, dimethylaluminum chloride, dimethylaluminum methoxide, methylaluminum dichloride, methylaluminum sesquichloride, triethylaluminum, diethylaluminum chloride, diethyl Aluminum bromide, die Rualuminum ethoxide, ethylaluminum dichloride, ethylaluminum sesquichloride, tripropylaluminum, tributylaluminum, tri (2-methylpropyl) aluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. Particularly preferred. It is also possible to use a mixture of these compounds.

  Although there is no restriction | limiting in particular in the usage-amount of an organometallic compound (A-3), It is preferable that it is 0.01 times or more and 20 times or less in molar ratio with respect to alcohol (A-2), 0.1 times or more and 10 times Or less, more preferably 0.5 times or more and 2.5 times or less. If the amount of the organometallic compound (A-3) used is 0.01 times or more in terms of the molar ratio to the alcohol (A-2), excess alcohol can be efficiently removed, and organic If the usage-amount of a metal compound (A-3) is 20 times or less by the molar ratio with respect to alcohol (A-2), an organometallic compound (A-3) will be an organometallic compound (A-3) in a catalyst manufacturing process. Does not adversely affect the subsequent steps of the reaction. Furthermore, if the amount of the organometallic compound (A-3) used is 0.5 to 2.5 times the molar ratio to the alcohol (A-2), the alcohol necessary for improving the catalyst characteristics Can be left in the catalyst. Moreover, it is preferable that it is 0.01 times or more and 20 times or less by molar ratio with respect to the magnesium atom contained in a support | carrier (A-1), and it is still more preferable that they are 0.1 times or more and 10 times or less. Although there is no restriction | limiting in particular about the temperature of reaction, The range which is 25 degreeC or more and 200 degrees C or less and less than the boiling point of a reaction medium is preferable.

Next, the titanium compound (A-4) that is preferably used will be described.
As the titanium compound (A-4), a titanium compound represented by the following general formula (4) is used.
^{_{Ti (OR 13) i X (}} 4-i) - (4)
(In the formula, i is a real number of 0 or more and 4 or less, R ¹³ is a hydrocarbon group of 1 to 20 carbon atoms, and X is a halogen atom.)
Examples of the hydrocarbon group represented by R ¹³ include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, and allyl groups, cyclohexyl, and 2-methylcyclohexyl. , An alicyclic hydrocarbon group such as cyclopentyl group, and an aromatic hydrocarbon group such as phenyl and naphthyl group. An aliphatic hydrocarbon group is preferable. Examples of the halogen atom represented by X include chlorine, bromine and iodine, with chlorine being preferred. Specifically, titanium tetrachloride is preferable. Two or more kinds of titanium compounds (A-4) selected from the above can be mixed and used.

  Although there is no restriction | limiting in particular in the usage-amount of a titanium compound (A-4), About the load with respect to a support | carrier (A-1), 0.01 or more 20 by molar ratio with respect to the magnesium atom contained in a support | carrier (A-1). The following is preferable, and 0.05 or more and 10 or less are particularly preferable. If the amount of the titanium compound (A-4) supported on the carrier (A-1) is too small, the polymerization activity per catalyst is low, and if it is too large, the polymerization activity per titanium tends to be low. If the amount of the titanium compound (A-4) supported on the carrier (A-1) is 0.01 or more in terms of the molar ratio to the magnesium atom contained in the carrier (A-1), the polymerization activity per catalyst is sufficiently high. If it is high and 20 or less, the polymerization activity per titanium is sufficiently high. Although there is no restriction | limiting in particular about the reaction temperature in the case of carrying | supporting, It is preferable to carry out in 25 to 150 degreeC.

When carrying | supporting a titanium compound (A-4), it is preferable to carry | support by making a titanium compound (A-4) and an organometallic compound (A-5) react. This organometallic compound (A-5) is a compound represented by the aforementioned general formula (3), and may be the same as or different from the aforementioned organometallic compound (A-3).
^{_{M 2 R 5 f Q (h}} -f) - (3)

  The order of the reaction between (A-4) and (A-5) is not particularly limited, and (A-5) is added following (A-4). Following (A-5), (A- Any method of adding 4) and adding (A-4) and (A-5) simultaneously is possible, and it is preferable to add (A-5) following (A-4). The molar ratio of (A-5) to (A-4) is preferably 0.1 to 10, particularly preferably 0.5 to 5. The reaction between (A-2) and (A-5) is carried out in an inert hydrocarbon solvent, but it is preferable to use an aliphatic hydrocarbon solvent such as hexane or heptane. Although there is no restriction | limiting in particular about the temperature of reaction, The range which is 25 degreeC or more and 200 degrees C or less and less than the boiling point of a reaction medium is preferable.

  Next, the organometallic compound [B] that is preferably used will be described. The organometallic compound [B] is preferably an organoaluminum compound represented by the following general formula (5) or a specific organomagnesium compound represented by the following general formula (6).

The organoaluminum compound preferably used is represented by the following general formula (5).
R ¹⁴ _(3-j) AlQ ′ _j − (5)
(Wherein R ¹⁴ is a hydrocarbon group having 1 to 12 carbon atoms, Q ′ is a group belonging to the group consisting of a hydrogen atom, a halogen atom, and OR ¹⁵ , and R ¹⁵ is a group having 1 to 20 carbon atoms. And j is a real number of 0 or more and 2 or less)
Examples of R ¹⁴ include methyl, ethyl, propyl, butyl, 2-methylpropyl, pentyl, 3-methylbutyl, hexyl, octyl, decyl, phenyl, tolyl, and the like. Of these, an ethyl group and a 2-methylpropyl group are particularly preferable. Two or more kinds of these hydrocarbon groups may be contained. h is preferably 0.05 or more and 1.5 or less, and particularly preferably 0.1 or more and 1.2 or less.

Next, the organomagnesium compound is represented by the following general formula (6).
(M ³ ) _γ (Mg) _δ (R ¹⁵ ) _m (R ¹⁶ ) _n- (6)
(In the formula, M ³ is a metal atom other than magnesium belonging to the group consisting of Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹⁵ and R ¹⁶ each have 2 to 20 carbon atoms. The following hydrocarbon groups, γ, δ, m, and n are real numbers that satisfy the following relationship: 0 ≦ γ, 0 <δ, 0 ≦ k, 0 ≦ m, pγ + 2δ = m + n (where p is M Valence of ³ ))

  This organomagnesium compound is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds It is. The relationship between the symbols γ, δ, m and n, pγ + 2δ = m + n, indicates the stoichiometry between the valence of the metal atom and the substituent.

In the general formula (6), the hydrocarbon group represented by R ¹⁵ and R ¹⁶ is an alkyl group, a cycloalkyl group, or an aryl group. For example, methyl, ethyl, propyl, butyl, propyl, hexyl, octyl, Examples include decyl, cyclohexyl, and phenyl groups, and R ¹⁵ and R ¹⁶ are preferably alkyl groups. When γ> 0, as the metal atom M ³ , a metal element belonging to Groups I to III of the periodic table can be used, and examples thereof include lithium, sodium, potassium, beryllium, zinc, boron, and aluminum. However, aluminum, boron, beryllium, and zinc are particularly preferable.

The ratio δ / γ of magnesium to metal atom M ³ is not particularly limited, but is preferably 0.1 or more and 30 or less, more preferably 0.5 or more and 10 or less. In addition, when an organomagnesium compound in which γ = 0 is used, for example, when R ¹⁵ is 1-methylpropyl or the like, it is soluble in an inert hydrocarbon solvent, and such a compound also has preferable results in the present invention. give. In the above general formula (6), when γ = 0, R ¹⁵ and R ¹⁶ are preferably any one of the following three groups (1), (2) and (3): Is done.

(1) At least one of R ¹⁵ and R ¹⁶ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ¹⁵ and R ¹⁶ have 4 to 6 carbon atoms. Yes, at least one of which is a secondary or tertiary alkyl group.
(2) R ¹⁵ and R ¹⁶ are alkyl groups having different carbon atoms, preferably R ¹⁵ is an alkyl group having 2 or 3 carbon atoms, and R ¹⁶ is an alkyl having 4 or more carbon atoms. Be a group.
(3) At least one of R ¹⁵ and R ¹⁶ is a hydrocarbon group having 6 or more carbon atoms, preferably an alkyl group that becomes 12 or more when the number of carbon atoms contained in R ¹⁵ and R ¹⁶ is added. .

  These groups are specifically shown below. Examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (1) include 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2-methylbutyl, 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group and the like are used, and 1-methylpropyl group is particularly preferable.

  Next, in (2), examples of the alkyl group having 2 or 3 carbon atoms include ethyl, 1-methylethyl, propyl group and the like, and the ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include butyl, pentyl, hexyl, heptyl, octyl group and the like, and butyl and hexyl groups are particularly preferable.

  Furthermore, examples of the hydrocarbon group having 6 or more carbon atoms in (3) include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like. Among the hydrocarbon groups, an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable. In general, an increase in the number of carbon atoms contained in an alkyl group facilitates dissolution in an inert hydrocarbon solvent. However, the use of an unnecessarily long alkyl group is not preferred in terms of handling because the solution viscosity increases. The organomagnesium compound is used as an inert hydrocarbon solution, but it can be used as long as a trace amount of Lewis basic compounds such as ethers, esters, and amines are contained or remain in the solution.

These organomagnesium compounds include organomagnesium compounds belonging to the group consisting of general formulas R ¹⁵ MgX and R ¹⁵ ₂ Mg (R ¹⁵ is as defined above, X is halogen), and general formula M ³ R ¹⁶ _k. And an organometallic compound belonging to the group consisting of M ³ R ¹⁶ _(k-1) H (M ³ , R ¹⁶ , k are as defined above) in an inert hydrocarbon solvent at 25 ° C. or higher and 150 ° C. or lower. It is synthesized by the method of reacting between them.

  The catalyst thus obtained is characterized by a high activity per titanium and a very high activity per catalyst, especially for the polymerization of ethylene and the copolymerization of ethylene and an α-olefin having 3 or more carbon atoms.

  As the polymerization solvent, an inert hydrocarbon solvent usually used for slurry polymerization is preferably used. The polymerization temperature is usually from room temperature to 120 ° C., and preferably from 50 ° C. to 100 ° C. The polymerization pressure is usually carried out in the range of normal pressure to 10 MPa. The molecular weight of the resulting polymer can be adjusted by changing the concentration of hydrogen present in the polymerization system, changing the polymerization temperature, or changing the concentration of the organometallic compound [B].

  There is no restriction | limiting in particular in the manufacturing process of polyolefin using the said catalyst, It can apply also to any manufacturing method of the generally used solution method, a high pressure method, a high pressure bulk method, a gas method, and a slurry method. For example, the polymerization pressure is from 0.1 MPa to 200 MPa as the gauge pressure, the polymerization temperature is from 25 ° C. to 250 ° C., and propane, butane, isobutane, hexane, cyclohexane or the like is used as the solvent.

As a second preferred embodiment of the method for producing linear polyethylene (α), the metallocene-supported catalyst [I] is previously brought into contact with hydrogen and then introduced into the polymerization reactor together with the liquid promoter component [II]. Examples thereof include polymerization of ethylene alone or copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms.
The linear polyethylene (α) obtained by this production method has a low Mw / Mn and molecular weight distribution obtained by the gel permeation chromatography method, as well as a low molecular weight component unlike the production method described above. The oligomer component can be reduced, and since it does not contain chlorine in the production method, it has excellent cleanliness and is suitable for foamed films for semiconductor and pharmaceutical / medical packaging.

  Various known methods can be used as the polymerization method, such as fluidized bed gas phase polymerization or stirring gas phase polymerization in an inert gas, slurry polymerization in an inert solvent, bulk polymerization using a monomer as a solvent, and the like. Can be mentioned. As the polymerization method, slurry polymerization in an inert solvent is preferable.

(Metallocene supported catalyst [I])
The metallocene-supported catalyst [I] includes (Ia) support material, (Ib) organoaluminum, (Ic) transition metal compound having a cyclic η-bonding anion ligand, and (Id) It is preferable to use a metallocene-supported catalyst prepared from an activator capable of reacting with the transition metal compound having a cyclic η-bonding anion ligand to form a complex that exhibits catalytic activity.

  (Ia) The carrier material may be either an organic carrier or an inorganic carrier.

  Preferred examples of the organic carrier include C2-C20 α-olefin polymers, aromatic unsaturated hydrocarbon polymers, and polar group-containing polymers.

  Examples of the polymer of α-olefin having 2 to 20 carbon atoms include ethylene resin, propylene resin, 1-butene resin, ethylene-propylene copolymer resin, ethylene-1-hexene copolymer resin, propylene-1- Examples include butene copolymer resins and ethylene-1-hexene copolymers.

  Examples of the aromatic unsaturated hydrocarbon polymer include styrene resin and styrene-divinylbenzene copolymer resin.

  Examples of the polar group-containing polymer include acrylic ester resins, methacrylic ester resins, acrylonitrile resins, vinyl chloride resins, amide resins, and carbonate resins.

  Preferred examples of the inorganic carrier include inorganic oxides, inorganic halides, inorganic carbonates, sulfates, nitrates, and hydroxides.

As the inorganic oxide, _{e.g., SiO 2, Al 2 O 3} , MgO, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO, SiO 2 -MgO, SiO 2 -Al 2 O 3, SiO 2 - MgO and SiO ₂ —V ₂ O ₅ are included.

Examples of the inorganic halogen compound include MgCl ₂ , AlCl _3, and MnCl ₂ .

Examples of the inorganic carbonate, sulfate, and nitrate include, for example, Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ etc. are mentioned.

Examples of the hydroxide include Mg (OH) ₂ , Al (OH) ₃ , and Ca (OH) ₂ .

(Ia) The carrier material is preferably SiO ₂ .

  The particle size of the carrier is arbitrary, but the particle size distribution is preferably 1 to 3000 μm, and from the viewpoint of particle dispersibility, the particle size distribution is more preferably within the range of 10 to 1000 μm. .

  (Ia) The support material is treated with (Ib) organoaluminum as required.

  (Ib) The organoaluminum has a general formula: (—Al (R) O—) n (wherein R is a hydrocarbon group having 1 to 10 carbon atoms, and partially halogen atoms and / or RO groups) And n is the degree of polymerization, and is 5 or more, preferably 10 or more).

  Examples of (Ib) organoaluminum compounds include methylalumoxane, ethylalumoxane, and isobutylethylalumoxane, in which R is a methyl group, an ethyl group, or an isobutylethyl group.

  In addition to the above, (Ib) organic aluminum includes, for example, trialkylaluminum, dialkylhalogenoaluminum, sesquialkylhalogenoaluminum, armenylaluminum, dialkylhydroaluminum, and sesquialkylhydroaluminum.

Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum.
Examples of the dialkyl halogeno aluminum include dialkyl halogeno aluminum such as dimethyl aluminum chloride and diethyl aluminum chloride.

  Examples of the sesquialkylhalogenoaluminum include sesquimethylaluminum chloride and sesquiethylaluminum chloride.

  Examples of (Ib) organic aluminum include ethylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, and sesquiethylaluminum hydride.

  (Ib) The organic aluminum is preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride.

(Ic) Examples of the transition metal compound having a cyclic η-binding anion ligand include compounds represented by the following formula (7).

In the above formula (7), M is a transition metal belonging to Group 4 of the long-period periodic table having oxidation numbers of +2, +3, and +4 and having an η ⁵ bond with one or more ligands L. Titanium is preferable as the transition metal.

  L is a cyclic η-bonding anion ligand, each independently a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, or an octahydrofluorenyl group, These groups are hydrocarbon groups containing up to 20 non-hydrogen atoms, halogens, halogen-substituted hydrocarbon groups, aminohydrocarbyl groups, hydrocarbyloxy groups, dihydrocarbylamino groups, dihydrocarbylphosphino groups, silyl groups, aminosilyls Optionally having 1 to 8 substituents each independently selected from a group, hydrocarbyloxysilyl group and halosilyl group, wherein two Ls contain up to 20 non-hydrogen atoms, hydrocarbadiyl, halohydro Carbadiyl, hydrocarbyleneoxy, hydrocarbyleneamino, diladiyl, halo Diyl, it may be linked by a divalent substituent such as an aminosilane.

  Each X independently represents a monovalent anionic σ-bonded ligand having up to 60 non-hydrogen atoms, a divalent anionic σ-bonded ligand that binds to M in a divalent manner, or M and It is a divalent anion sigma-bonded ligand that binds to L each with one valence.

  X 'is each independently a neutral Lewis base coordinating compound selected from phosphines, ethers, amines, olefins, and / or conjugated dienes having 4 to 40 carbon atoms. l is an integer of 1 or 2.

  p is an integer of 0 to 2, and X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded bond that binds to M and L with one valence each. When it is a ligand, p is 1 or more less than the formal oxidation number of M, and when X is a divalent anionic σ-bonded ligand that binds to M in a divalent manner, p is the formal oxidation number of M. Less than 1 + 1.

  q is an integer of 0, 1 or 2.

  (Ic) The transition metal compound having a cyclic η-bonding anion ligand is preferably a compound in which l = 1 in the above formula (7).

(Ic) As a suitable compound of the transition metal compound having a cyclic η-bonding anion ligand, a compound represented by the following formula (8) may be mentioned.

  In the above formula (8), M is titanium, zirconium or hafnium having a formal oxidation number of +2, +3 or +4, and is preferably titanium.

Each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a composite group thereof, and each can have up to 20 non-hydrogen atoms. Further, adjacent R ³ may be cyclic by forming a bivalent derivative such as hydrocarbadiyl, diladiyl, or germanidiyl.

  Each X ″ is independently a halogen, a hydrocarbon group, a hydrocarbyloxy group, a hydrocarbylamino group, or a silyl group, each having up to 20 non-hydrogen atoms, and two X ″ having 5 carbon atoms ~ 30 neutral conjugated dienes or divalent derivatives may be formed.

Y is O, S, NR ^* or PR ^* .

Z is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ , or GeR ^* ₂ .

Each R ^* is independently an alkyl group having 1 to 12 carbon atoms or an aryl group.

  n is an integer of 1 to 3.

(Ic) More preferable examples of the transition metal compound having a cyclic η-bonding anion ligand include compounds represented by the following formula (9) or the following formula (10).

  In the above formulas (9) and (10), M is titanium, zirconium, or hafnium, and is preferably titanium.

Each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a composite group thereof, and each can have up to 20 non-hydrogen atoms.

  Z, Y, X, and X 'are as described above.

  p is an integer of 0 to 2, and q is an integer of 0 or 1.

  However, when p is 2 and q is 0, the oxidation number of M is +4, and X is halogen, hydrocarbon group, hydrocarbyloxy group, dihydrocarbylamino group, dihydrocarbyl phosphide group, hydrocarbyl sulfide group, silyl group A group or a combination thereof, having up to 20 non-hydrogen atoms. When p is 1 and q is 0, the oxidation number of M is +3, and X is an allyl group, 2- (N, N-dimethylaminomethyl) phenyl group or 2- (N, N-dimethyl) -A stabilized anionic ligand selected from aminobenzyl groups, or the oxidation number of M is +4 and X is a derivative of a divalent conjugated diene, or both M and X are metallocyclopentene groups Is forming. Further, when p is 0 and q is 1, the oxidation number of M is +2, and X ′ is a neutral conjugated or non-conjugated diene, optionally substituted with one or more hydrocarbons Often, X ′ can contain up to 40 carbon atoms and forms a π-type complex with M.

(Ic) As a more preferable compound of the transition metal compound having a cyclic η-bonding anion ligand, a compound represented by the following formula (11) or the following formula (12) may be mentioned.

  In the above formulas (11) and (12), M is titanium.

Each R ³ is independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

Y is O, S, NR ^* , or PR ^* , and Z ^* is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ₂ or GeR ^* ₂ .

Each R ^* is independently hydrogen, a hydrocarbon group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or a composite group thereof, and R ^* has up to 20 non-hydrogen atoms. can be, two R ^* s or Z ^* in R ^* and in Y medium R ^* may be a circular middle Z ^* as necessary.

  p is an integer of 0 to 2, and q is an integer of 0 or 1.

  However, when p is 2 and q is 0, the oxidation number of M is +4, and each X is independently a methyl group or a hydrobenzyl group. When p is 1 and q is 0, the oxidation number of M is +3 and X is a 2- (N, N-dimethyl) -aminobenzyl group, or the oxidation number of M is +4. And X is 2-butene-1,4-diyl. Further, when p is 0 and q is 1, the oxidation number of M is +2, and X ′ is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

  The dienes are examples of asymmetric dienes that form metal complexes, and are actually mixtures of geometric isomers.

  (Id) An activator capable of reacting with a transition metal compound having a cyclic η-bonding anion ligand to form a complex exhibiting catalytic activity (hereinafter simply referred to as “(Id) activator”) Examples of such a compound may include a compound represented by the following formula (13).

In the metallocene supported catalyst [I], a complex formed by (Ic) a transition metal compound having a cyclic η-bonding anion ligand and the above (Id) activator is an olefin having a high catalytic activity species. Shows polymerization activity.

In the above formula (13), [L-H] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base.

[M _m Q _t ] ^d- is a compatible non-coordinating anion, M is a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q is each independently hydride, dialkylamide. A group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted hydrocarbon group having up to 20 carbon atoms. However, Q which is a halide is 1 or less.

  m is an integer of 1 to 7, t is an integer of 2 to 14, d is an integer of 1 to 7, and t−m = d.

As a suitable compound of (Id) activator, the compound shown by following formula (14) is mentioned.

In the above formula (14), [LH] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base.

A _{[M m Q w (G u} (T-H) r) z] d- is a non-coordinating anion compatible, M is a metal or metalloid selected from Group 5 to Group 15 of the periodic table , Q are each independently a hydride, a dialkylamide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted hydrocarbon group having up to 20 carbon atoms. However, Q which is a halide is 1 or less.

  G is a polyvalent hydrocarbon group having a valence of r + 1 bonded to M and T, T is O, S, NR or PR, R is a hydrocarbyl group, a trihydrocarbylsilyl group, a trihydrocarbylgermanium group, or Hydrogen.

  m is an integer of 1-7, w is an integer of 0-7, u is an integer of 0 or 1, r is an integer of 1-3, z is an integer of 1-8, w + z-m = d.

As a more preferred compound of the (Id) activator, a compound represented by the following formula (15) can be mentioned.

In the above formula (15), [LH] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base.

[BQ ₃ Q ^* ] ⁻ is a compatible non-coordinating anion, B is a boron atom, Q is a pentafluorophenyl group, and Q ^* has 6 to 20 carbon atoms having one OH group as a substituent. A substituted aryl group.

  Compatible non-coordinating anions include triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p-tolyl) phenyl (hydroxyphenyl). ) Borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5 -Di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl,) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (pentafluoro) Phenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate and the like. And tris (pentafluorophenyl) (hydroxyphenyl) borate is preferable.

  Examples of the compatible non-coordinating anion include borates in which the hydroxy group of the borate exemplified above is replaced with NHR. Here, R is preferably a methyl group, an ethyl group or a t-butyl group.

  Protonated Bronsted acids include triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium, tri (n-octyl) ammonium, diethylmethylammonium, dibutylmethylammonium, dibutylethylammonium, Dihexylmethylammonium, dioctylmethylammonium, didecylmethylammonium, didodecylmethylammonium, ditetradecylmethylammonium, dihexadecylmethylammonium, dioctadecylmethylammonium, diicosylmethylammonium, bis (tallowalkyl hydrogenated) methylammonium Trialkyl group-substituted ammonium cations such as N, N-dimethyla Riniumu, N, N- diethyl anilinium, N, N-2,4,6 pentamethyl anilinium, N, N- N, such as dimethyl benzyl anilinium also include such N- dialkylanilinium cations.

(Liquid promoter component [II])
The liquid promoter component [II] may be described as an organomagnesium compound [III-1] soluble in a hydrocarbon solvent represented by the following formula (16) (hereinafter simply referred to as “organomagnesium compound [III-1]”). A hydrocarbon solvent synthesized by a reaction of the compound [III-2] selected from amines, alcohols, and siloxane compounds (hereinafter sometimes simply referred to as “compound [III-2]”). It is an organic magnesium compound that is soluble in water.

In the above formula (16), ^{M 1} is a metal atom belonging to Group 1-3 of the periodic table, ^{R 4} and ^{R 5} is a hydrocarbon group having 2 to 20 carbon atoms, a, b, c, d Is a real number that satisfies the following relationship.

0 ≦ a, 0 <b, 0 ≦ c, 0 ≦ d, c + d> 0, and e × a + 2b = c + d (e is the valence of M ¹ )

  The reaction between the organomagnesium compound [III-1] and the compound [III-2] is not particularly limited, but is not limited to aliphatic hydrocarbons such as hexane and heptane and / or aromatic hydrocarbons such as benzene and toluene. The reaction is preferably performed at room temperature to 150 ° C. in an active reaction medium.

  There is no restriction | limiting in particular about the order added in reaction which manufactures a liquid promoter component, The method of adding compound [III-2] in organomagnesium compound [III-1], Organomagnesium compound to compound [III-2] Any method of adding [III-1] or adding both at the same time may be used.

  Although there is no restriction | limiting in particular about the reaction ratio of organomagnesium compound [III-1] and compound [III-2], Compound [III- with respect to all the metal atoms contained in liquid promoter component [II] synthesize | combined by reaction. The compound [III-2] is preferably added so that the molar ratio of 2] is 0.01 to 2, and more preferably 0.1 to 1.

  The liquid promoter component [II] is used as an impurity scavenger. The liquid promoter component [II] hardly reduces the polymerization activity even at a high concentration, and therefore can exhibit a high polymerization activity in a wide concentration range. Therefore, the polymerization activity of the olefin polymerization catalyst containing the liquid promoter component [II] can be easily controlled.

  The liquid promoter component [II] may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about the density | concentration of liquid promoter component [II] at the time of using for superposition | polymerization, The molar concentration of all the metal atoms contained in liquid promoter component [II] is 0.001 mmol / liter or more, 10 mmol / liter. Or less, more preferably 0.01 mmol / liter or more and 5 mmol / liter or less.

  If the molar concentration is 0.001 mmol / liter or more, the effect of impurities as a scavenger can be sufficiently exhibited, and if it is 10 mmol / liter or less, the polymerization activity can be sufficiently exhibited.

  The organomagnesium compound [III-1] is an organomagnesium compound that is soluble in the hydrocarbon solvent represented by the above formula (16).

As the above formula (16), the organomagnesium compound [III-1] is shown as a complex compound form of organomagnesium soluble in a hydrocarbon solvent, but (R ⁴ ) ₂ Mg and these and other metals It includes all complexes with compounds. The relational expression e × a + 2b = c + d of the symbols a, b, c, and d indicates the stoichiometry between the valence of the metal atom and the substituent.

In the above formula (16), the hydrocarbon group having 2 to 20 carbon atoms of R ⁴ and R ⁵ is an alkyl group, a cycloalkyl group or an aryl group, and is a methyl group, an ethyl group, a propyl group, or a 1-methylethyl group. A butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1,1-dimethylethyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group, and an alkyl group. Preferably, it is a primary alkyl group.

For a> 0, as the metal atom M ¹ is the periodic table can be used a metal element belonging to the group consisting of first to third group is, for example, lithium, sodium, potassium, beryllium, zinc, boron, aluminum and the like Of these, aluminum, boron, beryllium, and zinc are particularly preferable.

No particular limitation on the molar ratio b / a of magnesium to metal atom ^{M 1,} but preferably in the range of 0.1 to 50, more preferably in the range of 0.5 to 10.

When a = 0, the organomagnesium compound [III-1] is preferably an organomagnesium compound soluble in a hydrocarbon solvent, and R ⁴ and R ^{5 in} the above formula (16) are represented by the following three groups ( More preferably, it is any one of i), (ii), and (iii).

(I) At least one of R ⁴ and R ⁵ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably R ⁴ and R ⁵ are both 4 to 6 carbon atoms, and At least one is a secondary or tertiary alkyl group.

(Ii) R ⁴ and R ⁵ are alkyl groups different from each other in carbon number, preferably R ⁴ is an alkyl group having 2 or 3 carbon atoms, and R ⁵ is an alkyl group having 4 or more carbon atoms. is there.

(Iii) R at least one of ⁴ and R ⁵ are hydrocarbon groups having 6 or more carbon atoms, preferably R ⁴ and R ⁵ are both an alkyl group having 6 or more carbon atoms.

  Examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in (i) include 1-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 1-ethylpropyl group, 1, Examples include 1-dimethylpropyl group, 1-methylpentyl group, 1-ethylbutyl group, 1,1-dimethylbutyl group, 1-methyl-1-ethylpropyl group, and the like, and 1-methylpropyl group is preferable.

  Examples of the alkyl group having 2 or 3 carbon atoms in (ii) include an ethyl group and a propyl group, and an ethyl group is preferable. Examples of the alkyl group having 4 or more carbon atoms include a butyl group, an amyl group, a hexyl group, and an octyl group, and a butyl group and a hexyl group are preferable.

  Examples of the hydrocarbon group having 6 or more carbon atoms in (iii) include a hexyl group, an octyl group, a decyl group, a phenyl group, and the like. An alkyl group is preferable, and a hexyl group is more preferable.

  As the organomagnesium compound [III-1], increasing the number of carbon atoms of the alkyl group generally makes it easier to dissolve in a hydrocarbon solvent, but the solution tends to increase in viscosity, and an unnecessarily long alkyl group should be used. May be undesirable in handling. Although the organomagnesium compound [III-1] is used as a hydrocarbon solution, the solution may contain a slight amount of a complexing agent such as ether, ester, amine or the like, and the complex may be contained in the solution. Even if the agent remains, it can be used without any problem.

  Compound [III-2] is a compound belonging to the group consisting of an amine, an alcohol, and a siloxane compound.

  The amine compound is not particularly limited, and examples thereof include aliphatic, alicyclic or aromatic amines.

  Examples of amine compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, aniline. N-methylaniline, N, N-dimethylaniline, toluidine and the like.

  The alcohol compound is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1,1-dimethylethanol, pentanol, hexanol, 2-methylpentanol, 2 -Ethyl-1-butanol, 2-ethyl-1-pentanol, 2-ethyl-1-hexanol, 2-ethyl-4-methyl-1-pentanol, 2-propyl-1-heptanol, 2-ethyl-5 -Methyl-1-octanol, 1-octanol, 1-decanol, cyclohexanol, phenol are mentioned, and 1-butanol, 2-butanol, 2-methyl-1-pentanol and 2-ethyl-1-hexanol are preferable.

  Although there is no restriction | limiting in particular as a siloxane compound, The siloxane compound which has a structural unit shown by following formula (17) is mentioned.

The siloxane compound can be used in the form of a dimer or higher chain or cyclic compound composed of one type or two or more types of structural units.

In the formula (17), R ⁶ and R ⁷ are groups selected from the group consisting of hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, or a substituted hydrocarbon group having 1 to 40 carbon atoms.

  The hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, but is a methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1 , 1-dimethylethyl group, pentyl group, hexyl group, octyl group, decyl group, phenyl group, tolyl group and vinyl group. The substituted hydrocarbon group having 1 to 40 carbon atoms is not particularly limited, and examples thereof include a trifluoropropyl group.

  As siloxane compounds, symmetrical dihydrotetramethyldisiloxane, hexamethyldisiloxane, hexamethyltrisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, cyclic methylhydropentasiloxane, cyclic dimethyltetrasiloxane, cyclic methyltrifluoropropyl Tetrasiloxane, cyclic methylphenyltetrasiloxane, cyclic diphenyltetrasiloxane, (terminal methyl-capped) methylhydropolysiloxane, dimethylpolysiloxane, (terminal methyl-capped) phenylhydropolysiloxane, and methylphenylpolysiloxane are preferred.

(High pressure low density polyethylene (β))
The high pressure method low density polyethylene (β) (sometimes referred to as high pressure method low density polyethylene) that is preferably used in the polyethylene resin composition used in the present invention is an ethylene homopolymer or ethylene and one or more of them. It is preferable that it is a copolymer with the C3-C20 alpha olefin of this, and can obtain it by a well-known high pressure radical polymerization method.

The density of the high-pressure low-density polyethylene used in the present embodiment (beta) is preferably from 910~930kg / ^{m 3,} more preferably from 915~928kg / ^{m 3.} The density of the high-pressure method low-density polyethylene (β) can be measured by the method described in Examples below. Moreover, the density of the high-pressure method low-density polyethylene (β) in the resin composition can be measured by fractionating the high-pressure method low-density polyethylene by a method such as a cross fractionation chromatography method (CFC method).
The MFR of the high-pressure low-density polyethylene (β) used in the present embodiment is preferably 0.1 to 10 g / 10 minutes, and more preferably 1.0 to 5 g / 10 minutes. The MFR of the high-pressure method low-density polyethylene (β) can be measured by the method described in Examples below. Further, the MFR of the high-pressure low-density polyethylene (β) in the resin composition can be determined from the blending ratio of the MFR of the resin composition and the high-pressure low-density polyethylene.

In the gel permeation chromatography method, the molecular weight distribution (Mw / Mn) of the high-pressure method low-density polyethylene (β) used in the present embodiment is preferably 8 to 24, more preferably 10 to 24, and further Preferably it is the range of 13-24. Such a high-pressure low-density polyethylene (β) having a broad molecular weight distribution can be obtained by radical polymerization of ethylene in an autoclave type reactor.
If the molecular weight distribution of the high-pressure method low-density polyethylene (β) is within the above range, there are many branched side chains of the high-pressure method low-density polyethylene (β), and the linear polyethylene (α) starting from the branch point Is crystallized, and it is estimated that a network structure is formed during foam molding in linear polyethylene (α) and high-pressure low-density polyethylene (β). Therefore, it is possible to obtain a foamed film having a good foamed state and having excellent surface appearance and heat insulating properties with suppressed bubble breakage on the film surface.
In particular, when the molecular weight distribution of the high pressure method low density polyethylene (β) is 8 or more, the linear polyethylene (α) and the high pressure method in a blend of the linear polyethylene (α) and the high pressure method low density polyethylene (β) are used. It is presumed that the low-density polyethylene (β) can be made in a good compatible state and the crystal state of both can be prevented from phase separation. For this reason, it is possible to obtain a foamed film having a good foamed state and excellent surface appearance and heat insulation.
The molecular weight distribution can be determined by a gel permeation chromatography method, and more specifically, can be measured by the method described in Examples described later. The molecular weight distribution of the high-pressure method low-density polyethylene (β) in the resin composition can be measured by a method such as a cross-fractionation chromatography method (CFC method).

The melt tension ratio (hereinafter abbreviated as MTR ₂ ) of the high pressure method low density polyethylene (β) used in the present embodiment is represented by the following formula [2], and the value is preferably 0.7 or more. More preferably, it is 0.8 or more. Further, the relationship between the melt flow rate ratio (hereinafter abbreviated as FRR) and the melt tension (hereinafter abbreviated as MT) preferably satisfies the following formula [3]. It is particularly preferable to satisfy both conditions.
MTR ₂ = (MT ₂₄₀ ° C.) / (MT ₁₉₀ ° C.) [2]
(MT ₁₉₀ ° C.) ≧ 0.65 (FRR) −20 [3]
(However, in the above formulas [2] and [3], MTR ₂ is the melt tension ratio, MT is the melt tension, MT is the melt tension measurement temperature, FRR is temperature = 190 ° C., load = 2. (This is the value obtained by dividing MFR at 6 kg by MFR at temperature = 190 ° C. and load = 2.16 kg.)
Here, MTR ₂ of 0.7 or more means that the value of the melt tension with respect to the processing temperature of the resin does not change greatly. Further, the above formula [3] ], The deterioration of foam molding processability can be suppressed. As described above, the relationship between the MTR ₂ and FRR and the melt tension of the high-pressure low-density polyethylene (β) in the polyethylene-based resin composition of the present embodiment is within the above range from the viewpoint of foam molding processability and molded appearance. preferable.
High-pressure low-density polyethylene (β) having such characteristics can be obtained by radical polymerization of ethylene in an autoclave type reactor, has very little temperature dependence of melt tension, has a broader molecular weight distribution, and is branched. There are more side chains. By using this, it is possible to obtain a foamed film having excellent foam molding processability, a good foamed state, and a good appearance on the surface of the molded body.

  The high-pressure process low-density polyethylene (β) may be a copolymer of ethylene and other α-olefin, vinyl acetate, acrylate ester or the like as long as the object of the present invention is not impaired.

  The polyethylene resin composition used in the present invention is a resin composition comprising linear polyethylene (α) as described above and high pressure method low density polyethylene (β). A polymer blend of such a linear polyethylene (α) having a narrow molecular weight distribution and a high pressure method low density polyethylene (β) having a wide molecular weight distribution (Mw / Mn) of 8 to 24 and generally having many branched side chains. By doing so, it is possible to easily obtain a foam film having excellent foam molding processability, good foamed state, and excellent surface appearance and heat insulating properties.

  In general, blend systems of high-density polyethylene and low-density polyethylene are incompatible, and the crystalline state of both phase separates (for example, see Non-Patent Document 1), so blend high-density polyethylene and low-density polyethylene. In such a composition, the foamed state of the foamed molded product is generally poor.

However, the molecular weight distribution Mw / Mn is as narrow as 3-7, linear polyethylene (α) having a uniform molecular weight, and the molecular weight distribution (Mw / Mn) is as wide as 8-24, and there are many branched side chains. In a preferred embodiment in which a polymer blend is blended with a high-pressure method low-density polyethylene (β) in a predetermined ratio range, a tendency to increase the crystallization speed and to decrease the crystal size and make the crystal state uniform is recognized. This suggests that the polyethylene (α) and high-pressure low-density polyethylene (β) are co-crystallized in a compatible state. Along with such a phenomenon, there is a tendency that the foaming processability of the foamed film comprising the polyethylene resin composition is improved. These tendencies are more prominent when the blend amount of the high-pressure low-density polyethylene (β) is about 20% by mass with the linear polyethylene (α) as the base resin.
The polyethylene resin composition used in the present invention is characterized in that it can be obtained from one having a low expansion ratio to one having a high expansion ratio. Such characteristics include linear polyethylene (α) having a narrow molecular weight distribution and high-pressure low-density polyethylene (β) having a wide molecular weight distribution (Mw / Mn) of 8 to 24 and a large number of branched side chains. This is achieved by polymer blending to obtain a resin composition having a high melt tension at a low temperature of 160 ° C. close to the processing temperature of foam molding.

Although known additives can be added to the polyethylene resin composition used in the present invention as needed within a range not impairing the object of the present invention, it is essentially preferable to add no additives. Polyethylene polymerized with a Ziegler-Natta catalyst requires a neutralizing agent to supplement chlorine and an antioxidant as a heat stabilizer. Examples of the neutralizing agent include metal salts of higher fatty acids such as calcium stearate and zinc stearate and hydrotalcites. Antioxidants include phenolic stabilizers and organic phosphite stabilizers. All of them are eluted in high-purity chemicals and cause contamination. Polyethylene polymerized with a metallocene-based catalyst is preferable because it does not require these neutralizing agents and antioxidants and can be used in a foamed film without being added. That is, it is preferable that the foamed film of this embodiment does not substantially contain any of the neutralizing agent and the antioxidant that cause dust generation. Here, “substantially does not contain” means that these are not intentionally added, and specifically means that they are two or more orders of magnitude lower than the upper limit of the following addition amount.
Although it is essentially preferable to add no additives, the neutralizing agent is preferably 150 PPM or less, more preferably 100 ppm or less, depending on the type of chemical in the contents. The antioxidant is preferably 800 PPM or less, more preferably 300 ppm or less.
It is most preferable to add a metal salt of a higher fatty acid as a neutralizing agent, which serves as a lubricant in molding processability, and the surface state of the foam film is relatively good.
It is most preferable to add a phenolic antioxidant as the antioxidant, which can prevent oxidative degradation due to resin chemicals and suppress discoloration and degradation of the container.
Additives include phenolic stabilizers, organic phosphite stabilizers, organic thioester stabilizers, stabilizers as metal salts of higher fatty acids, organic or inorganic pigments, UV absorbers, dyes, nucleating agents, lubricants, Examples include inorganic fillers or reinforcing materials such as carbon black, talc and glass fiber, compounding agents added to polyolefins such as flame retardants and neutron blocking agents.

  Examples of the phenol-based stabilizer include 2,6-di-t-butyl-4-methylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6- Di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6- t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, Tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate) methane, 2,2-methyle Bis (4-methyl-6-tert-butylphenol), 4,4-butylidenebis (3-methyl-6-tert-butylphenol), 4,4-thiobis (3-methyl-6-tert-butylphenol), 2,2 -Thiobis (4-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, 3,5-tris (2-methyl-4-hydroxy-5-tert-butylphenol) methane, tetrakis (methylene (3,5-di-butyl-4-hydroxyphenyl) propionate) methane, β- (3,5- Di-t-butyl-4-hydroxylphenol) propionic acid alkyl ester, 2,2-oxamide bis (ethyl-3- (3,5-di-t-butyl-4-hydride) Loxyphenyl) propionate, tetrakis (methylene (2,4-di-t-butyl-4-hydroxyl) propionate), n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6-di-t-butyl-p-cresol, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzylthiono-1,3,5-triazine, 2,2 -Methylenebis (4-methyl-6-tert-butylphenol), 4,4-methylenebis (2,6-di-tert-butylphenol), 2,2-methylenebis (6- (1-methylcyclohexyl) -p-cresol) Bis (3,5-bis (4-hydroxy-3-tert-butylphenyl) butyric acid) glycol ester, 4,4-butylidenebis (6-tert-butyl) Ru-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-) 4-t-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate, 1,3,5-tris ((3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl) isocyanurate, 2 -Octylthio-4,6-di (4-hydroxy-3,5-di-t-butyl) phenoxy-1,3,5-triazine, 4,4-thiobis (6-t-butyl-m-cresol), etc. Raised It is.

  Examples of organic phosphite stabilizers include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite. , Tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4- Hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4,4-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite , Tris (mono or dinonylphenyl) Phosphite, hydrogenated-4,4-isopropylidenediphenol polyphosphide, bis (octylphenyl) bis (4,4-butylidenebis (3-methyl-6-tert-butylphenol)) 1,6-hexaneol diphos Phosphide, phenyl-4,4-isopropylidenediphenol pentaerythritol diphosphide, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphide, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphide, tris ((4,4, -isopropylidenebis (2-t-butylphenol)) phosphide, di (nonylphenyl) pentaerythritol diphosphide, tris (1,3-di- Stearoyloxyisopropyl) phosphite, 4,4- Sopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphide, 9,10-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-) t-butylphenyl) -4,4-biphenylene diphosphide and the like.

  Organic thioester stabilizers include dialkylthiopropionates such as dilauryl-, dimyristyl-, distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- (for example, glycerin, Esters of trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate), specifically, dilauryl thiopropionate, dimyristyl thiopropionate, distearyl thiodipropionate, Examples include lauryl stearyl thiodipropionate, distearyl thiodibutyrate, and pentaerythritol tetralauryl thiopropionate.

  Stabilizers as metal salts of higher fatty acids include, for example, alkalis such as magnesium, calcium, and barium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, caprylic acid, arachidic acid, palmitic acid, and behenic acid. Earth metal salts, cadmium salts, zinc salts, lead salts, sodium salts, potassium salts, lithium salts, and the like are used.

Specific examples of stabilizers as metal salts of higher fatty acids include magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, barium stearate, barium laurate, barium laurate, magnesium, stearin. Zinc oxide, zinc oleate, zinc stearate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, and calcium 12-hydroxystearate .
Examples of inorganic fillers and antiblocking agents include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, and examples of lubricants include higher fatty acid amides such as stearic acid amide. .
Furthermore, examples of the antistatic agent include fatty acid partial esters such as glycerin fatty acid monoester, and examples of the metal deactivator include triazines, phosphones, epoxies, triazoles, hydrazides, and oxamides. .

The foaming agent is, for example, a thermal decomposition type chemical foaming agent that is liquid or solid at normal temperature and generates a gas upon heating, and may be any thermal decomposition type chemical foaming agent of an inorganic compound or an organic compound.
Specific examples of the inorganic compound include sodium bicarbonate, ammonium carbonate, ammonium nitrite and the like. On the other hand, specific examples of the organic compound include azide compounds such as azodicarbonamide, azobisformamide, isobutyronitrile, diazoaminobenzene, N, N′-dinitrosopentatetramine, N, N′-dimethyl-dinitroterephthalate. Illustrative are nitroso compounds such as amides.
In addition, this foaming agent may be used independently and may be used together 2 or more types.
The amount of the foaming agent added is 0.05 to 6.0 parts by weight, preferably 0.3 to 5.0 parts by weight, more preferably 0.5 to 100 parts by weight of the polyethylene resin composition of the present invention. It is preferable that it is the range of -4.0 mass parts.

  The polyethylene-based resin composition used in the present invention can be produced by polymer blending linear polyethylene (α) and high-pressure method low-density polyethylene (β) using a known method.

  Examples of the polymer blending method include a melt mixing method using a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, a heated roll kneader, and the like. Among them, it is preferable to melt knead and mix the linear polyethylene (α) and the high-pressure low-density polyethylene (β) using a twin-screw extruder. As preferable kneading conditions, the cylinder set temperature in the cylinder zone for plasticizing the resin is 150 to 230 ° C., the die set temperature is 180 to 230 ° C., the screw rotation speed is 150 to 200 rpm, and the resin discharge amount is 30 to 60 kg / hr, and nitrogen blowing amount under the hopper of 0.5 to 5.0 L / min. Nitrogen blowing under the hopper is more preferable because the oxygen and nitrogen can be sufficiently replaced when the resin enters the extruder, and the amount of oxygen entering the extruder can be reduced.

As a method of adding the above various additives to the polyethylene resin composition, when the linear polyethylene (α) and the high pressure method low density polyethylene (β) are mixed, the various additives are added in advance to the linear polyethylene (α ) Or a high-pressure method low-density polyethylene (β) mixed and added directly, or when mixing linear polyethylene (α) and high-pressure method low-density polyethylene (β), various high-concentration additives are added in advance. It is also possible to employ a method in which a master batch is prepared by mixing with linear polyethylene (α) or high-pressure low-density polyethylene (β) together and dry blended at the time of molding.
The foamed film of the present invention can be obtained, for example, by molding the polyethylene resin composition used in the present invention by any known method of inflation molding or T-die molding. Among these methods, the inflation molding method is preferable from the viewpoint of equipment and the simplicity of the molding operation.
The apparent density of the foam film of the present embodiment is usually 180 g / L or more and 800 g / L or less.
If the apparent density is 180 g / L or more and 800 g / L or less, the foam film has excellent rigidity and good buffering properties, has a good foamed state, and has excellent surface appearance and heat insulating properties. Can be obtained.
In the present embodiment, the apparent density can be measured by the method described in the following examples.
The foamed film comprising the polyethylene resin composition preferably has a thickness of 10 to 500 μm, more preferably 60 to 300 μm, and still more preferably 100 to 200 μm.
If thickness is 10 micrometers or more, when it is set as a foamed film, it is excellent in buffering property. Moreover, if thickness is 100 micrometers or more, when it is set as a foamed film, it is excellent in heat insulation. If thickness is 500 micrometers or less, the foamed film which has favorable rigidity with the outstanding buffer property and heat insulation can be obtained.

  Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples, but the present embodiment is not limited to only these examples. The measurement method and the evaluation method used in this embodiment are as follows.

(1) Density The density was measured according to JIS-K-7112: 1999.

(2) Melt flow rate (MFR)
Measured according to JIS-K-7210: 1999 (temperature = 190 ° C., load = 2.16 kg). In order to obtain the melt flow rate ratio, the measurement was also performed at a temperature = 190 ° C. and a load = 21.6 kg.

(3) Mw / Mn (molecular weight distribution) by gel permeation chromatography
Using a Waters 150-C ALC / GPC apparatus, Shodex AT-807S and Tosoh TSK-gelGMH-H6 were used in series as a column, and measurement by gel permeation chromatography was performed. The measurement was performed at 140 ° C. using trichlorobenzene containing 10 ppm of Irganox 1010 as a solvent. A calibration curve was prepared using commercially available monodisperse polystyrene as a standard substance.

(4) Melting point peak by differential scanning calorimeter (° C)
A differential scanning calorimeter (Perkin Elmer DSC-7 type apparatus) was used and measured under the following conditions. 1) About 5 mg of a polymer sample was packed in an aluminum pan, heated to 200 ° C. at 200 ° C./min, and held at 200 ° C. for 5 minutes. 2) Next, the temperature was decreased from 200 ° C. to 50 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed. 3) Next, the temperature was raised from 50 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. The maximum temperature at the melting peak position was determined as the melting point peak (° C.) from the endothermic curve observed in the process of 3).
(5) Melt tension (MT)
Manufactured by Toyo Seiki Co., Ltd. equipped with a capillary having a diameter of 2.095 mm, a length of 8.0 mm, and an inflow angle of 90 °; using Capilograph 1D, the polyethylene resin was extruded at 160 ° C., 190 ° C. or 240 ° C. at 60 mm / min. It was obtained by measuring the tension at the time of taking up at 2 m / min in an environment of room temperature (about 25 ± 2 ° C.). The melt tension when extruded at 160 ° C. is expressed as MT ₁₆₀ ° C., the melt tension when extruded at ₁₉₀ ° C. is expressed as MT ₁₉₀ ° C., and the melt tension when extruded at ₂₄₀ ° C. is expressed as MT ₂₄₀ ° C. Further, from these, the melt tension ratio (MTR) was determined according to the following formulas [1] and [2].
MTR ₁ = (MT ₁₆₀ ° C.) / (MT ₁₉₀ ° C.) [1]
MTR ₂ = (MT ₂₄₀ ° C.) / (MT ₁₉₀ ° C.) [2]

(6) Melt flow rate ratio (FRR)
The melt flow rate ratio was obtained by dividing MFR (temperature = 190 ° C., load = 21.6 kg) defined by JIS-K-7210: 1999 by MFR (temperature = 190 ° C., load = 2.16 kg). .
(7) Die Swell 2.095 mm diameter, length 8.0 mm, manufactured by Toyo Seiki Co., Ltd. equipped with a capillary die of 90 °; using Capillograph 1D, polyethylene resin composition was 190 ° C., piston descending speed Extruded into a string in a constant speed of 10 mm / min at room temperature (about 25 ± 2 ° C.). And the diameter of this string-like thing is measured at 190 degreeC, and the die swell in 190 degreeC of a polyethylene-type resin composition is computed based on a following formula.
Die swell of polyethylene resin composition at 190 ° C. = string diameter (mm) / capillary die inner diameter (mm)
(8) Strain hardenability and strain hardening degree (λmax)
It measured by the following method.
Equipment: ARES manufactured by TA Instruments
Jig: Ext. Viscosity Fixture (EVF) Elongation Viscosity Measurement Jig Measurement Temperature: 134 ° C
Strain rate: 0.5 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and thickness 0.7 mm is formed by press molding.
(Calculation method)
The elongational viscosity at a strain rate of 0.5 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongational viscosity ηE (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before the rise of elongational viscosity (indicating strain hardening) is approximated by a straight line to obtain the maximum value (ηmax) of the elongational viscosity ηE, and on the approximated line up to that time The viscosity is ηlin. FIG. 1 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
(9) Tensile modulus Measured according to JIS K7161: 1994.
(10) Foam processability The foam processability of the foam film was evaluated as follows.
◯: When the foamed film is obtained without tearing the foamed film due to outgassing during film formation of the foamed film.
X: When the foamed film is torn, the foamed film is broken due to outgassing, and the foamed film cannot be obtained.
(11) Apparent density The foam film was cut into a predetermined size, and its volume and weight were measured to obtain an apparent density.
(12) Surface appearance The surface of the foamed film was observed by magnifying it 10 times with a microscope.
A: The bubbles are uniform.
○: A state in which bubbles with slightly uneven bubbles are mixed.
X: Air bubbles are not uniform.
(13) Thermal insulation (sensory test)
A commercially available coffee beverage can (steel can with an internal capacity of 150 g) is conditioned in a hot air oven at 70 ° C. for 1 hour and then taken out. The test was conducted with 10 panelists and evaluated according to the following criteria.
A: When 8 or more panelists are held with bare hands for 30 seconds or more.
○: When 6 to 7 panelists are held with bare hands for 30 seconds or more.
X: When there are 5 or more panelists who cannot be held with bare hands for 30 seconds or more.

<Resin sample preparation>
・ Linear polyethylene (α-i)
(1) Preparation of solid catalyst [A-1] (1-1) Synthesis of complex soluble in inert hydrocarbon solvent 175 g of dibutyl magnesium and 30 g of triethylaluminum together with 1 liter of hexane and made of stainless steel with a capacity of 4 liters placed in a vessel, by reacting with stirring for 2 hours at 85 ° C., it was synthesized complex composition _{AlMg 5 (C 2 H 5)} 3 (C 4 H 9) 10.
(1-2) Preparation of support 2740 ml of trichlorosilane (HSiCl ₃ ) as a 2 mol / l n-heptane solution was charged into a 15 liter reactor sufficiently purged with nitrogen, and kept at 50 ° C. with stirring. in the composition formula _{AlMg 6 (C 2 H 5)} 3 (n-C 4 H 9) 10.8 (On-C 4 H 9) the organomagnesium component represented by _1.2 n-heptane solution 7 liters (magnesium terms 5 mol) was added over 1 hour, and the mixture was further reacted with stirring at 50 ° C. for 1 hour. After completion of the reaction, the supernatant was removed and washed 4 times with 7 liters of n-hexane to obtain a solid material slurry. As a result of separation and drying analysis of this solid, it contained 8.62 mmol of Mg, 17.1 mmol of Cl, and 0.84 mmol of n-butoxy group (On-C ₄ H ₉ ) per gram of the solid.
(1-3) Preparation of Solid Catalyst A slurry containing 500 g of the solid was reacted with 2160 ml of n-butyl alcohol 1 mol / liter n-hexane solution at 50 ° C. for 1 hour with stirring. After completion of the reaction, the supernatant was removed and washed once with 7 liters of n-hexane. The slurry was kept at 50 ° C., and 970 ml of n-hexane solution of 1 mol / liter of diethylaluminum chloride was added with stirring and reacted for 1 hour. After completion of the reaction, the supernatant was removed and washed twice with 7 liters of n-hexane. The slurry was kept at 50 ° C., 270 ml of n-hexane solution of 1 mol / liter of diethylaluminum chloride and 270 ml of n-hexane solution of 1 mol / liter of titanium tetrachloride were added and reacted for 2 hours. After completion of the reaction, the supernatant was removed and washed with 7 liters of n-hexane four times while maintaining the internal temperature at 50 ° C. to obtain a solid catalyst component as a hexane slurry solution. This solid catalyst was separated, dried and analyzed, and as a result, 0.52 mmol of titanium was contained per gram of the solid catalyst.
(2) Polymerization A combination of solid catalyst [A-1] and triisobutylaluminum was used as the catalyst.
A stainless steel polymerization vessel having a reaction volume of 300 liters was used for the polymerization. The sum of the volume of the solvent in the polymerization vessel and the volume of polyethylene measured by a level gauge using γ-rays is 170 L, and the rate per volume at which the solvent and polyethylene are constantly extracted from the polymerization vessel is 51 L. Liter / h. Therefore, the average residence time was 1.1 hours. The polymer was withdrawn from the polymerization vessel 1 at a rate of 10 kg / h. Under the conditions of a polymerization temperature of 86 ° C. and a polymerization pressure of 0.6 MPa, the catalyst is 0.5 g / h of the solid catalyst [A-1] and 20 mmol / h of the organoaluminum compound [B-1] in terms of Al atom. h and hexane were introduced at a rate of 40 l / h. Hydrogen is used as the molecular weight regulator, ethylene, hydrogen and propylene, so that the gas phase concentration of hydrogen is 43 mol%, the gas phase concentration of propylene is 2.4 mol%, and the supply amount of ethylene is 10 kg / h. The polymerization was carried out by feeding to a polymerization vessel. The catalytic activity in the polymerization vessel was 20000 g / g / h.
By the polymerization, powdery linear polyethylene (α-i) was produced. The density of the obtained linear polyethylene (α-i) is 951 kg / m ³ , MFR is 7.8, Mw / Mn is 4.4, the melting point is 131 ° C., the number is 1, and the crystallization temperature is The peak number of the exothermic curve was 115 ° C.
・ Linear polyethylene (α-ii to iv)
[Preparation of metallocene supported catalyst [I]]
Silica P-10 [manufactured by Fuji Silysia Co., Ltd. (Japan)] was calcined at 400 ° C. for 5 hours in a nitrogen atmosphere and dehydrated. The amount of surface hydroxyl groups of dehydrated silica was 1.3 mmol / g-SiO ₂ . 40 g of this dehydrated silica was placed in an autoclave having a capacity of 1.8 liters, and 800 cc of hexane was added and dispersed to obtain a slurry. While the obtained slurry was kept at 50 ° C. with stirring, 60 cc of a hexane solution of triethylaluminum (concentration 1 mol / liter) was added, and then stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silica to be treated with triethylaluminum. A component [IV] containing silica and a supernatant liquid and having all surface hydroxyl groups of the silica treated with triethylaluminum capped with triethylaluminum was obtained. Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation to remove unreacted triethylaluminum in the supernatant liquid. Thereafter, an appropriate amount of hexane was added to obtain 800 cc of a hexane slurry of silica treated with triethylaluminum.

On the other hand, 200 mmol of [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added to Isopar E [exon. Product name of hydrocarbon mixture manufactured by Chemical Co. (USA)] 1 mol of a composition formula AlMg ₆ (C ₂ H ₅ ) ₃ (n-C ₄ H ₉ ) ₁₂ dissolved in 1000 cc and previously synthesized from triethylaluminum and dibutylmagnesium 20 cc / liter hexane solution was added, and further hexane was added to adjust the titanium complex concentration to 0.1 mol / liter to obtain component [V].

  Further, 5.7 g of bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter referred to as “borate”) was added to 50 cc of toluene and dissolved, and borate Of 100 mmol / liter of toluene was obtained. 5 cc of a 1 mol / liter hexane solution of ethoxydiethylaluminum was added to this toluene solution of borate at room temperature, and further hexane was added so that the borate concentration in the solution was 70 mmol / liter. Then, it stirred at room temperature for 1 hour and obtained the reaction mixture containing a borate.

  46 cc of this reaction mixture containing borate was added to 800 cc of the slurry of component [IV] obtained above with stirring at 15 to 20 ° C., and the borate was supported on silica by physical adsorption. Thus, a slurry of silica carrying borate was obtained. Further, 32 cc of the component [V] obtained above was added and stirred for 3 hours to react the titanium complex with borate. Thus, a metallocene-supported catalyst [I] containing silica and a supernatant liquid and having catalytically active species formed on the silica was obtained.

[Preparation of liquid promoter component [II]]
Organomagnesium compounds as _[III-1], using an organic magnesium compound represented by the _{AlMg 6 (C 2 H 5)} 3 (n-C 4 H 9) 12. Methyl hydropolysiloxane (viscosity 20 centistokes at 25 ° C.) was used as compound [III-2].

To a 200 cc flask, 40 cc of hexane and AlMg ₆ (C ₂ H ₅ ) ₃ (n-C ₄ H ₉ ) ₁₂ were added with stirring while adding 37.8 mmol of Mg and Al, and methylhydropolysiloxane was added at 25 ° C. Liquid promoter component [II] was prepared by adding 40 cc of hexane containing 2.27 g (37.8 mmol) with stirring, and then raising the temperature to 80 ° C. and reacting with stirring for 3 hours.

[Preparation of ethylene homopolymer which is linear polyethylene (α-ii to iv) and copolymer of ethylene and α-olefin]
(Α-ii) The metallocene-supported catalyst [I] and the liquid promoter component [II] obtained as described above are brought into contact with hydrogen by supplying a necessary amount of hydrogen as a chain transfer agent to the catalyst transfer line, thereby causing a polymerization reaction. Introduced into a vessel, hexane was used as a solvent, and ethylene and 1-butene were used as monomers. The reaction temperature was 78 ° C, and a mixed gas of ethylene, 1-butene, and hydrogen (the gas composition was such that the molar ratio of 1-butene to ethylene + 1-butene was 0.30, and the molar ratio of hydrogen to ethylene + hydrogen was 0.0032. A copolymer of ethylene and 1-butene, which is linear polyethylene (α-ii), was polymerized with a total pressure of 0.8 MPa. The obtained linear polyethylene (α-ii) ethylene-1-butene copolymer has a density of 947 kg / m ³ , an MFR of 5.0 g / 10 min, and a molecular weight determined by gel permeation chromatography. Distribution (Mw / Mn) was 3.5.

(Α-iii) The density is the same as (α-ii) except that a mixed gas of ethylene and hydrogen (the gas composition is adjusted so that the molar ratio of hydrogen to ethylene + hydrogen can be maintained at 0.48). 966 kg / m ³ , MFR 12 g / 10 min, molecular weight distribution: Mw / Mn 3.5. An ethylene homopolymer (α-iii), which is a linear polyethylene, was obtained.
(Α-iv) Except for the mixed gas of ethylene, 1-butene and hydrogen (the gas composition is adjusted so that the molar ratio of 1-butene and ethylene + 1-butene can be maintained at 0.36) (α-ii) In the same manner, an ethylene-1-butene copolymer (α-iv) which is a linear polyethylene having a density of 941 kg / m ³ , MFR of 2.5 g / 10 min, and molecular weight distribution: Mw / Mn of 4.2. )
(Α-v) Linear polyethylene (α-v) is obtained by polymerization of ethylene and 1-butene having physical properties described in Table 1 polymerized using a Ziegler catalyst by the method described in JP-A-60-4506. It is a copolymer.

[Preparation of ethylene polymer as high-pressure low-density polyethylene (β)]
High pressure low density polyethylene (β-i) is obtained by radical polymerization of ethylene in an autoclave type reactor. The polymerization conditions were set to a temperature of 200 to 300 ° C. and a polymerization pressure of 100 to 250 MPa in the presence of peroxide, a density of 921 kg / m ³ , an MFR of 0.6 g / 10 minutes, and a molecular weight distribution: Mw / Mn of 14. 7. A branched high pressure method in which the melt tension ratio (MTR ₂ ) is 0.93, the melt tension (MT ₁₉₀ ° C.) is 143 mN, the melt flow rate ratio (FRR) is 46.5, and the relationship of the formula [3] is established. Low density polyethylene (β-i) was obtained.

[Examples 1 to 5]
A polymer blend obtained by mixing linear polyethylene (α) and branched high-pressure method low-density polyethylene (β) in the proportions shown in Table 1 was used as TEX-44 (screw diameter 44 mm, L / D = 35, manufactured by Nippon Steel Works). ) Was melt-kneaded and granulated at a temperature of 220 ° C. to obtain a polyethylene resin composition.
The evaluation results of the obtained polyethylene resin composition are also shown in Table 2.

“Polyslen EE275F (manufactured by Eiwa Kasei Kogyo Co., Ltd.)” as a sodium hydrogen carbonate-based foaming agent concentrate as a foaming agent is added to 100 parts by mass of this polyethylene-based resin composition at a ratio shown in Table 3, and dry blended with a pellet blender. Went. Inflation film manufacturing apparatus manufactured by Sumitomo Heavy Industries Modern Co., Ltd. (screw diameter 50 mm, screw: L (extrusion screw length) / D (extrusion screw diameter) = 28, lip diameter: 100 mm, lip gap: 1.0 mm, air Using a ring (single lip, for φ100, fixed type), a blown film was obtained by performing inflation molding at a cylinder temperature of 180 ° C., a die temperature of 180 ° C., and a predetermined blow ratio described in Table 3.
The evaluation results of the obtained foamed film are also shown in Table 3.

[Comparative Example 1]
This was carried out in the same manner as in the Examples except that only the linear polyethylene (α-iv) was used and the branched high-pressure method low-density polyethylene (β-i) was not blended. The foamed film was broken due to the break-out, and the foamed film could not be obtained.
[Comparative Example 2]
Linear polyethylene (α-v) and branched high-pressure low-density polyethylene (β-i) were blended in the proportions shown in Table 1, and a polyethylene resin composition was obtained in the same manner as in the examples. Further, a foamed film was prepared from the polyethylene resin composition by the same method as in the examples.
The evaluation results of the obtained polyethylene resin composition are shown in Table 2, and the evaluation results of the obtained foamed film are shown in Table 3.

  The present invention provides a foamed film having good rigidity and foamed state, excellent surface appearance and heat insulation, and has high utility value in various fields of industry. For example, gifts for ceremonial occasions, gifts, souvenirs, packaging films for frozen and chilled frozen foods, decorative films, agricultural coating films, tape substrates, vibration absorbing materials, light reflecting materials, shielding Suitable as a material, a heat insulating material, etc.

Claims (8)

Polyethylene resin composition having a density of 930 to 960 kg / m ³ , 190 ° C., a melt flow rate of 0.1 to 20 g / 10 min at a load of 2.16 kg, and a die swell of 1.30 to 2.00 at 190 ° C. A foamed film comprising:   2. The foamed film according to claim 1, wherein the polyethylene-based resin composition has strain-hardening properties in measurement of elongational viscosity and has a strain-hardening degree (λmax) of 2.0 to 30. 3. The foamed film according to claim 1 or 2, wherein the polyethylene resin composition satisfies the following requirements 1) to 4).
1) 90 to 40% by mass of linear polyethylene (α) and 10 to 60% by mass of high-pressure low-density polyethylene (β) are included.
2) The melting point peak of the endothermic curve obtained in the temperature rise measurement by the differential scanning calorimeter is one.
3) The melt tension ratio (MTR ₁ ) represented by the following formula [1] is 2.5 or more.
MTR ₁ = (MT ₁₆₀ ° C.) / (MT ₁₉₀ ° C.) [1]
(However, in the above formula [1], the subscript of MT is the measurement temperature of melt tension.)
4) The tensile elastic modulus is 400 MPa or more. The linear polyethylene (α) satisfies the following requirements (α-1) to (α-4), and the high-pressure method low-density polyethylene (β) is represented by the following (β-1) to (β-3). The foamed film according to any one of claims 1 to 3, wherein the requirement is satisfied.
(Α-1) An ethylene homopolymer or a copolymer comprising a repeating unit derived from ethylene and a repeating unit derived from one or two or more α-olefins having 3 to 20 carbon atoms.
(Α-2) The density is 935 to 975 kg / m ³ .
(Α-3) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 20 g / 10 min.
((Alpha) -4) Mw / Mn calculated | required by the gel permeation chromatography method is 3-7.
(Mn is a number average molecular weight, Mw is a weight average molecular weight, and Mw / Mn is an index representing a molecular weight distribution.)
(Β-1) The density is 910 to 930 kg / m ³ .
(Β-2) The melt flow rate at 190 ° C. and a load of 2.16 kg is 0.1 to 10 g / 10 min.
(Β-3) Molecular weight distribution determined by gel permeation chromatograph: Mw / Mn is 8-24.   The linear polyethylene (α) comprises (a) a carrier material, (b) an organoaluminum, (c) a transition metal compound having a cyclic η-binding anion ligand, and (d) the cyclic η-binding anion arrangement. It is produced by polymerization using a metallocene-supported catalyst [I] prepared from an activator capable of reacting with a transition metal compound having a ligand to form a complex that exhibits catalytic activity, and a liquid promoter component [II]. The foam film of any one of Claims 1-4 which is a thing. The foamed film according to any one of claims 1 to 5, wherein the high-pressure low-density polyethylene (β) satisfies the following requirement (β-4).
(Β-4) The melt tension ratio (MTR ₂ ) represented by the following formula [2] is 0.7 or more, and the relationship between the melt flow rate ratio (FRR) and the melt tension (MT) is [3] is satisfied.
MTR ₂ = (MT ₂₄₀ ° C.) / (MT ₁₉₀ ° C.) [2]
(MT ₁₉₀ ° C.) ≧ 0.65 (FRR) −20 [3]
(However, in the above formulas [2] and [3], the subscript of MT is the measurement temperature of melt tension, FRR is MFR at temperature = 190 ° C., load = 21.6 kg, temperature = 190 ° C., load = (The value divided by MFR at 2.16 kg.)   The foam film according to any one of claims 1 to 6, wherein an apparent density is 180 g / L or more and 800 g / L or less and a thickness is 10 to 500 µm.   The method for producing a foamed film according to any one of claims 1 to 7, wherein the polyethylene resin composition is molded by an inflation molding method or a T-die molding method.