JP2013124300A - Polyethylene-based resin composition for non-crosslinked foaming - Google Patents

Abstract

Non-crosslinked foaming polyethylene resin composition capable of obtaining a foam having a good foaming state, such as a high closed cell ratio, a small bubble diameter, uniform bubble uniformity, and good surface appearance, and uses thereof I will provide a.
A melt flow rate at a density of 930 to 960 kg / m ³ , 190 ° C. and a load of 2.16 kg is 0.1 to 20 g / 10 minutes, has strain-hardening properties in measurement of elongational viscosity, and strain hardening. A polyethylene resin composition for non-crosslinking foaming having a degree (λmax) of 2.0 to 30 and its use.
[Selection figure] None

Description

  The present invention relates to a polyethylene-based resin composition for non-crosslinking foaming. More specifically, for example, a non-crosslinked foaming polyethylene resin composition that can be used as a heat insulating material for building materials, industrial materials, adhesive tape base materials, furniture, household electrical appliances, heat insulating / cooling agents, etc. It is about.

Conventionally, polyolefin-based resins are widely used for various heat insulating materials, cushioning materials, levitation materials and the like because they are excellent in lightness, heat resistance, heat insulation, flexibility, mechanical strength and the like. And recently, it is used as a vehicle interior material such as a ceiling, a door, and a deck of an automobile, or as a composite building material such as a flooring material for a building material and a heat insulating material for a floor.
Above all, polyethylene resin foams have a high closed cell ratio, small cell diameter, and uniform foaming, and therefore take advantage of their excellent cushioning, heat insulation, cutting workability, flexibility, and resilience. It is used for a wide range of purposes. For example, if it is a sheet-like material, it is a packaging material for precision equipment, a heat insulating mat for a bathroom, if it is a rod-like material, a joint material that fills the gaps in the building, if it is a board-like material, a beat plate, cutting processing If it is, it has been applied to buffer pads for large electrical equipment.

Among the polyethylene-based resins having such characteristics, low-density polyethylene has a long chain branch having an appropriate length in its molecular chain, so that the melt viscosity during melting is relatively high due to the entanglement between the molecular chains. high. 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 ethylene resins.
In the use of the above-described heat insulating material and cushioning material, characteristics such as rigidity as a foam material are also required. Since it is difficult to show sufficient rigidity with low-density polyethylene alone, high-density polyethylene is preferable from that viewpoint. However, since high-density polyethylene has few branches in its molecular chain, its melt viscosity at the time of melting is very low, its crystallinity is high, and its crystallization speed is high. For this reason, it is necessary to adjust the melt viscosity suitable for foaming, and it is difficult to produce high-density polyethylene by foaming high-density polyethylene, having a high closed cell ratio, small cell diameter, and uniform foaming. I was doing.
A method of increasing the melt tension of high-density linear polyethylene as a method for obtaining a high-quality foam having closed cells and a foamed molded article having a high expansion ratio using high-density linear polyethylene There is.
As a method for increasing the melt tension of linear polyethylene having a high density, specifically, (1) a method of mixing high molecular weight polyethylene having a high melt tension (for example, see Patent Document 1), (2) chromium-based polyethylene A method of mixing polyethylene having a high melt tension produced by a catalyst (for example, see Patent Document 2), (3) A method of mixing low-density polyethylene produced by a high-pressure radical polymerization method (for example, Patent Document 3, Patent Document) 4), (4) a method of increasing melt tension by adding a crosslinking agent or a peroxide to polyethylene and modifying it (see, for example, Patent Document 5), and the like.

  Further, in order to give a higher melt tension than the above-described method, (5) a method using a special long-chain branched high-density polyethylene (for example, see Patent Document 6 and Patent Document 7), (6) Melting A study focusing on die swell, which is one of the indices of elastic properties (for example, see Patent Document 8) has also been proposed.

Japanese Patent Laid-Open No. 10-7726 JP-A-2-132109 Japanese Unexamined Patent Publication No. 7-134359 JP 2010-24820 A JP 2003-327757 A JP 2006-96910 A JP 2008-222818 A JP 2005-290329 A JP 2004-043813 A

Yamaguchi et al., Polymer, Vol. 42, 2001, p. 8663 L. A. UTRACKI, Toshio Nishi, “Polymer Alloy and Polymer Blend”, Tokyo Kagaku Doujin, 1st Edition, December 6, 1991, p. 75

Thus, as a result of paying attention to strain hardening, which is one of the indicators of the physical properties of the resin, it was possible to obtain a polyethylene resin composition for non-crosslinking foaming that yielded a foam having a good foamed state.
The problem to be solved by the present invention is a non-crosslinked foaming polyethylene which can obtain a foam having a good foaming state, such as a high closed cell ratio, a small bubble diameter, a uniform bubble and a good surface appearance. System resin composition.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventor has developed a specific non-crosslinked structure preferably containing linear polyethylene (α) and high-pressure low-density polyethylene (β) each having specific physical properties. Since the foamed polyethylene resin composition has strain hardening, which is one of the physical properties of the resin, the closed cell ratio is high, the bubble diameter is small, the uniformity of the bubbles, and the surface appearance. It is a non-crosslinked foaming polyethylene resin composition that provides a foam having a good foamed state, such as being good, and has been found to be suitable for solving the above-mentioned problems, and based on this finding, the present invention is made. It came.

That is, this invention relates to the polyethylene-type resin composition for non-crosslinking foaming of the specific structure shown below.
[1]
Density is 930 to 960 kg / m ³ , 190 ° C., melt flow rate at a load of 2.16 kg is 0.1 to 20 g / 10 min, strain hardening property in measurement of elongational viscosity, and strain hardening degree (λmax) Is a polyethylene-based resin composition for non-crosslinking foaming, characterized by being 2.0-30.
[2]
The non-crosslinked foaming polyethylene resin composition according to [1], wherein a die swell at 190 ° C is 1.30 to 2.00.
[3]
The polyethylene resin composition for non-crosslinking foaming according to [1] or [2], which satisfies the following requirements 1) to 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.
[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 polyethylene-based resin composition for non-crosslinking foaming 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) The occupation ratio of the component having a converted molecular weight of 10 ⁶ or more determined by gel permeation chromatography is 1.5 to 9.0% by mass of the whole high-pressure method low-density polyethylene (β).
[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 polyethylene-based resin composition for non-crosslinking foaming according to [3] or [4].
[6]
A foamed molded article comprising the non-crosslinked foaming polyethylene resin composition according to any one of [1] to [5].
Here, “comprising” means that the entire foamed molded article is composed of the non-crosslinked foaming polyethylene resin composition, and a part of the foamed molded article is used for the noncrosslinked foaming. When it is comprised with the polyethylene-type resin composition, it is the meaning containing both.
[7]
The foamed molded product according to [6], which is a non-crosslinked extruded foam sheet.

  The non-crosslinked foamed polyethylene resin composition of the present invention comprises a polyethylene-based resin non-crosslinked foamed molded article having a high closed cell ratio, a small cell diameter, good cell uniformity, and good surface appearance. The foaming state is good. Such a foam-molded product is suitable, for example, as a heat insulating material for building materials, industrial materials, pressure-sensitive adhesive tape base materials, furniture, household electric appliances, buffering agents such as heat and cold insulation agents, and heat insulating materials.

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

  Hereinafter, the present invention will be specifically described.

The density of the non-crosslinked foaming polyethylene resin composition of the present invention is 930 to 960 kg / m ³ , preferably 940 to 960 kg / m ³ , and more preferably 945 to 960 kg / 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 the component to be used, for example, each density and compounding quantity of a linear polyethylene ((alpha)) and a high pressure method low density polyethylene ((beta)).

If the density of the polyethylene resin composition for non-crosslinking foaming is 930 kg / m ³ or more, the heat-resistant stability of the polyethylene resin non-crosslinking foamed molded article can be obtained when the polyethylene resin composition for non-crosslinking foaming is used. It is excellent in the foaming state of a polyethylene-based resin non-crosslinked foamed molded article together with mechanical properties. If the density of the polyethylene-based resin composition for non-crosslinking foaming is 960 kg / m ³ or less, the foamed state of the polyethylene-based resin non-crosslinking foamed molded product is good as well as the mechanical properties and impact properties of the polyethylene-based resin non-crosslinked foamed molded product. Can be both.

  The density of the polyethylene-based resin composition for non-cross-linking foaming may balance the mechanical properties and impact properties of the polyethylene-based resin non-cross-linking foamed molded product with the good foaming state of the polyethylene-based resin non-cross-linking foam molded product. It is preferable that it exists in the said range at the point which can be performed.

The MFR of the polyethylene-based resin composition for non-crosslinking foaming of the present invention is 0.1 to 20 g / 10 min at 190 ° C. and 2.16 kg load, preferably 2.0 to 10 g / 10 min, more preferably. Is 4.0 to 8.0 g / 10 min. The MFR of the polyethylene-based resin composition for non-crosslinking foaming can be measured by the method described in Examples below. The MFR of the polyethylene-based resin composition for non-crosslinking foaming can be adjusted by the components used, for example, the MFR and the blending amount of each of the linear polyethylene (α) and the high-pressure low-density polyethylene (β).
When the MFR of the polyethylene-based resin composition for non-crosslinking foaming is 0.1 g / 10 min or more and 20 g / 10 min or less, the processability of the polyethylene resin non-crosslinking foamed molded article is excellent.
The non-crosslinking foaming polyethylene resin composition used in the present invention has strain-hardening properties in the measurement of elongational viscosity.
The melt tension is improved by increasing the molecular weight of the resin (decreasing the melt flow rate), but the conventional linear high-density polyethylene resin does not exhibit strain hardening in uniaxial elongational flow, Both cannot be identified. 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. The present inventors have found that a foam holding air bubbles independent of the membrane can be obtained.
The polyethylene resin composition for non-crosslinking foaming of the present invention has a strain hardening degree (λmax) in the measurement of elongational viscosity of 2.0 to 30, preferably 5.0 to 25, more preferably 10 to 20. . When the strain hardening degree (λmax) is in the range of 2.0 to 30, the foamed state is good and the surface appearance is excellent.
That is, the present inventors have found that it is effective to use the degree of strain hardening (λmax) obtained from the measurement of the extensional viscosity as one of the indexes of foamability of the resin. The strain hardening degree (λmax) is an index representing the strength at the time of melting. When this value is large, there is an effect of improving the 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, regarding the method of measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial elongation viscosity can be measured. Details of the measuring method and measuring instrument are described in Non-Patent Document 2, for example. However, preferable measurement 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 having a size of 18 mm × 10 mm and a thickness of 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.
In the non-crosslinked foaming polyethylene resin composition of the present invention, the die swell at 190 ° C. is preferably 1.30 to 2.00, more preferably 1.40 to 1.90, still more preferably 1.50. ~ 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 is excellent. This is because if the die swell of the polyethylene-based resin composition at 190 ° C. is too small, the bubble stability at the time of foaming is reduced and bubble breakage occurs, resulting in a decrease in the closed cell ratio or an inadequate bubble state. It becomes uniform, the appearance of the molded body tends to be poor in appearance, the foamed state is good, and the highly foamed foamed molded article with excellent surface appearance cannot be obtained.
In addition, if the die swell at 190 ° C. is too large, shrinkage after the thermoforming process of the foamed molded product is large, and the elongation 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 for non-crosslinking foaming of the present invention can be set to a 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.

In addition, the die swell at 190 ° C. of the polyethylene-based resin composition for non-crosslinking foaming was measured by the method described in JIS K7199: 1999 “Plastic-capillary rheometer and plastic flow property test method using slit direometer”. Say. 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 shape at a constant speed of piston lowering rate of 10 mm / min in an environment of 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)

The polyethylene resin composition for non-crosslinking foaming of the present invention is preferably composed of linear polyethylene (α) and high pressure method 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, and still more preferably the linear polyethylene (α) is 80 to 70% by mass. It is 20-30 mass% of low density polyethylene ((beta)).
If the blending ratio of the high-pressure method low density polyethylene (β) is 10% by mass or more and 60% by mass or less, the closed cell ratio is high, the cell diameter is small, the cell uniformity, the surface appearance is good, etc. A non-crosslinked foaming polyethylene resin composition having a good foamed state can be easily obtained.
The melting point peak of the endothermic curve obtained in the temperature rise measurement with a differential scanning calorimeter of the polyethylene resin composition for non-crosslinking foaming of the present invention is preferably 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 molded article having a good foamed state, such as a high closed cell ratio, a small bubble diameter, and good bubble uniformity and surface appearance.
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. Can be obtained. By using linear polyethylene (α) having a narrow molecular weight distribution, the compatibility between the two is considered to be enhanced.

  Polyethylene resin compositions having such characteristics have, for example, a large proportion of linear polyethylene (α) having a narrow molecular weight distribution (Mw / Mn) and a high molecular weight component required by gel permeation chromatography. It can be obtained by blending high-pressure low-density polyethylene (β) having more branched side chains. 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 strain-hardening properties when measuring an elongational viscosity.

(Linear polyethylene (α))
The linear polyethylene (α) preferably used in the polyethylene resin composition for non-crosslinking foaming of the present invention is an ethylene homopolymer or a repeating unit derived from ethylene and one or two or more kinds of α having 3 to 20 carbon atoms. -A copolymer comprising repeating units derived from olefins is preferred. “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 .

If the density of the linear polyethylene (α) is 935 kg / m ³ or more, the flexibility, mechanical properties, and the non-crosslinked foamed polyethylene resin composition when the non-crosslinked foamed polyethylene resin composition is used, and Excellent heat resistance stability. If the density of the linear polyethylene (α) is 975 kg / m ³ or less, the flexibility, mechanical properties, and heat resistance of the polyethylene resin non-crosslinked foamed molded article are obtained when the polyethylene resin composition for non-crosslinking foam is used. It has excellent stability and good moldability.
The density of the linear polyethylene (α) is excellent in flexibility, mechanical properties and heat resistance stability when it is made into a polyethylene resin non-crosslinked foamed molded article comprising a polyethylene resin composition for non-crosslinking foaming and polyethylene. It is preferable that it exists in the said range at the point from which the moldability of a resin-based non-crosslinked foamed molded article is also obtained.
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, molding of a polyethylene-based resin non-crosslinked foamed molded article comprising a non-crosslinked foaming polyethylene-based resin composition Excellent workability and good foamed state.
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 molecular weight uniformity, the closed cell ratio is high, the bubble diameter is small, the bubble uniformity, and the surface appearance are good. For example, there can be obtained a foamed molded article comprising a non-crosslinking foaming polyethylene resin composition having a good foamed state.

  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 polyethylene resin non-crosslinked foamed molded article having a good foamed state, such as a high closed cell ratio, a small bubble diameter, a good bubble uniformity, and a good surface appearance.

  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 polyethylene resin composition can be measured by a method such as a cross-fractionation chromatography method (CFC method).

The linear polyethylene (α) preferably 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. And 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 peak of the endothermic curve and the peak of the exothermic curve of the linear polyethylene (α) preferably used in the present invention, can be determined in the temperature rise measurement and temperature drop 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 polyethylene resin non-crosslinked foamed molded article having a good foamed state, such as a high closed cell ratio, a small bubble diameter, a good bubble uniformity, and a good surface appearance.
The crystallization temperature which is the peak of the exothermic curve obtained in the temperature drop measurement of the linear polyethylene (α) by a differential scanning calorimeter is 110 ° C to 130 ° C, preferably 115 ° C to 125 ° C. . When the crystallization temperature is 110 ° C. or higher and the crystallization temperature is 130 ° C. or lower, a polyethylene resin non-crosslinked foamed molded article having a good foamed state can be obtained.
The differential scanning calorimeter can be measured using a differential scanning calorimeter (Pyris 1 type DSC device manufactured by Perkin Elmer) 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 the solution 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 of the organomagnesium compound preferably used with the chlorinating agent 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 to 200 degreeC 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 to 10 is 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 to 200 degreeC 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 the solution 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 gel permeation chromatography, as well as a low molecular weight component, unlike the production method described above. Oligomer components can be reduced, and chlorine is not included in the manufacturing process, so it is excellent in cleanliness, and it is a buffer for building insulation, industrial materials, adhesive tape base materials, furniture, household electrical appliances, heat insulation / cooling agents, etc. Suitable for non-crosslinking foaming polyethylene resin compositions for agents and heat insulating materials.

  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 for non-crosslinking foaming of the present invention is an ethylene homopolymer or ethylene and 1 or 2 It is preferable that it is a copolymer with a C3-C20 alpha olefin more than a seed | species, 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.

The occupation ratio of the component having a converted molecular weight of 10 ⁶ or more of the high-pressure method low-density polyethylene (β) used in the present embodiment is determined in the gel permeation chromatography method, and preferably 1.5 to 9.0% by mass. More preferably, it is 2.0-8.0 mass%, More preferably, it is the range of 2.5-7.0 mass%. Such a high-pressure low-density polyethylene (β) having a high molecular weight component can be obtained by radical polymerization of ethylene in an autoclave type reactor.
If the high molecular weight low density polyethylene (β) component occupancy ratio of 10 ⁶ or more is within the above range, there are many branched side chains of the high pressure low density polyethylene (β) and the branch point is the starting point. It is presumed that the linear polyethylene (α) is crystallized to form a network structure during the foam molding process in the linear polyethylene (α) and the high-pressure low-density polyethylene (β). Therefore, a non-crosslinked foamed molded article comprising a non-crosslinked foaming polyethylene resin composition having a good foaming state, such as a high closed cell ratio, a small bubble diameter, good cell uniformity, and good surface appearance. Can be obtained.
In particular, if the occupation ratio of the component having a converted molecular weight of 10 ⁶ or more of the high pressure method low density polyethylene (β) is 1.5% by mass or more, a blend of linear polyethylene (α) and high pressure method low density polyethylene (β) In this case, it is presumed that the linear polyethylene (α) and the high-pressure low-density polyethylene (β) can be made in a good compatibility state and the crystal state of both can be prevented from phase separation. For this reason, non-crosslinked foam molding comprising a non-crosslinked foaming polyethylene resin composition having a good foaming state, such as a high closed cell ratio, a small bubble diameter, good bubble uniformity, and good surface appearance. You can get a body.
The occupation ratio of the component having a reduced molecular weight of 10 ⁶ or more can be determined by gel permeation chromatography, and more specifically can be measured by the method described in the examples described later. Moreover, the occupation rate of the component of the high molecular weight low density polyethylene (β) having a converted molecular weight of 10 ⁶ or more in the polyethylene resin composition can also be measured by a method such as a cross fractionation chromatographic method (CFC method).
The high-pressure low-density polyethylene (β) having such characteristics can be obtained by radical polymerization of ethylene in an autoclave type reactor, and has a higher occupancy ratio of components having a converted molecular weight of 10 ⁶ or more. More chains are present. By using this, a non-crosslinked foaming polyethylene-based resin composition having a good foaming state such as a high closed cell ratio, a small bubble diameter, a good bubble uniformity, and a good surface appearance can be obtained. A crosslinked foamed molded article can be easily obtained.

  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 for non-crosslinking foaming of the present embodiment is a resin composition composed of the linear polyethylene (α) and the high pressure method low density polyethylene (β) as described above. Such a linear polyethylene (α) having a narrow molecular weight distribution and a component having a converted molecular weight of 10 ⁶ or more that can be determined by gel permeation chromatography method are as high as 1.5 to 9.0% by mass. , By polymer blending with high-pressure low-density polyethylene (β) having many branched side chains, the closed cell ratio is high, the bubble diameter is small, the uniformity of the bubbles, the surface appearance is good, etc. A non-crosslinked foamed molded article comprising a non-crosslinked foaming polyethylene resin composition having a good foamed state can be easily obtained.

  In general, blend systems of high-density polyethylene and low-density polyethylene are incompatible, and the crystalline state of the two phase-separates (for example, see Non-Patent Document 2), 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 to 7, linear polyethylene (α) having a uniform molecular weight, and occupation of components having a converted molecular weight of 10 ⁶ or more that can be determined by gel permeation chromatography method In a preferred embodiment in which a high-pressure low-density polyethylene (β) having a high ratio of 1.5 to 9.0% by mass and a large number of branched side chains is polymer-blended in a predetermined ratio range, the crystallization rate is As the speed increases, the crystal size tends to become smaller and the crystal state tends to be uniform, suggesting that linear polyethylene (α) and high-pressure low-density polyethylene (β) are co-crystallized in a compatible state. The Along with such a phenomenon, a tendency to improve the foam molding processability of the polyethylene resin non-crosslinked foamed molded article comprising the non-crosslinked foaming polyethylene resin composition is recognized. 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.

In the non-crosslinked foaming polyethylene resin composition of the present invention, known additives can be added as necessary within a range not impairing the object of the present invention. preferable. 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 molded article without being added. That is, it is preferable that the foamed molded article comprising the non-crosslinked foaming polyethylene resin composition of the present embodiment substantially does not contain any neutralizing agent and 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, it is preferably 150 ppm or less, more preferably 100 ppm or less as a neutralizing agent 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 acts as a lubricant in molding processability, and the surface state of the foamed molded product 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.

  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, and zinc stearate. 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. .

As the foaming agent, for example, a thermally decomposable chemical foaming agent that is liquid or solid at normal temperature and generates a gas upon heating can be used, and any thermal decomposable chemical foaming agent of an inorganic compound or an organic compound may be used.
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 addition amount of the foaming agent is 0.05 to 6.0 parts by weight, preferably 0.3 to 5.0 parts by weight, more preferably 0, per 100 parts by weight of the polyethylene resin composition used in the present invention. It is preferable that it is the range of 0.5-4.0 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, and when mixing linear polyethylene (α) and high-pressure method low-density polyethylene (β) A method may be employed in which a masterbatch is prepared by mixing the additive together with linear polyethylene (α) or high-pressure low-density polyethylene (β), and this is dry-blended at the time of molding.
In producing a polyethylene resin non-crosslinked foamed molded article, it is preferable to mix a polyethylene resin composition, a foaming agent, and various other additives as desired. For example, a linear polyethylene (α) and a high-pressure low-density polyethylene (β) are kneaded together with various additives and a blowing agent in advance using an extruder, preferably a vented extruder, and the round attached to the extruder. A method of obtaining foamed molding by foaming simultaneously with extrusion molding through a die such as a rod-shaped die, T-die, or annular die, and a method of obtaining foamed molding by heating and foaming after forming into an unfoamed sheet. Alternatively, a method of obtaining a foamed molded article by adding a foaming agent after once forming a molded article such as a sheet can be exemplified.
As the foaming agent in this case, in addition to the thermal decomposition type chemical foaming agent mentioned above, for example, inorganic gas foaming agents such as carbon dioxide, nitrogen, argon, air; propane, butane, pentane, hexane, cyclobutane, cyclohexane, Volatile foaming agents such as trichlorofluoromethane and dichlorodifluoromethane can also be used. The amount of the foaming agent added is 1 to 100 parts by mass of the polyethylene resin composition constituting the polyethylene resin foam sheet. The amount is preferably 20 parts by mass, and particularly preferably in the range of 5 to 15 parts by mass.
A foamed molded article comprising a polyethylene-based resin composition for non-crosslinking foaming will be described.
The non-crosslinking foaming polyethylene resin composition is characterized in that it can be obtained from one having a low expansion ratio to one having a high expansion ratio. Such a characteristic is that the occupancy ratio of the component having a converted molecular weight of 10 ⁶ or more which can be determined by linear polyethylene (α) having a narrow molecular weight distribution and gel permeation chromatography method is 1.5 to 9.0 mass. % And high-pressure low-density polyethylene (β) having many branched side chains.
The polyethylene resin non-crosslinked foamed molded article of the present embodiment has an apparent density of 20 g / L or more and 800 g / L or less. When the apparent density is 20 g / L or more and 800 g / L or less, the closed cell ratio is high, the bubble diameter is small, the bubble uniformity is good, the surface appearance is good, etc. Further, it is possible to obtain a polyethylene resin non-crosslinked foamed molded article having good mechanical properties and heat resistance stability and further having good buffering properties.
The apparent density can be measured by the method described in the following examples.
The polyethylene resin non-crosslinked foamed molded article of the present embodiment has a closed cell ratio of 70% or more, preferably 80% or more, more preferably 90% or more.
When the closed cell ratio is 70% or more, the polyethylene resin non-crosslinked foamed molded article having good cell uniformity and surface appearance is excellent.
The closed cell ratio can be measured by the method described in the following examples.
The polyethylene resin non-crosslinked foamed molded article of the present embodiment has an average cell diameter of 150 μm or less, preferably 125 μm or less, more preferably 100 μm or less.
If the average cell diameter is 150 μm or less, it is possible to obtain a polyethylene resin non-crosslinked foamed molded article having a small cell diameter and particularly good surface appearance due to the uniformity of the cells.
The average cell diameter of the polyethylene-based resin non-crosslinked foamed molded product here is a cross-section obtained by cutting the foamed molded product perpendicular to the extrusion molding direction, measuring the cell diameters in the width direction and the thickness direction, respectively. About the average value of the whole bubble diameter of the width direction and the thickness direction was made into the average bubble diameter.
In this Embodiment, an average bubble diameter can be measured by the method as described in a following example.

  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).

(3) using the apparatus of occupancy Waters Co. ALLIANCE GPCV 2000 of Mw / Mn (molecular weight distribution) and in terms of molecular weight 10 ⁶ or more component by gel permeation chromatography, Shodex manufactured by AT-807S and Tosoh as column Using TSK-gelGMH-H6 manufactured in series, the 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)
Using a differential scanning calorimeter (Pyris type 1 DSC device manufactured by Perkin Elmer), the measurement was performed 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) Die swell 2.095 mm diameter, length 8.0 mm, manufactured by Toyo Seiki Co., Ltd. equipped with a capillary die having an inflow angle of 90 °; using Capillograph 1D, the polyethylene resin composition was 190 ° C., and the 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)
(6) 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 having a size of 18 mm × 10 mm and a thickness of 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 the extension viscosity (indicating strain hardening) is approximated by a straight line to obtain the maximum value (ηmax) of the extension viscosity ηE, and on the approximate 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.
(7) Apparent density The uncrosslinked foamed molded article was cut into a predetermined size, and its volume and weight were measured to obtain an apparent density.

(8) Closed cell ratio It measured according to ASTM D-2856, and calculated | required by the following formula.

Vx: Actual volume (cm ³ ) of polyethylene resin foam molded article
Va: Apparent volume (cm ³ ) of polyethylene-based resin foam molding
ρf: Density (g / cm ³ ) of polyethylene-based resin foam molding
ρs: density of polyethylene-based resin composition (g / cm ³ )

(9) Average cell diameter The cross-section cut out of the foamed molded product perpendicular to the extrusion molding direction was observed with a microscope at a magnification of 4 to 10, and the cell diameters in the width direction and the thickness direction were measured, respectively. The average value of the entire cell diameter in the width direction and the thickness direction was defined as the average cell diameter.
(10) Uniformity of foaming A cross section of the foamed molded product cut out perpendicular to the extrusion molding direction was visually observed with the naked eye.
A: The bubbles are uniform.
○: A state in which air bubbles are slightly mixed.
X: Air bubbles are not uniform.
(11) Heat resistance stability The foam molded body is cut into a predetermined size (15 cm × 15 cm), and an orthogonal marked line with a length of 10 cm each parallel to each side is written at the center. Put in a circulating oven, heat for 2 hours, take out, and cool naturally until it reaches room temperature. The heat shrinkage was calculated by measuring the length and thickness of each marked line of the heat-treated sample. Evaluation was made according to the following evaluation criteria.
◯: When the heat shrinkage rate of each marked line is 2% or less and the heat shrinkage rate in the thickness direction is 5% or less.
X: When the heat shrinkage rate of each marked line exceeds 2% or the heat shrinkage rate in the thickness direction exceeds 5%.
(12) Surface appearance The surface of the foamed molded product was visually observed with the naked eye.
A: The surface has no unevenness, the surface is glossy, the surface is smooth and the appearance is extremely good.
○: The surface has no irregularities and the appearance is good.
X: The surface has irregularities and the appearance is poor.

<Resin sample preparation>
・ Linear polyethylene (α)
[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 as linear polyethylene (α) and copolymer of ethylene and α-olefin]
(Α) 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, and then brought into the polymerization reactor. Then, hexane was used as a solvent and ethylene was used as a monomer. The reaction temperature is 78 ° C., and a mixed gas of ethylene and hydrogen (the gas composition is adjusted so that the molar ratio of hydrogen and ethylene + hydrogen can be maintained at 0.48) is a linear polyethylene (α) with a total pressure of 0.8 MPa An ethylene homopolymer was polymerized. The resulting ethylene homopolymer, linear polyethylene (α), had a density of 966 kg / m ³ , MFR of 12 g / 10 min, and molecular weight distribution: Mw / Mn of 3.5.

[Preparation of ethylene polymer as high-pressure low-density polyethylene (β)]
The high-pressure low-density polyethylene (β) is obtained by radical polymerization of ethylene in an autoclave type reactor. The polymerization conditions are set to a temperature of 200 to 300 ° C. and a polymerization pressure of 100 to 250 MPa in the presence of peroxide, and a density obtained by a gel permeation chromatograph with a density of 923 kg / m ³ , MFR 5.0 g / 10 min. A high-pressure low-density polyethylene (β) in which the occupation ratio of components having a molecular weight of 10 ⁶ or more was 2.1% by mass was obtained.

[Example 1]
A polymer blend obtained by mixing 80% by mass of linear polyethylene (α) and 20% by mass of branched high-pressure method low-density polyethylene (β) was TEX-44 (screw diameter 44 mm, L / D = Using the twin screw extruder of 35), the mixture was melt kneaded and granulated at a temperature of 220 ° C.
The evaluation results of the obtained non-crosslinked foaming polyethylene resin composition were as follows: density 957 kg / m ³ , MFR 9.5 g / 10 min, strain hardening (λmax) 15.7, die swell 1.36, melting point peak The melting point was 134 ° C. (Note that the melt tension at 190 ° C. of the resin composition measured by the method described in Patent Document 9: JP-A-2004-043813 is 7.7 mN, and the product of the melt tension value and the MFR value is 73.2, which is less than 100.)
Manufactured by adding 1.5 parts by mass of “Polyslen EE515 (manufactured by Eiwa Kasei Kogyo Co., Ltd.)” as a sodium hydrogen carbonate-based foaming agent concentrate as a foaming agent to 100 parts by mass of a non-crosslinking polyethylene-based resin composition did. An extruded foam sheet was molded at a cylinder temperature of 200 ° C., a die temperature of 200 ° C., and a take-up speed of 1.2 m / min using a T-die molding machine (screw system: 30 mm, die width: 300 mm) manufactured by Yamaguchi Seisakusho.
The obtained extruded foamed sheet had a thickness of 1.0 mm and an apparent density of 0.467 g / cm ³ , and the evaluation results are shown below.
The closed cell ratio was 82.8%, the average cell diameter was 97 μm, the foaming uniformity was ◎, the heat resistance stability was ○, and the surface appearance was ◎.
[Comparative Example 1]
A polyethylene resin composition was obtained in the same manner as in the Examples except that only the linear polyethylene (α) was used and the high-pressure method low-density polyethylene (β) was not blended. Furthermore, although this polyethylene-type resin composition was performed by the method similar to an Example, the extrusion foaming sheet was not obtained.

  The present invention is a non-crosslinked foaming polyethylene resin composition having a good foaming state, such as a high closed cell ratio, a small bubble diameter, a uniform cell uniformity, and a good surface appearance. It can be widely used for heat insulating materials for building materials, industrial materials, adhesive tape base materials, furniture, household electrical appliances, buffering and heat insulating materials such as heat and cold insulation agents.

Claims (7)

Density is 930 to 960 kg / m ³ , 190 ° C., melt flow rate at a load of 2.16 kg is 0.1 to 20 g / 10 min, strain hardening property in measurement of elongational viscosity, and strain hardening degree (λmax) Is a polyethylene-based resin composition for non-crosslinking foaming, characterized by being 2.0-30.   2. The non-crosslinked foaming polyethylene resin composition according to claim 1, wherein the die swell at 190 ° C. is 1.30 to 2.00. The polyethylene-based resin composition for non-crosslinking foaming according to claim 1 or 2, wherein the following requirements 1) to 2) are satisfied.
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. 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 polyethylene-based resin composition for non-crosslinking foaming 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) The occupation ratio of the component having a converted molecular weight of 10 ⁶ or more determined by gel permeation chromatography is 1.5 to 9.0% by mass of the whole high-pressure method low-density polyethylene (β).   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 polyethylene-type resin composition for non-crosslinking foaming of Claim 3 or 4 which is a thing.   The foaming molding which comprises the polyethylene-type resin composition for non-crosslinking foaming of any one of Claims 1-5.   The foam molded article according to claim 6, which is a non-crosslinked extruded foam sheet.