JP2011006678A - Resin composition for cross-linked foaming and cross-linked foam body - Google Patents

Abstract

The present invention provides a crosslinked foaming resin composition suitable for producing a crosslinked foam having an excellent expansion ratio.
A resin composition containing 100 parts by weight of the following component (A) and 1 to 70 parts by weight of the following component (B) with respect to 100 parts by weight of the component (A) is irradiated with ionizing radiation. A resin composition for cross-linking foaming obtained.
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate ( An ethylene-α-olefin copolymer having an MFR) of 0.01-100 g / 10 min, a bimodal molecular weight distribution, and a single melting peak observed by a differential scanning calorimeter (DSC) Combined component (B): Thermal decomposition type foaming agent whose decomposition temperature is 120-240 ° C

Description

  The present invention relates to a crosslinked foamed resin composition and a crosslinked foam.

Foams made of an ethylene-α-olefin copolymer are excellent in flexibility and heat insulating properties, and thus are used in various applications such as buffer materials and heat insulating materials. As a method for producing a foam made of such an ethylene resin, an ethylene resin and a thermally decomposable foaming agent are melt-mixed at a temperature at which the thermally decomposable foaming agent is not decomposed and molded into a sheet, A method is known in which the sheet is irradiated with an electron beam to crosslink the sheet, and then the sheet is heated to a temperature equal to or higher than the decomposition temperature of the pyrolytic foaming agent to foam.
As one of ethylene-α-olefin copolymers, a copolymer polymerized using a metallocene catalyst is known. An ethylene-α-olefin copolymer polymerized using a metallocene catalyst is excellent in mechanical strength such as impact strength and tensile strength. Therefore, when a foam having the same mechanical strength as that of a conventional foam is produced using the ethylene-α-olefin copolymer, a foam having a higher expansion ratio than that of the conventional product can be obtained. It is expected to be possible. However, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst has a high extrusion load during extrusion and a low melt tension and swell ratio. Was demanded.

  In contrast, recently, a novel metallocene catalyst has been investigated, and a crosslinked foamed resin composition and a crosslinked foam using an ethylene-α-olefin copolymer polymerized by the catalyst and improved in molding processability are provided. Proposed.

JP 2008-1792 A

However, the ethylene-α-olefin copolymer as described in Patent Document 1 is still not sufficiently satisfactory in strain hardening characteristics, and the ethylene-α-olefin copolymer as described in Patent Document 1 is not yet satisfactory. When a crosslinked foam is produced by the above-described method using coalescence, a crosslinked foam having a high expansion ratio may not be obtained if the amount of electron beam to be irradiated is reduced.
Under such circumstances, the problem to be solved by the present invention is that a crosslinked foamed resin composition suitable for the production of a crosslinked foam excellent in the expansion ratio, and a crosslinked foamed product produced using the crosslinked foamed resin composition And a cross-linked foam having an excellent expansion ratio.

That is, the first of the present invention is an ionizing property in a resin composition containing 100 parts by weight of the following component (A) and 1 to 70 parts by weight of the following component (B) with respect to 100 parts by weight of the component (A). It is a crosslinked foaming resin composition obtained by irradiating with radiation.
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate ( Ethylene-α-olefin copolymer having a MFR) of 0.01-100 g / 10 min, a bimodal molecular weight distribution, and a single melting peak observed by a differential scanning calorimeter (DSC) Combined component (B): Pyrolytic foaming agent having a decomposition temperature of 120 to 240 ° C. The second aspect of the present invention is the following component (A) 100 parts by weight and the following component (A) 100 parts by weight: It is a resin composition for crosslinked foaming obtained by irradiating a resin composition containing 1 to 70 parts by weight of the component (B) with ionizing radiation.
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate ( MFR) is 0.01 to 100 g / 10 min, has a bimodal molecular weight distribution, and has an ethylene-α-olefin copolymer component (B ): Thermal decomposition type foaming agent having a decomposition temperature of 120 to 240 ° C. The third aspect of the present invention is the following component (A) 100 parts by weight and the following component (B) with respect to 100 parts by weight of the component (A). Is a resin composition for crosslinking and foaming obtained by irradiating a resin composition containing 1 to 70 parts by weight of ionizing radiation.
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate ( MFR) is 0.01 to 100 g / 10 min, has a bimodal molecular weight distribution, and satisfies the following relational expression: ethylene-α-olefin copolymer 0.084 × ln (MFR) +0. 69 <k1 / k2 <0.126 × ln (MFR) +1.03
In the fourth aspect of the present invention, the crosslinked foamed resin composition is kneaded at a temperature at which the thermally decomposable foaming agent is not decomposed to obtain a crosslinked foam original fabric, and ionizing radiation from at least one surface of the crosslinked foam original fabric. Is then heated to a temperature equal to or higher than the decomposition temperature of the pyrolytic foaming agent to produce a crosslinked foamed product.
A fifth aspect of the present invention is a crosslinked foam obtained by the above method.

According to the present invention, a crosslinked foamed resin composition suitable for the production of a crosslinked foam having an excellent expansion ratio, a method for producing a crosslinked foam using the crosslinked foamed resin composition, and a crosslinked foam having an excellent expansion ratio are provided. Can be provided.

The resin composition for cross-linking foaming of the present invention irradiates a resin composition containing an ethylene-α-olefin copolymer as a component (A) and a pyrolytic foaming agent as a component (B) with ionizing radiation. It is a resin composition for cross-linking foaming obtained. The ethylene-α-olefin copolymer of component (A) in the present invention is one or more types of copolymers selected from the following three types of copolymers (1) to (3).
(1) having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate (MFR) An ethylene-α-olefin copolymer having a bimodal molecular weight distribution and a single melting peak observed by a differential scanning calorimeter (DSC) (0.01 to 100 g / 10 min) 2) having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate (MFR) of An ethylene-α-olefin copolymer having a bimodal molecular weight distribution of 0.01 to 100 g / 10 min and having a branch number of 5 or more carbon atoms of 0.05 or more (3) based on ethylene Monomer unit and 3-20 carbon atoms - have a monomer unit based on an olefin, the density (d) is 860~950kg / m ^3, a melt flow rate (MFR) is 0.01 to 100 g / 10 min, the molecular weight distribution of bimodal And satisfying the following relational expression, ethylene-α-olefin copolymer 0.084 × ln (MFR) +0.69 <k1 / k2 <0.126 × ln (MFR) +1.03



It has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, has a density (d) of 860 to 950 kg / m ³ , and a melt flow rate (MFR) of 0.00. It contains an ethylene-α-olefin copolymer that is 01-100 g / 10 min, has a bimodal molecular weight distribution, and has a single melting peak observed by a differential scanning calorimeter (DSC).
First, characteristics common to all the ethylene-α-olefin copolymers of the above (1) to (3) will be described. Hereinafter, when distinguishing and describing the above three types of ethylene-α-olefin copolymers, the ethylene-α-olefin copolymer of (1) is referred to as the first ethylene-α-olefin copolymer, (2 ) Ethylene-α-olefin copolymer is described as the second ethylene-α-olefin copolymer, and (3) ethylene-α-olefin copolymer is described as the third ethylene-α-olefin copolymer. . When it is not necessary to distinguish these, it describes as the ethylene-alpha-olefin copolymer of a component (A).

  The ethylene-α-olefin copolymer of component (A) in the present invention is an ethylene-α-olefin copolymer containing a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. It is a polymer. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4 -Methyl- 1-hexene etc. are mention | raise | lifted and these may be used independently and 2 or more types may be used together. The α-olefin is preferably 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.

  The ethylene-α-olefin copolymer of the component (A) in the present invention includes the above-described monomer units based on ethylene and monomer units based on α-olefins having 3 to 20 carbon atoms. In the range which does not impair, you may have a monomer unit based on another monomer. Examples of other monomers include conjugated dienes (for example, butadiene and isoprene), non-conjugated dienes (for example, 1,4-pentadiene), acrylic acid, acrylic acid esters (for example, methyl acrylate and ethyl acrylate), and methacrylic acid. Methacrylic acid esters (for example, methyl methacrylate and ethyl methacrylate), vinyl acetate and the like.

  Content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of the component (A) in the present invention is based on the total weight (100% by weight) of the ethylene-α-olefin copolymer. Usually 50 to 99.5% by weight. The content of the monomer unit based on the α-olefin is usually 0.5 to 50% by weight based on the total weight (100% by weight) of the ethylene-α-olefin copolymer of the component (A). .

  The ethylene-α-olefin copolymer of component (A) in the present invention is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms. More preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 5 to 20 carbon atoms, more preferably a monomer unit based on ethylene and carbon. It is a copolymer having a monomer unit based on α-olefin of several 6-8.

  Examples of the ethylene-α-olefin copolymer of the component (A) in the present invention include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-4-methyl-1-pentene copolymer. Polymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-octene A copolymer, an ethylene-1-hexene-1-octene copolymer, and the like, preferably an ethylene-1-hexene copolymer, an ethylene-4-methyl-1-pentene copolymer, and an ethylene-1-butene. A -1-hexene copolymer, an ethylene-1-butene-1-octene copolymer, and an ethylene-1-hexene-1-octene copolymer.

The density of the ethylene-α-olefin copolymer of the component (A) in the present invention (hereinafter sometimes referred to as “d”) is 860 to 950 kg / m ³ . From the viewpoint of increasing the mechanical strength of the obtained molded body, it is preferably 940 kg / m ³ or less, more preferably 935 kg / m ³ or less. Further, from the viewpoint of enhancing the rigidity of the molded product obtained, preferably 870 kg / m ³ or more, more preferably 880 kg / m ³ or more, more preferably 890 kg / m ³ or more, particularly preferably 900 kg / m ³ or more. The density is measured according to a method defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. Moreover, the density of the ethylene-alpha-olefin copolymer of a component (A) can be changed with content of the monomer unit based on ethylene in an ethylene-alpha-olefin copolymer.

  The melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene-α-olefin copolymer of component (A) in the present invention is usually 0.01 to 100 g / 10 min. The melt flow rate is preferably 0.1 g / 10 min or more from the viewpoint of reducing the extrusion load during molding. Moreover, from a viewpoint of improving the mechanical strength of the obtained molded object, Preferably it is 50 g / 10min or less, More preferably, it is 30 g / 10min or less, More preferably, it is 15 g / 10min or less. The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. Further, the melt flow rate of the ethylene-α-olefin copolymer of the component (A) can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later. When the hydrogen concentration or the polymerization temperature is increased, The melt flow rate of the ethylene-α-olefin copolymer is increased.

The ethylene-α-olefin copolymer of the component (A) in the present invention exhibits a bimodal molecular weight distribution. Here, the bimodal distribution means that the molecular weight distribution curve measured by gel permeation chromatography (GPC) method has two peaks. When the molecular weight distribution is a unimodal distribution, the extrusion load becomes high. In order to lower the extrusion load, the shape of the bimodal molecular weight distribution is such that the peak position on the low molecular weight side is 35,000 or less in Mw and the peak position on the high molecular weight side is 150,000 or more. It is preferable. Moreover, from the viewpoint of increasing the mechanical strength of a molded product obtained using the copolymer, the peak position on the low molecular weight side is preferably 5,000 or more, more preferably 7,000 or more in terms of Mw.
The ratio of the heights of the two peaks in the molecular weight distribution curve measured by the GPC method is preferably such that the peak height on the low molecular weight side is L and the peak height on the high molecular weight side is H. 0.1 <H / L <0.45 and 0.1 <H / L <0.35. When H / L is too small, the mechanical strength of the foam obtained using the ethylene-α-olefin copolymer is lowered. When H / L is too large, the extrusion load tends to increase.

  The first ethylene-α-olefin copolymer in the present invention is an ethylene-α-olefin copolymer that satisfies the above-mentioned requirements of density and MFR and exhibits a bimodal molecular weight distribution, and is a differential scanning. In the melting curve obtained from calorimetry, the copolymer has a single melting peak in the range from 25 ° C. to the end of melting temperature. The presence of a plurality of melting peaks means that there is a melting peak different from the maximum melting peak (melting peak having the highest peak height) in the melting curve of the ethylene-α-olefin copolymer, It means that the composition distribution of the ethylene-α-olefin copolymer (distribution of the content ratio of monomer units among the polymer components contained in the ethylene-α-olefin copolymer) is wide. That is, the fact that the melting peak is single means that the composition distribution of the ethylene-α-olefin copolymer is narrow. When the number of melting peaks is large, the heat resistance of the obtained foam tends to be low.

  In addition, the melting curve of the ethylene-α-olefin copolymer was measured by using a differential scanning calorimeter (for example, a differential scanning calorimeter DSC-7 manufactured by Perkin Elmer), for example, an aluminum pan in which about 10 mg of a sample was sealed. (1) Hold at 150 ° C. for 5 minutes, (2) Decrease in temperature from 150 ° C. to 20 ° C. at 5 ° C./minute, (3) Hold at 20 ° C. for 2 minutes, and (4) 20 ° C. at 5 ° C./minute. It is a differential scanning calorimetry curve obtained by measuring (4) by raising the temperature from 0 ° C. to the melting end temperature + about 20 ° C. (usually about 150 ° C.).

The second ethylene-α-olefin copolymer in the present invention is an ethylene-α-olefin copolymer that satisfies the above-mentioned requirements for density and MFR, and exhibits a bimodal molecular weight distribution, and has a carbon number. A copolymer having a branch number of 5 or more (hereinafter sometimes referred to as “N _LCB ”) of 0.05 or more. N _LCB is preferably 0.07 / 1000 C or more, more preferably 0.12 / 1000 C or more, from the viewpoint of further reducing the extrusion load during the molding process. Moreover, from a viewpoint of raising the mechanical strength of the foam obtained, Preferably it is 2 / 1000C or less, More preferably, it is 1 / 1000C or less, More preferably, it is 0.7 / 1000C or less. Further, the N _LCB can be changed in the production method described later, for example, depending on the concentration of the electron donating compound or the use ratio of the transition metal compound (A1) and the transition metal compound (A2). It can also be controlled by carrying out prepolymerization.

N _LCB is a branch having 5 or more carbon atoms, where the sum of the areas of all peaks observed at 5 to 50 ppm is 1000 from the ¹³ C-NMR spectrum measured by the carbon nuclear magnetic resonance ( ¹³ C-NMR) method. Is obtained by determining the area of the peak derived from the methine carbon to which is bound. The peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded is around 38.2 ppm (reference: academic literature “Macromolecules”, (USA), American Chemical Society, 1999, Vol. 32, p.3817-3819) Observed at. Since the position of the peak derived from the methine carbon to which a branch having 5 or more carbon atoms is bonded may be shifted depending on the measurement apparatus and measurement conditions, it is usually determined by measuring the standard for each measurement apparatus and measurement conditions. To do. In the spectrum analysis, it is preferable to use a negative exponential function as the window function.

The third ethylene-α-olefin copolymer in the present invention is an ethylene-α-olefin copolymer that satisfies the above-mentioned requirements of density and MFR and exhibits a bimodal molecular weight distribution, and has an extensional viscosity. The nonlinear exponential ratio (k1 / k2) is expressed by the relational expression 0.084 × ln (MFR) +0.69 <k1 / k2 <0.126 × ln (MFR) +1.03 (6)
Is satisfied, more preferably the relational expression of the formula (6) ′ is satisfied, and still more preferably the relational expression of the formula (6) ″.
0.090 × ln (MFR) +0.73 <k1 / k2 <0.121 × ln (MFR) +0.99 (6) ′
0.095 × ln (MFR) +0.77 <k1 / k2 <0.116 × ln (MFR) +0.95 (6) ″
The elongational viscosity nonlinear exponent ratio (k1 / k2) is the ratio of the strain hardening strength in the high strain region to the strain hardening strength in the low strain region.

Here, k1 is the slope of lnα (t) when the time t is between 2.0 seconds and 2.5 seconds, and k2 is lnα (t) when the time t is between 1.5 seconds and 2.0 seconds. Is the slope of That is, the elongational viscosity nonlinear index elongational viscosity nonlinear index ratio k1 / k2 is a large value when sufficient strain hardening is exhibited even in a high strain region, and a small value when strain hardening is insufficient in the high strain region. Become. Although the conventional ethylene-α-olefin copolymer has insufficient strain hardening in the high strain region, the third ethylene-α-olefin copolymer in the present invention surprisingly has a high strain. Even in the region, it exhibits high strain hardening characteristics.
The reason for the extensional viscosity non-linear index ratio is unknown, but the dependence of MFR is strong, and when the measured data is plotted to investigate the tendency, the horizontal axis is ln (MFR) and the vertical axis is k1 / k2. Sometimes it turns out that a straight line is a very good approximation. With respect to the relational expression of equation (6), all data in the example plotted with the horizontal axis as MFR and the vertical axis as k1 / k2 are fitted with y = Aln (x) + B using Microsoft Excel. 20% of the values of the coefficient A and the coefficient B obtained at the time of fitting with respect to the approximate expression k1 / k2 = 0.1053 × ln (MFR) +0.8594 obtained by The upper limit was derived by adding to the coefficient B, and the lower limit was derived by subtracting. Equations (6) ′ and (6) ″ were derived in exactly the same manner as Equation (6) except that the parts obtained by adding 20% of the absolute values of A and B were changed to 15% and 10%, respectively. .

In the first ethylene-α-olefin copolymer or the second ethylene-α-olefin copolymer in the present invention, the elongational viscosity nonlinear index ratio (k1 / k2) is further expressed by the relational expression of formula (6). 0.084 × ln (MFR) +0.69 <k1 / k2 <0.126 × ln (MFR) +1.03 (6)
Is satisfied, more preferably the relational expression of the formula (6) ′ is satisfied, and still more preferably the relational expression of the formula (6) ″.
0.090 × ln (MFR) +0.73 <k1 / k2 <0.121 × ln (MFR) +0.99 (6) ′
0.095 × ln (MFR) +0.77 <k1 / k2 <0.116 × ln (MFR) +0.95 (6) ″

The ethylene-α-olefin copolymer of the component (A) in the present invention is an ethylene-α-olefin copolymer that satisfies the above-mentioned density and MFR requirements and exhibits a bimodal molecular weight distribution, It is preferable to satisfy all three requirements.
(Requirement 1) Single melting peak observed by a differential scanning calorimeter (DSC) (Requirement 2) The number of branches having 5 or more carbon atoms (N _LCB ) is 0.05 or more (Requirement 3) Extension viscosity The nonlinear exponent ratio (k1 / k2) satisfies the relational expression of Expression (6) 0.084 × ln (MFR) +0.69 <k1 / k2 <0.126 × ln (MFR) +1.03 (6)
The component (A) ethylene-α-olefin copolymer has an N _LCB of preferably 0.1 / 1000 C or more, more preferably 0.12 / 1000 C, from the viewpoint of further reducing the extrusion load during molding. That's it. Moreover, from a viewpoint of improving the mechanical strength of the foam obtained, Preferably it is 2 / 1000C or less, More preferably, it is 1 / 1000C or less, More preferably, it is 0.7 / 1000C.
The ethylene-α-olefin copolymer of component (A) is
0.090 × ln (MFR) +0.73 <k1 / k2 <0.121 × ln (MFR) +0.99
More preferably,
0.095 × ln (MFR) +0.77 <k1 / k2 <0.116 × ln (MFR) +0.95
Is more preferable.

  The weight average molecular weight (hereinafter sometimes referred to as “Mw”) and the number average molecular weight (hereinafter referred to as “Mn”) of the ethylene-α-olefin copolymer of component (A) in the present invention may be described. The ratio (hereinafter sometimes referred to as “Mw / Mn”) is preferably 4 to 30, and the Z-average molecular weight (hereinafter sometimes referred to as “Mz”) and the weight. The ratio to the average molecular weight (Mw) (hereinafter sometimes referred to as “Mz / Mw”) is preferably 5 to 15. If Mw / Mn is too small, the extrusion load at the time of molding may increase. Mw / Mn is more preferably 4.5 or more, further preferably 5.5 or more, and particularly preferably 6 or more. When Mz / Mw is too small, it tends to be difficult to obtain a foam having a high expansion ratio. Mz / Mw is preferably 6 or more. If Mw / Mn is too large or Mz / Mw is too large, the mechanical strength of the resulting foam may be lowered. Mw / Mn is preferably 25 or less, more preferably 20 or less, and even more preferably 17 or less. Mz / Mw is preferably 15 or less, and more preferably 13 or less. The Mw / Mn and the Mz / Mw are determined by measuring the number average molecular weight (Mn), the weight average molecular weight (Mw) and the Z average molecular weight (Mz) by the GPC method, dividing Mw by Mn, Is divided by Mw. Further, the Mw / Mn can be changed by, for example, the hydrogen concentration in the production method described later, and when the hydrogen concentration is increased, the Mw / Mn of the ethylene-α-olefin copolymer is decreased. The Mz / Mw can be changed, for example, depending on the use ratio of the transition metal compound (A1) and the transition metal compound (A2) in the production method described later.

The swell ratio (hereinafter sometimes referred to as “SR”) of the ethylene-α-olefin copolymer of component (A) in the present invention is preferably 1.6 or more. When the swell ratio is too small, it tends to be difficult to obtain a foam having a high expansion ratio or a foam having a large thickness. Further, the swell ratio is preferably 3.0 or less, more preferably 2.8 or less, from the viewpoint of improving the smoothness of the foam surface. When the melt flow rate (MFR) is measured, the swell ratio is obtained from an ethylene-α-olefin copolymer extruded at a length of about 15 to 20 mm from an orifice at a temperature of 190 ° C. and a load of 21.18 N. The strand was cooled in air, and the obtained solid strand was measured for the diameter D (unit: mm) of the strand at a position of about 5 mm from the upstream end of the extrusion. It is a value (D / D ₀ ) divided by 095 mm (D ₀ ). In addition, the swell ratio can be changed by, for example, the hydrogen concentration, the ethylene pressure or the electron donating compound concentration during polymerization in the production method described later. When the hydrogen concentration is increased or the ethylene pressure is decreased, ethylene- The swell ratio of the α-olefin copolymer is increased. In addition, the swell ratio can be controlled by performing prepolymerization at the time of polymerization.

  The characteristic relaxation time of the ethylene-α-olefin copolymer of the component (A) in the present invention (hereinafter sometimes referred to as “τ”) is preferably 5 seconds or more from the viewpoint of increasing the expansion ratio. More preferably, it is 10 seconds or more, and further preferably 15 seconds or more. The characteristic relaxation time is a numerical value indicating the length of the long chain branch of the ethylene-α-olefin copolymer. When the long chain branch is short, the characteristic relaxation time becomes a small value, and when the long chain branch is long, The characteristic relaxation time is a large value. The characteristic relaxation time can be changed, for example, depending on the polymerization conditions such as hydrogen concentration and ethylene pressure and the use ratio of the transition metal compound (A1) and the transition metal compound (A2). Transition metal compound (A1): transition When the metal compound (A2) is used in the range of 60: 1 to 12.5: 1 and the proportion of the transition metal compound (A2) used is reduced, the characteristic relaxation time of the ethylene-α-olefin copolymer can be extended. .

The characteristic relaxation time is calculated from a master curve showing the dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. on the angular frequency (unit: rad / sec), which is created based on the temperature-time superposition principle. It is a numerical value. Specifically, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (the unit of melt complex viscosity is (Pa · sec, unit of angular frequency is rad / sec.) Is superposed on the melt complex viscosity-angular frequency curve at 190 ° C based on the temperature-time superposition principle, and a master curve is obtained. It is a value calculated by approximating the master curve by the following formula (I).
η = η ₀ / [1+ (τ × ω) ⁿ ] (I)
η: Complex melt viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ: Characteristic relaxation time (unit: sec)
η ₀ : Constant determined for each ethylene-α-olefin copolymer (unit: Pa · sec)
n: Constant determined for each ethylene-α-olefin copolymer For the above calculation, commercially available calculation software may be used. 4.4.4.

  The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1. It is performed under the conditions of 5 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.

The melt tension of the ethylene-α-olefin copolymer of component (A) in the present invention (hereinafter sometimes referred to as “MT”) preferably satisfies the relational expression (1) with respect to MFR. .

Formula (1)
8.72 × MFR ^−0.56 <MT <56.28 × MFR ^−0.62 (1)
The winding speed is increased during the MT measurement, and the MT value at the time of fracture is expressed by the following empirical formula (2) with respect to the MFR.
MT = αexp (βMw) (2)
It is reported by the literature (D. Ancierno et al. Journal of Rheology, 29 (3), 323-334 (1985)). Also, the relational expression between Mw and MFR is empirically expressed by the formula (3)
Mn = A + Blog (MFR) (3)
Can be expressed in the literature (Mortimer et al. Journal of Applied Polymer Science, 8, 839-847 (1964), etc.). When these equations are combined, MT is empirically determined using MFR. C ・ MFR ^D (C and D are constants) (4)
It can be expressed by. Although C and D vary depending on the ratio of the transition metal compound described below, the values of C and D can be regarded as almost constant if the polymerization conditions other than the hydrogen concentration are substantially the same. Therefore, based on the data in the examples, the transition metal compound (A1): transition metal compound (A2) = 60: 1 and the MT and MFR plots of the examples in which the polymerization conditions other than the hydrogen concentration were made almost constant. Using Microsoft Excel, fitting was performed using equation (4), and 30% of the C value obtained during the fitting was added to the C and D coefficient portions of the fitting result to obtain the right side. Significant figures were two decimal places. Similarly, the transition metal compound (A1): transition metal compound (A2) = 12.5: 1 and the MT and MFR plots of the examples in which the polymerization conditions other than the hydrogen concentration were made almost constant (4 ), And the left side was obtained by subtracting 30% of the absolute values of C and D obtained at the time of fitting from the C and D coefficient parts of the fitting result.

If the melt tension is too small, the expansion ratio may be reduced. The melt tension preferably satisfies the relational expression (1) ′ between MFR and MT, and more preferably satisfies the relational expression (1) ″ between MFR and MT. Relational expressions (1) ′ and (1) ″ are obtained by adding 20% and 10% respectively to the parts obtained by adding 30% of the value of C when the right and left sides of relational expression (1) are derived. It was derived in exactly the same way except that it was changed to pull.
9.97 × MFR ^−0.56 <MT <51.95 × MFR ^−0.62 (1) ′
11.21 × MFR ^−0.56 <MT <47.62 × MFR ^−0.62 (1) ″

The melt tension was obtained by extruding molten ethylene-α-olefin copolymer from an orifice having a diameter of 2.095 mm and a length of 8 mm at a temperature of 190 ° C. and an extrusion speed of 0.32 g / min. -The filamentous ethylene-α-olefin copolymer was cut from the start of the take-up at the tension when taking the α-olefin copolymer into a filament at a take-up rate of 6.3 (m / min) / min. It is the maximum tension until. In addition, the melt tension can be changed by, for example, the pressure of ethylene during polymerization in the production method described later. When the pressure of ethylene during polymerization is lowered, the melt tension of the ethylene-α-olefin copolymer is increased. Become. The melt tension can also be increased by carrying out prepolymerization under appropriate conditions.

The elongational viscosity nonlinear index k representing the strain hardening strength of the ethylene-α-olefin copolymer of the component (A) in the present invention is preferably larger than 0.4, more preferably larger than 0.5. More preferably, it is larger than 0.6, and most preferably larger than 0.7. When k is small, it means that sufficient strain hardening is not exhibited, and it tends to be difficult to obtain a foam having a high expansion ratio.

The elongational viscosity nonlinearity index k is the viscosity-time curve σ ₁ (t) of the molten resin when uniaxially stretched at a temperature of 130 ° C. and a strain rate of 1 s ⁻¹ at Hencky strain, and is 0 at 130 ° C. and Hencky strain. the viscosity of the molten resin when uniaxially stretched at a strain rate of .1s ^-1 - obtained by dividing by the time curve σ _0.1 (t) curve _{α (t) = σ 1 (} t) / σ 0.1 (t (5)
On the other hand, t is a value calculated as the slope of lnα (t) between 1.5 seconds and 2.5 seconds.

  The measurement of the viscosity-time curve σ (t) of the molten resin is performed using a viscoelasticity measuring device (for example, ARES manufactured by TA Instruments). Note that the measurement is performed in a nitrogen atmosphere.

  The catalyst for producing an ethylene-α-olefin copolymer of the component (A) of the present invention comprises the following component (A1), the following component (A2), the following component (B), and the following component (C). A catalyst for copolymerization of ethylene and α-olefin formed by contact, wherein the molar ratio ((A1) / (A2)) of component (A1) to component (A2) is 1 to 90 Is.

［式中、Ｍ^１は、元素周期律表の第４族の遷移金属原子を表し、Ｊ^１は、元素周期律表の第１４族の原子を表し、ｍは、１〜５の整数を表し、Ｘ^１、Ｒ^１およびＲ^２は、それぞれ同一または相異なり、水素原子、ハロゲン原子、置換されていてもよい炭素数１〜２０のハイドロカルビル基、置換されていてもよい炭素数１〜２０のハイドロカルビルオキシ基、炭素数１〜２０のハイドロカルビルシリル基または炭素数１〜２０のハイドロカルビルアミノ基を表し、複数のＸ¹は互いに同じであっても異なっていてもよく、複数のＲ^１は互いに同じであっても異なっていてもよく、複数のＲ^２は互いに同じであっても異なっていてもよい。］ Component (A1): Transition metal compound represented by the following general formula (1)

[Wherein M ¹ represents a transition metal atom of Group 4 of the periodic table of elements, J ¹ represents an atom of Group 14 of the periodic table of elements, and m represents an integer of 1 to 5] , X ¹ , R ¹ and R ² are the same or different and each is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 1 to 1 carbon atoms. 20 hydrocarbyloxy groups, 1 to 20 carbon hydrocarbylsilyl groups or 1 to 20 carbon hydrocarbylamino groups, and a plurality of X ¹ may be the same or different from each other. The plurality of R ¹ may be the same as or different from each other, and the plurality of R ² may be the same as or different from each other. ]

［式中、Ｍ^２は、元素周期律表の第４族の遷移金属原子を表し、Ｊ^２は、元素周期律表の第１４族の原子を表し、ｎは１〜５の整数を表し、Ｘ^２、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ同一または相異なり、水素原子、ハロゲン原子、置換されていてもよい炭素数１〜２０のハイドロカルビル基、置換されていてもよい炭素数１〜２０のハイドロカルビルオキシ基、炭素数１〜２０のハイドロカルビルシリル基または炭素数１〜２０のハイドロカルビルアミノ基を表し、複数のＸ^２は互いに同じであっても異なっていてもよく、複数のＲ^３は互いに同じであっても異なっていてもよく、複数のＲ^４は互いに同じであっても異なっていてもよく、複数のＲ^５は互いに同じであっても異なっていてもよい。］ Component (A2): transition metal compound represented by the following general formula (2)

[Wherein M ² represents a transition metal atom of Group 4 of the Periodic Table of Elements, J ² represents an atom of Group 14 of the Periodic Table of Elements, and n represents an integer of 1 to 5, X ² , R ³ , R ⁴ and R ⁵ are the same or different and each is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number. 1 to 20 hydrocarbyloxy groups, 1 to 20 carbon hydrocarbylsilyl groups or 1 to 20 carbon hydrocarbylamino groups, and a plurality of X ² may be the same or different. The plurality of R ³ may be the same or different from each other, the plurality of R ⁴ may be the same or different from each other, and the plurality of R ⁵ may be the same or different from each other. May be. ]

Component (B): Catalyst component formed by contacting the following component (b1), the following component (b2), and the following component (b3) (b1): a compound represented by the following general formula (3)
M ³ L _x (3)
[Wherein, M ³ represents a lithium atom, a sodium atom, a potassium atom, a rubidium atom, a cesium atom, a beryllium atom, a magnesium atom, a calcium atom, a strontium atom, a barium atom, a zinc atom, a germanium atom, a tin atom, a lead atom, It represents an antimony atom or a bismuth atom, and x represents a number corresponding to the valence of M ³ . L represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and when a plurality of Ls are present, they may be the same as or different from each other. ]
(B2): Compound represented by the following general formula (4)
R ⁶ _t-1 T ¹ H (4)
[Wherein, T ¹ represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and t represents a number corresponding to the valence of T ¹ . R ⁶ represents a halogen atom, an electron-withdrawing group, a group containing a halogen atom or a group having an electron-withdrawing group, and when a plurality of R ⁶ are present, they may be the same as or different from each other. . ]
(B3): Compound represented by the following general formula (5)
R ⁷ _s-2 T ² H ₂ (5)
[Wherein T ² represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and s represents a number corresponding to the valence of T ² . R ⁷ represents a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms or a halogenated hydrocarbyl group having 1 to 20 carbon atoms.
Component (C): Organoaluminum compound

M ² of M ¹ and of general formula (1) (2) represents a transition metal atom of Group 4 of the Periodic Table of the Elements, for example, titanium atom, zirconium atom, hafnium atom.

J ² of J ¹ and of general formula (1) (2) represents an atom of the Group XIV of the Periodic Table of the Elements. Preferably, they are a carbon atom or a silicon atom.

  M in the general formula (1) and n in the general formula (2) are integers of 1 to 5. m is preferably 1 to 2. n is preferably 1-2.

X ¹ , R ¹ , R ^{2 in} the general formula (1) and X ² , R ³ , R ^4, and R ⁵ in the general formula (2) are the same or different and are each a hydrogen atom, a halogen atom or a substituted A C1-C20 hydrocarbyl group, an optionally substituted C1-C20 hydrocarbyloxy group, a C1-C20 hydrocarbylsilyl group or a C1-C20 hydro a Karubiruamino group, a plurality of X ¹ may be different be the same as each other, a plurality of R ^1, R ² may be different be the same as each other, a plurality of X ² are each They may be the same or different, and a plurality of R ³ and R ⁴ may be the same or different from each other.

Examples of the halogen atom for X ¹ , R ¹ , R ² , X ² , R ³ , R ⁴ and R ⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the optionally substituted hydrocarbyl group having 1 to 20 carbon atoms for X ¹ , R ¹ , R ² , X ² , R ³ , R ⁴ and R ⁵ include an alkyl group having 1 to 20 carbon atoms, carbon Examples thereof include halogenated alkyl groups having 1 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-dodecyl group, n-tridecyl group, n -Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.

  Examples of the halogenated alkyl group having 1 to 20 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, and tribromomethyl. Group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group , Pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl Group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, Perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopenta Examples include decyl group and perbromoeicosyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethylphenyl). ) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4 , 6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3 , 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4, -Tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropyl) (Phenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthra Cenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenyl Methyl, diphenylethyl group, diphenylpropyl group, diphenylbutyl group. Moreover, the halogenated aralkyl group etc. which these aralkyl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. Group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethyl Phenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2 , 3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, se -Butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl Examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Moreover, the halogenated aryl group etc. which these aryl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  The optionally substituted hydrocarbyl group having 1 to 20 carbon atoms includes a hydrocarbyl group substituted with a hydrocarbylsilyl group, a hydrocarbyl group substituted with a hydrocarbylamino group, hydro And hydrocarbyl group substituted with a carbyloxy group.

  Hydrocarbyl groups substituted with hydrocarbylsilyl groups include trimethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylphenyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, Examples thereof include bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis (trimethylsilyl) phenyl group, and triphenylsilylmethyl group.

  Hydrocarbyl groups substituted with hydrocarbylamino groups include dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl, dimethylaminobutyl, dimethylaminophenyl, bis (dimethylamino) methyl, bis Examples thereof include (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group, diphenylaminophenyl group and the like.

  Hydrocarbyl groups substituted with hydrocarbyloxy groups include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, sec-butoxymethyl group, tert-butoxy Methyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl group, phenoxyethyl group, methoxy- n-propyl group, ethoxy-n-propyl group, n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propyl group, sec-butoxy-n-propyl group, tert-butoxy -N-propyl group, phenoxy-n-propyl group Methoxyisopropyl group, ethoxyisopropyl group, n-propoxyisopropyl group, isopropoxyisopropyl group, n-butoxyisopropyl group, sec-butoxyisopropyl group, tert-butoxyisopropyl group, phenoxyisopropyl group, methoxyphenyl group, ethoxyphenyl group, n -Propoxyphenyl group, isopropoxyphenyl group, n-butoxyphenyl group, sec-butoxyphenyl group, tert-butoxyphenyl group, phenoxyphenyl group and the like.

Examples of the optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms for X ¹ , R ¹ , R ² , X ² , R ³ , R ⁴ and R ⁵ include an alkoxy group having 1 to 20 carbon atoms, Examples thereof include an aralkyloxy group having 7 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neo Pentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyl group Examples include oxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosoxy group and the like. . Further, halogenated alkoxy groups in which these alkoxy groups are substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom can be mentioned.

  Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Enyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy Group, anthracenylmethoxy group and the like. In addition, a halogenated aralkyloxy group in which these aralkyloxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethyl Phenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5 -Tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethyl Ruphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n- Examples include decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. Moreover, the halogenated aryloxy group etc. which these aryloxy groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mentioned.

C 1-20 hydrocarbylsilyl group of X ¹ , R ¹ , R ² , X ² , R ³ , R ⁴ and R ⁵ is a silyl substituted with a C 1-20 hydrocarbyl group. Examples of the hydrocarbyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Examples of the hydrocarbylsilyl group having 1 to 20 carbon atoms include a monohydrocarbylsilyl group having 1 to 20 carbon atoms, a dihydrocarbylsilyl group having 2 to 20 carbon atoms, and a trihydro having 3 to 20 carbon atoms. Examples of the monohydrocarbylsilyl group having 1 to 20 carbon atoms include a methylsilyl group, an ethylsilyl group, an n-propylsilyl group, an isopropylsilyl group, an n-butylsilyl group, and a sec-butylsilyl group. Group, tert-butylsilyl group, isobutylsilyl group, n-pentylsilyl group, n-hexylsilyl group, phenylsilyl group and the like. Examples of the dihydrocarbylsilyl group having 2 to 20 carbon atoms include dimethylsilyl Group, diethylsilyl group, di-n-propylsilyl group, diisopropylsilyl group, di-n- Examples of the trihydrocarbylsilyl group having 3 to 20 carbon atoms include trimethylsilyl group, triethylsilyl group, di-sec-butylsilyl group, di-tert-butylsilyl group, diisobutylsilyl group, and diphenylsilyl group. Silyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyl-dimethylsilyl group, Examples thereof include a tri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, and a triphenylsilyl group.

The hydrocarbylamino group having 1 to 20 carbon atoms of X ¹ , R ¹ , R ² , X ² , R ³ , R ⁴ and R ⁵ is an amino substituted with a hydrocarbyl group having 1 to 20 carbon atoms. Examples of the hydrocarbyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. As a C1-C20 hydrocarbyl amino group, a C1-C20 monohydrocarbyl amino group, a C2-C20 dihydrocarbyl amino group, etc. are mentioned, for example, C1-C20 Examples of the monohydrocarbylamino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group, and isobutylamino. Group, n-hexylamino group, n-octylamino group, n-decylamino group, phenylamino group, benzylamino group and the like. Examples of the dihydrocarbylamino group having 2 to 20 carbon atoms include dimethylamino Group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino Group, di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n -Decylamino group, diphenylamino group, dibenzylamino group, tert-butylisopropylamino group, phenylethylamino group, phenylpropylamino group, phenylbutylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroisoin For example, a drill base.

X ¹ is preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group and a benzyl group.

R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.

R ² is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

X ² is preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group and a benzyl group.

R ³ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.

R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom.

R ⁵ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

As the transition metal compound of the component (A1) represented by the general formula (1), M ¹ is a zirconium atom, X ¹ is a chlorine atom, methylenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis ( Cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride,

Methylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (methylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (methylcyclopentadienyl) ) Zirconium dichloride, ethylenebis (methylcyclopentadienyl) zirconium dichloride,

Methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (methyl Cyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride,

Methylene bis (2,3-dimethylcyclopentadienyl) zirconium dichloride, methylene bis (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene bis (2,5-dimethylcyclopentadienyl) zirconium dichloride, methylene bis (3,4 -Dimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,3-dimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2, 5-dimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methyl Bis (2,3-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,5-dimethylcyclohexane) Pentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (3,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (2,3-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (2 , 4-Dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (2,5-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (3,4-dimethylsilane) Lopentadienyl) zirconium dichloride, ethylenebis (2,3-dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,5-dimethylcyclopentadienyl) Zirconium dichloride, ethylenebis (3,4-dimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (cyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (cyclopentadi) Enyl) zirconium dichloride, dicyclohexylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride, di (p-tolyl) silanediylbis (cyclopentadienyl) zirconium dichloride, divinylsilanediyl Bis (cyclopentadienyl) zirconium dichloride, diallylsilanediylbis (cyclopentadienyl) zirconi Mudichloride, (methyl) (vinyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (allyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (Methyl) (n-propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (cyclopentadienyl) zirconium dichloride, (Methyl) (phenyl) silanediylbis (cyclopentadienyl) zirconium dichloride,

Dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis ( Methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (methylcyclopentadienyl) ) Zirconium dichloride, (methyl) (n-propyl) silanediylbis (methylcyclopentadienyl) zirconium Dichloride, (methyl) (isopropyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (methylcyclopentadienyl) Zirconium dichloride,

Dimethylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediyl (cyclopentadienyl) ) (Methylcyclopentadienyl) zirconium dichloride, diisopropylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenyl Silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediyl (cyclopentadienyl) ) (Methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediyl (cyclopentadienyl) ( Methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) ) Zirconium dichloride,

Dimethylsilanediylbis (2,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,5-dimethylcyclopentadienyl) ) Zirconium dichloride, dimethylsilanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,3-dimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethyl) Cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,5-dimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (3,4-dimethylcyclope) Tadienyl) zirconium dichloride, di (n-propyl) silanediylbis (2,3-dimethylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, di (n -Propyl) silanediylbis (2,5-dimethylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (2,3-dimethylcyclo) Pentadienyl) zirconium dichloride, diisopropylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (2,5-dimethyl) Clopentadienyl) zirconium dichloride, diisopropylsilanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (2,3-dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (2 , 4-Dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilane diylbis (2,5-dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilane Diylbis (2,3-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopent Tadienyl) zirconium dichloride, diphenylsilanediylbis (2,5-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2 , 3-Dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2,5-dimethylcyclopentadienyl) ) Zirconium dichloride, (ethyl) (methyl) silanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,3 Dimethylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,5-dimethylcyclopentadiene) Enyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (2,3-dimethylcyclopentadienyl) zirconium dichloride, ( Methyl) (isopropyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (2,5-dimethylcyclopentadienyl) Zirconium dichloride, (methyl) (isopropyl) silanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (2,3-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) ) Bis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (2,5-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (3,4-dimethyl) Cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (2,3-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (2,4-di Methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (2,5-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (3,4-dimethylcyclopentadienyl) zirconium dichloride , Etc. can be illustrated.

In the above examples, when the η ⁵ -cyclopentadienyl group is substituted at the 1-position, the substituent at the 2-position, 3-position, 4-position and 5-position is a mono-substitution In the same manner, all combinations are included even if the crosslinking position is other than the 1-position. Bi- or higher substituents similarly include all combinations of substituents and crosslinks. Further, X ¹ dichloride of the above transition metal compound is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, dipropoxide, dibutoxide, bis (trifluoromethoxide), diphenyl, diphenoxide, bis (2, 6-di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide) Examples thereof include compounds changed to dibenzyl and the like. Furthermore, the zirconium M ¹ of the transition metal compound may be exemplified compound was changed to titanium or hafnium.

  The transition metal compound of the component (A1) represented by the general formula (1) is preferably dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride or isopropylidenebis (cyclopentadienyl) zirconium dichloride.

As the transition metal compound of the component (A2) represented by the general formula (2), M ² is a zirconium atom, X ² is a chlorine atom, and a bridging group [— (J ² (R ⁵ ) ₂ ) _n —] is used. As a diphenylmethylene group, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2, , 5-Trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetramethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2, , 5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tri-n-propyl-1-cyclo) Pentadienyl) (9-fluorenyl) zyl Nium dichloride, diphenylmethylene (2,3,5-tri-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium Chloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmeth Len (2,3,5-triphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclo Ntadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris ( Trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Trimethyl-1- Clopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclo) Pentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Triethyl-1- Clopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopenta Dienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7 -Dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Di-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (2 , 7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmeth Len (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tri-n-propyl- 1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1-cyclopentadienyl) (2,7-dimethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) ( 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-trif Nyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5- Tetraphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9- Fluorenyl) Jill Nium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) ) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Trimethyl-1- Clopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclo) Pentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Triethyl-1- Clopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopenta Dienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7 -Diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Di-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (2 , 7-diethyl-9-fluorenyl) zirconium dichloride, diphenylme Len (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tri-n-propyl- 1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1-cyclopentadienyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) ( 2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-trif Nyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5- Tetraphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9- Fluorenyl) Jill Nium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) ) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,5-di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4 -Di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirco Um dichloride, diphenylmethylene (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4) 5-tri-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2, 7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2 , 7-Di-t-butyl-9-fluorenyl) zirconium Chloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, dipheny Methylene (2,3,4-triphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-di-t -Butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl)- 1-cyclopentadienyl) (2,7-di-t- Til-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) ( 2,7-di-t-butyl-9-fluorenyl) zirconium dic It can be exemplified Lido like.

The dichloride of X ² in the transition metal compound, difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, Jipuropokishido, Jibutokishido, bis (trifluoromethyl methoxide), diphenyl, diphenoxide, bis (2,6 -Di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide), Examples include compounds changed to dibenzyl and the like. In addition, the diphenylmethylene group of the cross-linking group [— (J ² (R ⁵ ) ₂ ) _n —] of the transition metal compound is replaced with a methylene group, an ethylene group, an isopropylidene group, a methylphenylmethylene group, a dimethylsilanediyl group, or a diphenyl. Examples thereof include compounds changed to silanediyl groups, silacyclobutanediyl groups, silacyclohexanediyl groups, and the like. Furthermore, the zirconium M ² of the transition metal compound may be exemplified compound was changed to titanium or hafnium.

  The transition metal compound of the component (A2) represented by the general formula (2) is preferably diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride.

M ^{3 in the} general formula (3) is lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom, lead An atom, an antimony atom or a bismuth atom. Preferred is a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, more preferred is a magnesium atom, zinc atom, tin atom or bismuth atom, still more preferred. It is a zinc atom.

X in the general formula (3) represents a number corresponding to the valence of M ³ . For example, when M ³ is a zinc atom, x is 2.

  L in the general formula (3) represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and when a plurality of L are present, they may be the same or different from each other. It may be.

  Examples of the halogen atom for L include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the optionally substituted hydrocarbyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. Examples thereof include 1 to 20 halogenated alkyl groups.

  Examples of the alkyl group having 1 to 20 carbon atoms of L include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and neopentyl. Group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-dodecyl group, n-tridecyl group N-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like. Preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group.

  Examples of the halogenated alkyl group having 1 to 20 carbon atoms of L include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromo Methyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl Group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexene Sil group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, Perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopenta group Examples include decyl group and perbromoeicosyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms of L include, for example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3- (Dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3, , 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group , (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group , Anthracenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphth Nirumechiru group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group. Preferably, it is a benzyl group. Moreover, the C7-20 halogenated aralkyl group etc. with which these aralkyl groups were substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  Examples of the aryl group having 6 to 20 carbon atoms of L include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5 -Xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6 -Trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, ec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetra Examples include decylphenyl group, naphthyl group, anthracenyl group and the like. Preferably, it is a phenyl group. Moreover, the C6-C20 halogenated aryl group etc. which these aryl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  L is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, still more preferably carbon. It is an alkyl group of formula 1-20.

T ^{1 in the} general formula (4) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom.

The t in the general formula (4) represents a valence of T ^1, if T ¹ is an oxygen atom or a sulfur atom, t is 2, if T ¹ is a nitrogen atom or phosphorus atom, t is 3 .

R ^{6 in the} general formula (4) represents a halogen atom, an electron-withdrawing group, a group containing a halogen atom, or a group having an electron-withdrawing group, and represents a group containing an electron-withdrawing group or an electron-withdrawing group. , R ⁶ may be the same as or different from each other. As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known, and functional groups having positive Hammett's rule substituent constant σ are listed as electron withdrawing groups.

Examples of the halogen atom for R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the electron-withdrawing group for R ⁶ include a cyano group, a nitro group, a carbonyl group, a hydrocarbyloxycarbonyl group, a sulfone group, and a phenyl group.

Examples of the group containing a halogen atom of R ⁶ include a halogenated alkyl group having 1 to 20 carbon atoms, a halogenated aralkyl group having 7 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. A halogenated hydrocarbyl group having 1 to 20 carbon atoms such as a (halogenated alkyl) aryl group of the above; a halogenated hydrocarbyloxy group having 1 to 20 carbon atoms; a halogenated hydrocarbyloxycarbonyl having 2 to 20 carbon atoms Group. Examples of the group having an electron-withdrawing group represented by R ⁶ include a C 1-20 cyanated hydrocarbyl group such as a C 6-20 cyanated aryl group, and a C 6-20 nitrated aryl group. And a nitrated hydrocarbyl group having 1 to 20 carbon atoms.

Examples of the halogenated alkyl group having 1 to 20 carbon atoms of R ⁶ include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, and trichloro. Methyl group, tribromomethyl group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2 -Triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group 2,2,3,3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1- Lichloromethylethyl group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2 , 2,2-trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group Examples thereof include a 1,1-bis (triiodomethyl) -2,2,2-triiodoethyl group.

Examples of the halogenated aryl group having 6 to 20 carbon atoms of R ⁶ include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group , Pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl Group, perfluoro-2-naphthyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophene Group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5, 6-tetrachlorophenyl group, pentachlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1- Naphtyl group, perchloro-2-naphthyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl Group, 3,5-dibromophenyl group, 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6 -Tetrabromophenyl group, pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1 -Naphtyl group, perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenyl group, 3,4 -Diiodophenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, Pentaiodophenyl group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl Group, Payodo-1-naphthyl group, etc. Payodo-2-naphthyl group.

Examples of the (halogenated alkyl) aryl group having 7 to 20 carbon atoms of R ⁶ include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2 , 6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoro And methyl) phenyl group.

Examples of the C 6-20 cyanated aryl group for R ⁶ include a 2-cyanophenyl group, a 3-cyanophenyl group, a 4-cyanophenyl group, and the like.

Examples of the nitrated aryl group having 6 to 20 carbon atoms of R ⁶ include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4-nitrophenyl group.

Examples of the hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms of R ⁶ include an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, and the like. More specifically, a methoxycarbonyl group, an ethoxycarbonyl group, Examples thereof include n-propoxycarbonyl group, isopropoxycarbonyl group, phenoxycarbonyl group and the like.

Examples of the halogenated hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms of R ⁶ include a halogenated alkoxycarbonyl group, a halogenated aralkyloxycarbonyl group, and a halogenated aryloxycarbonyl group. More specifically, Examples thereof include a trifluoromethoxycarbonyl group and a pentafluorophenoxycarbonyl group.

R ⁶ is preferably a halogenated hydrocarbyl group having 1 to 20 carbon atoms, more preferably a halogenated alkyl group having 1 to 20 carbon atoms or a halogenated aryl group having 6 to 20 carbon atoms, Preferred are a fluorinated alkyl group having 1 to 20 carbon atoms, a fluorinated aryl group having 7 to 20 carbon atoms, a chlorinated alkyl group having 1 to 20 carbon atoms or a chlorinated aryl group having 6 to 20 carbon atoms, A fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aryl group having 6 to 20 carbon atoms is preferable. The fluorinated alkyl group having 1 to 20 carbon atoms is preferably a fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoro. A propyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group or a 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, more preferably trifluoro A methyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group or a 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group. The fluorinated aryl group having 6 to 20 carbon atoms is preferably a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, 3, 4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, penta Fluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group or Perfluoro-2-naphthyl group, more preferably 3,5-difluorophenyl group, 3,4,5-trifluorophenyl. Is a group or a pentafluorophenyl group. The chloroalkyl group having 1 to 20 carbon atoms is preferably a chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group. 2,2,2-trichloro-1-trichloromethylethyl group or 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group. As the chlorinated aryl group having 6 to 20 carbon atoms, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-triphenyl are preferable. A chlorophenyl group or a pentachlorophenyl group;

T ^{2 in the} general formula (5) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, more preferably an oxygen atom.

The s of the general formula (5) represents a valence of T ^2, if T ² is an oxygen atom or a sulfur atom, s is 2, if T ² is a nitrogen atom or a phosphorus atom, s is 3 .

R ^{7 in the} general formula (5) represents a hydrocarbyl group having 1 to 20 carbon atoms or a halogenated hydrocarbyl group having 1 to 20 carbon atoms. Examples of the hydrocarbyl group having 1 to 20 carbon atoms of R ⁶ include an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. The group illustrated as a C1-C20 alkyl group, a C7-C20 aralkyl group, and a C6-C20 aryl group can be illustrated. Examples of the halogenated hydrocarbyl group having 1 to 20 carbon atoms of R ⁶ include a halogenated alkyl group having 1 to 20 carbon atoms, a halogenated aralkyl group having 7 to 20 carbon atoms, and a halogenated aryl group having 6 to 20 carbon atoms. , raised and halogenated hydrocarbyl group having 1 to 20 carbon atoms such as (alkyl halide) aryl group having 7 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms of R ^5, carbon atoms 6 Examples thereof include groups exemplified as -20 halogenated aryl groups and (halogenated alkyl) aryl groups having 7 to 20 carbon atoms.

R ⁷ is preferably a halogenated hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a fluorinated hydrocarbyl group having 1 to 20 carbon atoms.

As the compound represented by the general formula (3) of the component (b1), as a compound in which M ³ is a zinc atom, dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc Dialkyl zinc such as diisobutyl zinc and di-n-hexyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; Methyl zinc, ethyl zinc chloride, n-propyl zinc chloride, isopropyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, n-hexyl zinc chloride, methyl zinc bromide, ethyl zinc bromide, n-propyl zinc bromide, Isopropyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl zinc bromide, yo Alkyl zinc halides such as methyl zinc iodide, ethyl zinc iodide, n-propyl zinc iodide, isopropyl zinc iodide, n-butyl zinc iodide, isobutyl zinc iodide, n-hexyl zinc iodide; zinc fluoride, Examples thereof include zinc halides such as zinc chloride, zinc bromide and zinc iodide.

  The compound represented by the general formula (3) of the component (b1) is preferably dialkyl zinc, and more preferably dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc. Diisobutylzinc or di-n-hexylzinc, particularly preferably dimethylzinc or diethylzinc.

  Examples of the compound represented by the general formula (4) of the component (b2) include amines, phosphines, alcohols, thiols, phenols, thiophenols, naphthols, naphthylthiols, and carboxylic acid compounds.

  Examples of the amine include di (fluoromethyl) amine, bis (difluoromethyl) amine, bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3, 3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl ) Amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) Amine, bis (2,4,6-trifluorophenyl) amine, bis (3,4,5-trifluorophenyl) amine, bis (penta Fluorophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di) (Trifluoromethyl) phenyl) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) Amine, (3-cyanophenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine, bis (1H, 1H-perfluorobutyl) amine, bis (1H, 1H-perfluoropentyl) amine, bis (1H, 1H-per Fluorohexyl) amine, bis (1H, 1H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoropentadecyl) amine, bis (1H, 1H-perfluoroeico) Syl) amine and the like. In addition, amines in which the fluoro of these amines is changed to chloro, bromo or iodo can be mentioned.

  Examples of the phosphine include compounds in which the nitrogen atom of the amine is changed to a phosphorus atom. Those phosphines are compounds represented by replacing the amine in the amine with phosphine.

  Examples of the alcohol include fluoromethanol, difluoromethanol, trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoro Fluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1H, 1H-perfluorobutanol, 1H, 1H-perfluoropentanol, 1H, 1H-perfluorohexanol, Examples thereof include 1H, 1H-perfluorooctanol, 1H, 1H-perfluorododecanol, 1H, 1H-perfluoropentadecanol, 1H, 1H-perfluoroeicosanol and the like. Moreover, the alcohol which changed fluoro of these alcohol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of the thiol include compounds in which the oxygen atom of the alcohol is changed to a sulfur atom. Those thiols are compounds represented by substituting the thiols in the alcohol with thiols.

  As phenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4 , 6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethylphenol 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol and the like. Moreover, the phenol which changed fluoro of these phenol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of the thiophenol include compounds in which the oxygen atom of the phenol is changed to a sulfur atom. Those thiophenols are compounds represented by replacing phenol in the phenol with thiophenol.

  As naphthol, perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7,8-pentafluoro-2-naphthol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) ) Phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, Examples include 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol. Moreover, the naphthol which changed fluoro of these naphthol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of naphthylthiol include compounds in which the oxygen atom of the naphthol is changed to a sulfur atom. Those naphthols are compounds represented by replacing naphthol in the naphthol with naphthylthiol.

  Examples of the carboxylic acid compound include pentafluorobenzoic acid, perfluoroethanoic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoro. Examples include heptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid.

  The compound represented by the general formula (4) of the component (b2) is preferably an amine, alcohol, or phenol compound, and the amine is preferably bis (trifluoromethyl) amine, bis (2,2,2-trimethyl). Fluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (Trifluoromethyl) -2,2,2-trifluoroethyl) amine or bis (pentafluorophenyl) amine, and the alcohol is preferably trifluoromethanol, 2,2,2-trifluoroethanol, 2,2 , 3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol Is 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, preferably 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol as phenol 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol or 3,4 , 5-tris (trifluoromethyl) phenol.

  More preferably, the compound represented by the general formula (4) of the component (b2) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3 , 5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol Or 2,4,6-tris (trifluoromethyl) phenol More preferably 3,5-difluorophenol, 3,4,5-fluorophenol, pentafluorophenol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol.

  Examples of the compound represented by the general formula (5) of the component (b3) include water, hydrogen sulfide, amine, aniline compound and the like.

  Examples of the amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, n-hexylamine, alkylamines such as n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine; benzylamine, (2-methylphenyl) methylamine, (3-methylphenyl) methylamine , (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) ) Methylamine, (3, -Dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3,4-trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) methylamine, (2,3,6) -Trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2,4,6-trimethylphenyl) methylamine, (2,3,4,5-tetramethylphenyl) methylamine, ( 2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n-propyl) Phenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (s c-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (neopentylphenyl) methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methyl Aralkylamines such as amine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthracenylmethylamine; allylamine; cyclopentadienylamine and the like.

  Examples of the amine include fluoromethylamine, difluoromethylamine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2- Trifluoro-1-trifluoromethylethylamine, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, Examples thereof include halogenated alkylamines such as perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, and perfluoroeicosylamine. In addition, amines in which the fluoro of these amines is changed to chloro, bromo or iodo can be mentioned.

  Examples of aniline compounds include aniline, naphthylamine, anthracenylamine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2 , 6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4 , 6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline Pentamethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-diethylaniline 2,4-diethylaniline, 2,5-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline, 2,3,4-triethylaniline, 2,3,5 -Triethylaniline, 2,3,6-triethylaniline, 2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline, 2,3,4,6- Examples thereof include tetraethylaniline, 2,3,5,6-tetraethylaniline, pentaethylaniline and the like. Moreover, the ethyl of these aniline compounds is n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n -An aniline compound changed to tetradecyl and the like.

  Examples of aniline compounds include 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4, 5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3 , 5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) aniline, 3,4,5-tri (trifluoromethyl) aniline, and the like. Moreover, the aniline compound which changed fluoro of these aniline compounds into chloro, bromo, iodo etc. can be mention | raise | lifted.

  The compound represented by the general formula (5) of the component (b3) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutyl. Amine, n-octylamine, aniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluoro Butylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroanily 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2 -(Trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4,6-tris (trifluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine , Perfluoropentadecylamine, 2-fluoroaniline, 3-fur Roaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoro Methyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4, 6-Tris (trifluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, most preferably water or pentafluoroaniline.

Component (B) is formed by bringing component (b1), component (b2) and component (b3) into contact. The contact order of the component (b1), the component (b2), and the component (b3) includes the following order.
[1] The component (b1) and the component (b2) are brought into contact with each other, and the contact product resulting from the contact is brought into contact with the component (b3).
[2] The component (b1) and the component (b3) are brought into contact with each other, and the contact product resulting from the contact is brought into contact with the component (b2).
[3] The component (b2) and the component (b3) are brought into contact with each other, and the contact product resulting from the contact is brought into contact with the component (b1).

  The contact with the component (b1), the component (b2) and the component (b3) is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Further, a solvent may be used for the contact, and these compounds may be directly contacted without being used.

  When a solvent is used, those that do not react with the component (b1), the component (b2) and the component (b3), and the contact products thereof are used. However, as described above, when each component is contacted step by step, even if the solvent reacts with a component at a certain stage, the solvent does not react with each component at another stage. The solvent can be used in other stages. That is, the solvents in each stage are the same or different from each other. Examples of the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, and nitrile solvents. Examples thereof include polar solvents such as solvents, nitro compounds, amine solvents, sulfur compounds and the like. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; dichloromethane, difluoromethane , Halogenated solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene Dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran Ether solvents such as tetrahydropyran; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Alcohol solvents such as ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, and glycerin; phenol solvents such as phenol and p-cresol; acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride Carbonyl solvents such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; Phosphoric acid derivatives such as oxamethylphosphoric triamide and triethyl phosphate; nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile; nitro compounds such as nitromethane and nitrobenzene; amine solvents such as pyridine, piperidine and morpholine; Examples thereof include sulfur compounds such as dimethyl sulfoxide and sulfolane.

The amount of component (b2) and component (b3) used per mole of component (b1) is preferably satisfied by the following relational formula (II).
| M ³ valence-Mole amount of component (b2) -2 × Mole amount of component (b3) | ≦ 1 (II)
Moreover, the usage-amount of the component (b2) per 1 mol of usage-amount of a component (b1) becomes like this. Preferably it is 0.01-1.99 mol, More preferably, it is 0.1-1.8 mol, Furthermore, Preferably it is 0.2-1.5 mol, Most preferably, it is 0.3-1 mol. Use amount of component (b1) Preferred use amount, more preferred use amount, more preferred use amount, and most preferred use amount of component (b3) per mole are the valence of M ^{3 and} the use of the above component (b1). The amount of component (b2) used per 1 mol is calculated by the relational expression (II).

  The amount of component (b1) and component (b2) used is preferably such that the metal atom derived from component (b1) contained in component (B) is the number of moles of metal atoms contained per gram of component (B). The amount is 0.1 mmol or more, more preferably 0.5 to 20 mmol.

  In order to advance the reaction faster, a heating step at a higher temperature may be added after the contact as described above. In the heating step, it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. In performing the heating step, the solvent used in the contact may be replaced with another solvent having a higher boiling point.

  As a result of such contact, the component (B) may remain as a raw material component (b1), component (b2) and / or component (b3). It is preferable to perform a cleaning treatment to remove. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Moreover, after such a contact or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 0 ° C or higher. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., and particularly preferably 2 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 4 to 18 hours at a temperature of 15 ° C to 160 ° C.

The component (B) is preferably a solid catalyst component formed by bringing the component (b1), the component (b2), the component (b3) and the following component (b4) into contact with each other.
(B4): particulate carrier

  As the particulate carrier of component (b4), a solvent for preparing the polymerization catalyst or a solid substance insoluble in the polymerization solvent is preferably used, and a porous substance is more preferably used. The role of the particulate carrier is described in, for example, “Catalyst Chemistry Applied Chemistry Series 6”.

  The particulate carrier of component (b4) is preferably of a uniform particle size, and the volume standard geometric standard deviation of the particle size of the particulate carrier of component (b4) is preferably 2.5 or less. More preferably, it is 2.0 or less, More preferably, it is 1.7 or less.

The average particle diameter of the particulate carrier of the component (b4) is usually 1 to 5000 μm, preferably 5 to 1000 μm, more preferably 10 to 500 μm, and further preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  As the porous substance of the particulate carrier of component (b4), an inorganic substance or an organic polymer is preferably used, and an inorganic substance is more preferably used.

  Inorganic substances include inorganic oxides, clays, clay minerals, and the like. A plurality of these may be mixed and used.

As the inorganic _{oxide, SiO 2, Al 2 O 3} , MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO 2, SiO 2 -MgO, SiO 2 -Al 2 O 3, SiO _{2 -TiO 2, SiO 2 -V 2} O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO, and, can be mentioned mixtures of two or more of these. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ (silica) is particularly preferable. The inorganic oxide is a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. Carbonic acid salts such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

  In addition, a hydroxyl group is usually generated and present on the surface of the inorganic oxide, but as the inorganic oxide, modified inorganic oxides in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used. . Examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane; triarylchlorosilanes such as triphenylchlorosilane; dialkyldichlorosilanes such as dimethyldichlorosilane; diaryldichlorosilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as methyltrichlorosilane; aryltrichlorosilanes such as phenyltrichlorosilane; trialkylalkoxysilanes such as trimethylmethoxysilane; triarylalkoxysilanes such as triphenylmethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane; Diaryl dialkoxy silanes such as diphenyldimethoxysilane; alkyltrimethoxy silanes such as methyltrimethoxysilane Coxysilane; aryltrialkoxysilane such as phenyltrimethoxysilane; tetraalkoxysilane such as tetramethoxysilane; alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane; tetrachlorosilane; methanol, ethanol Alcohols such as phenol; dialkylmagnesium such as dibutylmagnesium, butylethylmagnesium and butyloctylmagnesium; inorganic oxides contacted with alkyllithium such as butyllithium; and dialkyls such as diethylamine and diphenylamine after contact with trialkylaluminum Examples thereof include inorganic oxides contacted with alcohols such as amines, methanol and ethanol, and phenols.

  In addition, the strength of the inorganic oxide itself may increase due to hydrogen bonding between hydroxyl groups. In that case, if all the active hydrogens of the surface hydroxyl group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxyl group is not particularly limited. As this method, the method of changing the usage-amount of the compound used for a contact can be illustrated, for example.

  Clay or clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophyllite, talc, unmo group, smectite, montmorillonite group, hectorite, laponite, saponite, vermiculite, ryokdeite group, Examples include palygorskite, kaolinite, nacrite, dickite and halloysite. Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

  An inorganic oxide is preferably used as the inorganic substance. The inorganic substance is preferably dried and substantially free of moisture, and is preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method of drying by circulating an inert gas (for example, nitrogen or argon) dried during heating at a constant flow rate, a method of heating and depressurizing under reduced pressure, and the like.

  The organic polymer is preferably a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group.

  As functional groups having active hydrogen, primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group Sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, carbazolyl group and the like. Preferred are primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group and thiol group. Particularly preferred are a primary amino group, a secondary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  The non-proton-donating Lewis basic functional group is a functional group having a Lewis base moiety that does not have an active hydrogen atom, and includes pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, -Substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group , Alkoxy groups, alkyloxycarbonyl groups, N, N-substituted carbamoyl groups, thioalkoxy groups, substituted sulfinyl groups, substituted sulfonyl groups, substituted sulfonic acid groups, and the like. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  In the organic polymer, the content of the functional group having active hydrogen or the non-proton-donating Lewis basic functional group is preferably 0.01 to as the molar amount of the functional group per gram of polymer unit constituting the organic polymer. 50 mmol / g, more preferably 0.1 to 20 mmol / g.

  Examples of the method for producing a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group include, for example, a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and 1 Examples thereof include a method of homopolymerizing a monomer having one or more polymerizable unsaturated groups and a method of copolymerizing the monomer and another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

  Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group; alkynyl groups such as ethyne group and the like.

  Examples of monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, vinyl group-containing hydroxy compounds, and the like. be able to. Specific examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methyl. Amine, 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-butene-1- For example, all.

  Examples of monomers having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole and the like. be able to.

  Examples of other monomers having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound, and cyclic olefin. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentadiene. Two or more of these monomers may be used. Preferably, they are ethylene and styrene. Examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

  The organic polymer is preferably dried and substantially free of moisture, and is preferably dried by heat treatment. The temperature of the heat treatment is usually 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which a dry inert gas (for example, nitrogen or argon) is circulated and dried at a constant flow rate during heating, a method of heat drying under reduced pressure, and the like.

When the solid catalyst component formed by contacting the component (b1), the component (b2), the component (b3), and the component (b4) is used as the component (B), the component (b1), the component ( As the contact order of b2), component (b3) and component (b4)), the following order may be mentioned.
<1> The component (b1) and the component (b2) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b4).
<2> The component (b1) and the component (b2) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b3).
<3> The component (b1) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b2), and the contact product resulting from the contact is brought into contact with the component (b4).
<4> The component (b1) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b2).
<5> The component (b1) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b2), and the contact product resulting from the contact is brought into contact with the component (b3).
<6> The component (b1) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b2).
<7> The component (b2) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b4).
<8> The component (b2) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b1).
<9> The component (b2) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b3).
<10> The component (b2) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b1).
<11> The component (b3) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b2).
<12> The component (b3) and the component (b4) are brought into contact with each other, the contact with the contact is brought into contact with the component (b2), and the contact with the contact is brought into contact with the component (b1).

  The contact with the component (b1), the component (b2), the component (b3) and the component (b4) is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Further, a solvent may be used for the contact, and these compounds may be directly contacted without being used.

  When a solvent is used, a component that does not react with the component (b1), the component (b2), the component (b3), the component (b4), and their contacts is used. However, as described above, when each component is contacted step by step, even if the solvent reacts with a component at a certain stage, the solvent does not react with each component at another stage. The solvent can be used in other stages. That is, the solvents in each stage are the same or different from each other. Examples of the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, and nitrile solvents. Examples thereof include polar solvents such as solvents, nitro compounds, amine solvents, sulfur compounds and the like. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; dichloromethane, difluoromethane , Halogenated solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene Dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran Ether solvents such as tetrahydropyran; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Alcohol solvents such as ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, and glycerin; phenol solvents such as phenol and p-cresol; acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride Carbonyl solvents such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; Phosphoric acid derivatives such as oxamethylphosphoric triamide and triethyl phosphate; nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile; nitro compounds such as nitromethane and nitrobenzene; amine solvents such as pyridine, piperidine and morpholine; Examples thereof include sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When the contact (c) obtained by contacting the component (b1), the component (b2) and the component (b3) and the component (b4) are contacted, that is, the above <1>, <3>, <7 In each of the methods, the solvent (s1) for producing the contact product (c) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, as the solvent (s2) when the contact product (c) and the component (b4) are contacted, a polar solvent is preferable. As an index representing the polarity of the solvent, E _T ^N value (C.Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988).) And the like are known, 0.8 ≧ A solvent satisfying the range of E _T ^N ≧ 0.1 is particularly preferable.

  Examples of the polar solvent include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol Cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, Examples thereof include ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide, sulfolane and the like.

  More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). ) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, particularly preferably di-n-butyl ether, methyl- ert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol Most preferred are tetrahydrofuran, methanol, ethanol, 1-propanol, and 2-propanol.

  As the solvent (s2), a mixed solvent of these polar solvents and hydrocarbon solvents can be used. As the hydrocarbon solvent, compounds exemplified as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are used. Examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, heptane / methanol mixed solvent, heptane. / Ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent, xylene / Methanol mixed solvent, xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, xylene / 2-propanol mixed solvent and the like. Preferably, hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent It is. More preferred are a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent, and a toluene / ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent. Moreover, the preferable range of the ethanol fraction in a toluene / ethanol mixed solvent is 10-50 volume%, More preferably, it is 15-30 volume%.

  When the contact (c) formed by bringing the component (b1), the component (b2) and the component (b3) into contact with the component (b4), that is, the above <1>, <3>, In each method of <7>, a hydrocarbon solvent can also be used as the solvent (s1) and the solvent (s2). In this case, after the component (b1), the component (b2) and the component (b3) are contacted, it is preferable that the time until the obtained contact product (c) and the component (b4) are contacted is short. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. The temperature at which the contact (c) and the component (b4) are contacted is usually -100 ° C to 40 ° C, preferably -20 ° C to 20 ° C, and most preferably -10 ° C to 10 ° C. It is.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, both the above nonpolar solvent and polar solvent should be used. Can do. Preferably, it is a nonpolar solvent. This is because a contact product between component (b1) and component (b3) or a contact product between component (b1) and component (b2) and component (b3) is generally non-contact. Since the solubility in the polar solvent is low, when the component (b4) is present in the reaction system when these contact products are formed, the contact product precipitates on the surface of the component (b4) and is more easily immobilized. Because it is considered.

  In order to advance the reaction faster, a heating step at a higher temperature may be added after the contact as described above. In the heating step, it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. In performing the heating step, the solvent used in the contact may be replaced with another solvent having a higher boiling point.

  As a result of such contact, the component (B), the component (b1), the component (b2), the component (b3) and / or the component (b4) as raw materials may remain as unreacted materials. It is preferable to perform a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Moreover, after such a contact or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 0 ° C or higher. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., and particularly preferably 2 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 4 to 18 hours at a temperature of 15 ° C to 160 ° C.

  Examples of the organoaluminum compound of component (C) include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, dialkylaluminum hydride, alkyl (dialkoxy) aluminum, dialkyl (alkoxy) aluminum, alkyl (diaryloxy) aluminum, and dialkyl. (Aryloxy) aluminum and the like.

Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride, and alkylaluminum. Examples of the dichloride include methylaluminum dichloride, ethylaluminum dichloride, and n-propyl alcohol. Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, and di-n. -Butylaluminum hydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride and the like. Examples of the alkyl (dialkoxy) aluminum include methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert- Butoxy) aluminum and the like, and examples of dialkyl (alkoxy) aluminum include Examples thereof include dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, methyl (tert-butoxy) aluminum, and examples of alkyl (diaryloxy) aluminum include methyl (diphenoxy) aluminum and methylbis (2,6-diisopropyl). Phenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum, and the like. Examples of the dialkyl (aryloxy) aluminum include dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2 , 6-diphenylphenoxy) aluminum and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

  The organoaluminum compound is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, More preferred are triisobutylaluminum and tri-n-octylaluminum.

  In the contact of the component (A1), the component (A2), the component (B), and the component (C), the molar ratio ((A1) / (A2)) between the component (A1) and the component (A2) Are 1-90, and the contact amount of a component (B) and a component (C) is arbitrary.

  In the contact of the component (A1), the component (A2), the component (B), and the component (C), as the molar ratio ((A1) / (A2)) of the component (A1) and the component (A2), The lower limit is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, particularly preferably 25 or more, and the upper limit is preferably 80 or less, more preferably 70 or less. Yes, more preferably 65 or less.

  The total amount of component (A1) and component (A2) used is preferably 1 to 10000 μmol / g, more preferably 10 to 1000 μmol / g, and still more preferably, per 1 g of component (B). 20 to 500 μmol / g.

  The amount of component (C) used is preferably 0.1 to 1000 as the number of moles of aluminum atoms in the organoaluminum compound per mole of the total number of moles of component (A1) and component (A2). Preferably, it is 0.5-500, More preferably, it is 1-100.

  Further, in the preparation of the polymerization catalyst, in addition to the component (A1), the component (A2), the component (B) and the component (C), an electron donating compound (component (D)) may be contacted. The amount of the electron donating compound used is preferably 0.01 to 100, more preferably 0 as the number of moles of the electron donating compound per mole of the total number of moles of the component (A1) and the component (A2). .1 to 50, more preferably 0.25 to 5.

  Examples of the electron donating compound include triethylamine and trinormaloctylamine.

  The contact between the component (A1), the component (A2), the component (B), the component (C), and, if necessary, the component (D) is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 30 minutes to 100 hours. Further, the contact may be carried out in the polymerization reactor with each component being charged separately into the polymerization reaction vessel.

  The method for producing an ethylene-α-olefin copolymer of component (A) in the present invention comprises copolymerizing ethylene and an α-olefin in the presence of a catalyst for producing the ethylene-α-olefin copolymer. is there.

  Examples of the polymerization method include a gas phase polymerization method, a slurry polymerization method, and a bulk polymerization method. A gas phase polymerization method is preferable, and a continuous gas phase polymerization method is more preferable. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method for supplying the polymerization catalyst and each catalyst component to the polymerization reaction tank, a method for supplying the catalyst in a moisture-free state using an inert gas such as nitrogen or argon, hydrogen, ethylene, etc. A method of dissolving or diluting and supplying in a solution or slurry state is used.

  When vapor-phase polymerization of ethylene and α-olefin, the polymerization temperature is usually lower than the temperature at which the ethylene-α-olefin copolymer produced by polymerization is melted, preferably 0 to 150 ° C, More preferably, it is 30-100 degreeC. An inert gas may be introduced into the polymerization reaction tank, and hydrogen may be introduced as a molecular weight regulator. Further, an electron donating compound may be introduced.

  The α-olefin used for the polymerization is an α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1 -Decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like. These may be used independently and may use 2 or more types together. 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable.

  As a manufacturing method of the ethylene-alpha-olefin copolymer of the component (A) in this invention, a component (A1), a component (A2), a component (B), a component (C), and an electron as needed. A method of polymerizing olefins using a prepolymerized solid component obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization) using a donor compound as a polymerization catalyst component or a polymerization catalyst is preferable. .

  Examples of the olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene and cyclohexene. These can be used alone or in combination of two or more. Preferably, ethylene alone, or a combination of ethylene and α-olefin, more preferably ethylene alone, or at least one α-olefin selected from 1-butene, 1-hexene and 1-octene, and ethylene Is used in combination.

  The content of the prepolymerized polymer in the prepolymerized solid component is preferably 0.01 to 1000 g, more preferably 0.05 to 500 g, and still more preferably 0.001 g per 1 g of the component (B). 1 to 200 g.

  The preliminary polymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method. As a method of introducing the component (A1), the component (A2), the component (B), the component (C), and, if necessary, the electron donating compound into the polymerization reaction tank for performing prepolymerization, A method in which an inert gas such as nitrogen or argon, hydrogen, ethylene, or the like is used, is added in a moisture-free state, or a method in which each component is dissolved or diluted in a solvent and then introduced in a solution or slurry state.

  When the prepolymerization is performed by a slurry polymerization method, a hydrocarbon compound is usually used as the solvent, and examples thereof include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, and heptane. These may be used alone or in combination of two or more. As the hydrocarbon compound, those having a boiling point of 100 ° C. or less at normal pressure are preferable, those having a boiling point of 90 ° C. or less at normal pressure are more preferable, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, and cyclohexane are Further preferred.

  Moreover, when prepolymerization is performed by the slurry polymerization method, as the slurry concentration, the amount of the component (B) per liter of the solvent is usually 0.1 to 600 g, preferably 0.5 to 300 g. The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed, but the temperature at which the prepolymerization is started is preferably 45 ° C. or less, and preferably 40 ° C. or less. Moreover, the partial pressure of olefins in the gas phase part during prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  As a method of supplying the prepolymerized prepolymerized solid catalyst component to the polymerization reaction tank, a method of supplying an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in a state free from moisture, each component Is dissolved or diluted in a solvent and supplied in a solution or slurry state.

  The crosslinked foaming resin composition of the present invention contains a thermal decomposition type foaming agent having a decomposition temperature of 120 to 240 ° C. as the component (B). The pyrolytic foaming agent is not particularly limited, and a known pyrolytic foaming agent can be used. A plurality of pyrolytic foaming agents may be used in combination.

  Examples of the pyrolytic foaming agent include inorganic foaming agents such as ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, anhydrous monosodium citrate; azodicarbonamide, barium azodicarboxylate, Azobisbutyronitrile, nitrodiguanidine, N, N-dinitropentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosotephthalamide, p-toluenesulfonyl hydrazide, p-toluenesulfonyl cellcarbazide, Organic foams such as p, p'-oxybisbenzenesulfonyl hydrazide, azobisisobutyronitrile, p, p'-oxybisbenzenesulfonyl semicarbazide, 5-phenyltetrazole, trihydrazinotriazine, hydrazodicarbonamide Agents and the like. Among these, azodicarbonamide, sodium hydrogen carbonate, and p'-oxybisbenzenesulfonyl hydrazide are preferably used from the viewpoint of economy. It is particularly preferable to use a foaming agent containing azodicarbonamide and sodium hydrogen carbonate because a molding temperature range is wide and a crosslinked foamed molded article having fine bubbles is obtained.

  The thermal decomposition type foaming agent of component (B) has a decomposition temperature of 120 to 240 ° C. When using a thermal decomposition type foaming agent having a decomposition temperature higher than 200 ° C., it is preferable to use the foaming aid in combination with a decomposition temperature lowered to 200 ° C. or less. As foaming aids, metal oxides such as zinc oxide and lead oxide; metal carbonates such as zinc carbonate; metal chlorides such as zinc chloride; urea; zinc stearate, lead stearate, dibasic lead stearate, Metal soap such as zinc laurate, zinc 2-ethylhexoate, and dibasic lead phthalate; Organotin compounds such as dibutyltin dilaurate and dibutyltin dimale; Tribasic lead sulfate, dibasic lead phosphite, basic Examples thereof include inorganic salts such as lead sulfite.

  As the pyrolyzable foaming agent for component (B), a masterbatch composed of a pyrolyzable foaming agent, a foaming aid and a resin can also be used. The type of resin used in the masterbatch is not particularly limited as long as the effects of the present invention are not impaired, but the ethylene-α-olefin copolymer of component (A) contained in the resin composition of the present invention or the low pressure method It is preferably a density polyethylene. The total amount of the thermally decomposable foaming agent and foaming aid contained in the masterbatch is usually 5 to 90% by weight when the resin constituting the masterbatch is 100% by weight.

  In order to obtain a foam having finer bubbles, it is preferable to use a foam nucleating agent in combination. Foam nucleating agents include talc, silica, mica, zeolite, calcium carbonate, calcium silicate, magnesium carbonate, aluminum hydroxide, barium sulfate, aluminosilicate, clay, quartz powder, diatomaceous earth inorganic fillers; polymethyl methacrylate, polystyrene Examples of beads having a particle diameter of 100 μm or less; metal salts such as calcium stearate, magnesium stearate, zinc stearate, sodium benzoate, calcium benzoate, aluminum benzoate, and magnesium oxide, and combinations of two or more thereof May be.

  The resin composition for cross-linking and foaming of the present invention comprises 100 parts by weight of the above-described component (A) ethylene-α-olefin copolymer and 100 parts by weight of the component (A), and the thermal decomposition of the component (B). 1 to 70 parts by weight, preferably 10 to 50 parts by weight of the mold foaming agent is contained.

  The crosslinked foaming resin composition of the present invention contains known additives such as a crosslinking aid, a heat stabilizer, a weather stabilizer, a pigment, a filler, a lubricant, an antistatic agent, and a flame retardant as necessary. May be.

The resin composition for cross-linking and foaming of the present invention may contain a thermoplastic resin different from the ethylene-α-olefin copolymer of component (A) as necessary. Examples of the thermoplastic resin include linear low density polyethylene, high density polyethylene, medium density polyethylene, high pressure method low density polyethylene, ultra low density polyethylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer. Polymer, ethylene- (meth) acrylic acid copolymer metal salt, polypropylene, polystyrene, ABS resin, styrene / butadiene block copolymer and its hydrogenated product, styrene / isoprene block copolymer and its hydrogenated product, etc. Styrenic polymers, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 6, 66, polycarbonate, polymethyl methacrylate, polyacetal, poly E double sulfides, such as ethylene-propylene copolymer rubber.

  A cross-linked foam can be obtained by the following method using the resin composition for cross-linking and foaming as described above.

  First, the crosslinked foamed resin composition containing the component (A) and the component (B) is kneaded at a temperature at which the pyrolyzable foaming agent of the component (B) contained in the resin composition is not decomposed. Get anti. The shape of the cross-linked foam original fabric is not particularly limited. For example, as a method of forming into a sheet, a method of forming into a sheet form with a calendar roll, a method of forming into a sheet form with a press molding machine, a method of forming into a sheet form by melt extrusion from a T die or an annular die, and the like are included. . The kneading temperature is preferably 50 ° C. or more lower than the decomposition temperature of the thermally decomposable foaming agent and 20 ° C. or more higher than the melting point of the component (A).

  Next, crosslinking is performed by irradiating ionizing radiation from at least one surface of the cross-linked foam original fabric. Examples of the ionizing radiation applied to the cross-linked foam original fabric include α rays, β rays, γ rays, electron beams, neutron rays, and X rays. Of these, cobalt-60 gamma rays or electron beams are preferred.

  Irradiation with ionizing radiation is performed using a known ionizing radiation irradiation apparatus, and the irradiation amount is usually 5 to 200 kGy, preferably 30 to 100 kGy. The cross-linked foam molding resin composition of the present invention can produce a cross-linked foam excellent in expansion ratio with a small radiation dose as compared with a conventional cross-linked foam molding resin composition.

After crosslinking the cross-linked foam original fabric, the cross-linked foam can be obtained by heating to a temperature higher than the decomposition temperature of the thermally decomposable foaming agent to cause foaming.
As a method for heating and foaming the crosslinked cross-linked foam original fabric, a known method can be applied, and a cross-linked foam original fabric such as a vertical hot-air foaming method, a horizontal hot-air foaming method, a horizontal chemical liquid foaming method or the like can be used. A method capable of continuous heating and foaming is preferred. The heating temperature is a temperature equal to or higher than the decomposition temperature of the pyrolyzable foaming agent of component (B), and preferably 5 to 50 ° C. higher than the decomposition temperature of the pyrolyzable foaming agent. The heating time is usually 3 to 5 minutes when heated in an oven.

  In the case of crosslinking by ionizing radiation, a foam having excellent foaming ratio and strength can be obtained by using a crosslinking aid. The crosslinking aid is for increasing the degree of crosslinking of the crosslinking type thermoplastic resin composition and improving the mechanical properties of the thermoplastic resin composition. A compound having a plurality of double bonds in the molecule is preferred. Used. Examples of the crosslinking aid include N, N′-m-phenylene bismaleimide, toluylene bismaleimide, triallyl isocyanurate, triallyl cyanurate, p-quinone dioxime, nitrobenzene, diphenylguanidine, divinylbenzene, ethylene glycol. Examples include dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and allyl methacrylate. Moreover, you may use these crosslinking adjuvants in combination of multiple.

  The addition amount of the crosslinking aid can be selected in the range of 0.01 to 4.0 parts by weight with respect to 100 parts by weight of the total thermoplastic resin contained in the crosslinked foaming resin composition. Preferably it is 0.05-2.0 weight part. If the amount is less than 0.01 parts by weight, the effect of adding a crosslinking aid hardly appears, and if it exceeds 4 parts by weight, it is not economically advantageous.

  The cross-linked foam obtained by the present invention is suitably used for a buffer material, a heat insulating material, a sound insulating material, a heat insulation and cold insulation material, and the like.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

(1) Density (d, unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(2) Melt flow rate (MFR, unit: g / 10 minutes)
In the method defined in JIS K7210-1995, measurement was performed by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(3) Swell ratio (SR)
In the measurement of the melt flow rate in (2), an ethylene-α-olefin copolymer strand extruded at a length of about 15 to 20 mm from an orifice under conditions of a temperature of 190 ° C. and a load of 21.18 N Cooled to obtain a solid strand. Next, the diameter D (unit: mm) of the strand at a position of about 5 mm from the upstream end of extrusion of the strand was measured, and the value obtained by dividing the diameter D by the orifice diameter 2.095 mm (D ₀ ) (D / D ₀ ) was calculated and used as the swell ratio.

(4) Molecular weight distribution (Mw / Mn, Mz / Mw)
Using gel permeation chromatograph (GPC) method, z average molecular weight (Mz), weight average molecular weight (Mw) and number average molecular weight (Mn) are measured under the following conditions (1) to (8). Mw / Mn and Mz / Mw were obtained. The baseline on the chromatogram is a stable horizontal region with a sufficiently long retention time than the appearance of the sample elution peak and a stable horizontal region with a sufficiently long retention time than the solvent elution peak was observed. A straight line formed by connecting the points. The molecular weight at each peak position of the bimodal distribution is a value obtained by conversion to polyethylene by calibration.
(1) Equipment: Tosoh HLC-8121GPC / HT
(2) Separation column: Tosoh TSKgel GMH _HR- H (20) HT
(3) Measurement temperature: 152 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 0.1 mL / min
(6) Injection volume: 300μL
(7) Detector: Differential refraction
(8) Molecular weight reference material: Standard polystyrene

(5) Number of branches having 5 or more carbon atoms (N _LCB , unit: 1 / 1000C)
A carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured by the carbon nuclear magnetic resonance method under the following measurement conditions, and determined by the following calculation method.
<Measurement conditions>
Apparatus: AVANCE600 manufactured by Bruker
Measuring solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4
= 75/25 (volume ratio) mixed liquid Measurement temperature: 130 ° C
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Trimethylsilane Window function: Negative exponential function <Calculation method>
The peak area of the peak having a peak top in the vicinity of 38.22 to 38.27 ppm was determined with the sum of all peaks observed at 5 to 50 ppm being 1000. The peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side. In the measurement of the ethylene-1-octene copolymer under the present conditions, the position of the peak top of the peak derived from methine carbon to which a branch having 6 carbon atoms was bonded was 38.21 ppm.

(6) Melt complex viscosity (η *, unit: Pa · sec)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 190 ° C. was measured under the following measurement conditions, and a melt complex viscosity measured at an angular frequency of 100 rad / sec. Asked. The lower the melt complex viscosity, the better the extrusion load during extrusion molding.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(7) Measurement of extensional viscosity of molten resin Extensional viscosity of molten resin at 130 ° C. at a Henky speed of 0.1 s ⁻¹ and 1 s ⁻¹ using an extension viscosity measuring device (ARES manufactured by TA Instruments) A time curve was measured. As a measurement test piece, a sheet of 18 mm × 10 mm and thickness 0.7 mm obtained by press molding was used.

(8) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, an ethylene-α-olefin copolymer was melt-extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm at a temperature of 190 ° C. and an extrusion speed of 0.32 g / min. The melted ethylene-α-olefin copolymer was drawn into a filament by a take-up roll at a take-up rate of 6.3 (m / min) / min, and the tension during take-up was measured. The maximum tension from the start of take-up until the filamentous ethylene-α-olefin copolymer was cut was defined as the melt tension.

(9) Maximum take-up speed (MTV, unit: m / min)
In the measurement of the melt tension of (9), the take-up speed when the filamentous ethylene-α-olefin copolymer was cut was defined as the maximum take-up speed. The higher this value, the better the take-up property at the time of extrusion molding.

(10) Characteristic relaxation time (τ) (sec)
Using a viscoelasticity measuring apparatus (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), the melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software manufactured by Rheometrics R. Using 4.4.4, a master curve of the melt complex viscosity-angular frequency curve at 190 ° C. was prepared, and the characteristic relaxation time (τ) was obtained.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(11) Foam density (d, unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. Note that the foam sample was not annealed.

(12) Foaming ratio (unit: times)
From the density of the resin determined by the above (1) density method and the foam density determined in (11), it was calculated by the following formula.
Foaming ratio = resin density / foam density

Polymerization example 1
(1) Preparation of solid catalyst component In a reactor equipped with a nitrogen-replaced stirrer, 2.8 kg of silica (Sypolol 948, manufactured by Devison) and 24 kg of toluene, which were heat-treated at 300 ° C. under nitrogen flow, were stirred. . Then, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was kept for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

(2) Polymerization After vacuum drying, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.05 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 3.1 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3.125 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and diphenyl adjusted to a concentration of 1 μmol / ml 0.5 ml of a toluene solution of methylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component 73 obtained in (1) above was added. .6 mg was charged. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.33 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 82 g of an ethylene-1-hexene copolymer. The obtained copolymer was kneaded with a roll (Nisshin Kagaku Co., Ltd. test roll HR-20F type) so as to be uniform, and then the physical properties were evaluated. The kneading conditions were a front roll temperature of 150 ° C., a rear roll of 160 ° C., a roll gap of 5 mm, and a kneading time of 5 minutes (after sample melting). Table 1 shows the results of physical properties evaluation of the copolymer obtained by kneading.

Polymerization example 2
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, hydrogen was added so that the partial pressure became 0.01 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.7 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3.125 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and diphenyl adjusted to a concentration of 1 μmol / ml 0.5 ml of a toluene solution of methylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to the transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above. 52.3 mg of the catalyst component was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.11 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 82 g of an ethylene-1-hexene copolymer. The obtained copolymer was roll kneaded in the same manner as in Polymerization Example 1. Table 1 shows the results of physical properties evaluation of the obtained copolymer after roll kneading.

Polymerization example 3
(1) Polymerization After vacuum drying, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.02 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.2 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3.125 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and diphenyl adjusted to a concentration of 1 μmol / ml 0.5 ml of a toluene solution of methylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above. 48.2 mg of the catalyst component was charged. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.11 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 82 g of an ethylene-1-hexene copolymer. The obtained copolymer was roll kneaded in the same manner as in Polymerization Example 1. Table 1 shows the results of physical properties evaluation of the obtained copolymer after roll kneading.

Polymerization example 4
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.03 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.8 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3.125 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and diphenyl adjusted to a concentration of 1 μmol / ml 0.5 ml of a toluene solution of methylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above. 53.3 mg of the catalyst component was charged. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.19 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 58 g of an ethylene-1-hexene copolymer. The obtained copolymer was roll kneaded in the same manner as in Polymerization Example 1. Table 1 shows the results of physical properties evaluation of the obtained copolymer after roll kneading.

Polymerization example 5
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, charged with 180 ml of 1-hexene and 650 g of butane as a polymerization solvent, and heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenylmethylene (concentration adjusted to 1 μmol / ml) 0.1 ml of a toluene solution of 1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above 43.7 mg was added. During the polymerization, polymerization was carried out at 70 ° C. for 40 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.07 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 53 g of an ethylene-1-hexene copolymer. The obtained copolymer was roll kneaded in the same manner as in Polymerization Example 1. Table 1 shows the results of physical properties evaluation of the obtained copolymer after roll kneading.

Polymerization Example 6
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, hydrogen was added so that the partial pressure became 0.01 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.54 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenylmethylene (concentration adjusted to 1 μmol / ml) 0.1 ml of a toluene solution of 1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above 47.1 mg was charged. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.11 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 82 g of an ethylene-1-hexene copolymer. The obtained copolymer was roll kneaded in the same manner as in Polymerization Example 1. Table 1 shows the results of physical properties evaluation of the obtained copolymer after roll kneading.

Polymerization example 7
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.015 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.0 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenylmethylene (concentration adjusted to 1 μmol / ml) 0.1 ml of a toluene solution of 1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above 48.3 mg was charged. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.19 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 69 g of an ethylene-1-hexene copolymer. The obtained copolymer was roll kneaded in the same manner as in Polymerization Example 1. Table 1 shows the results of physical properties evaluation of the obtained copolymer after roll kneading.

Example 1
(1) Preparation of solid catalyst component In a reactor equipped with a nitrogen-replaced stirrer, silica heat-treated at 300 ° C. under nitrogen flow (Sypolol 948 manufactured by Devison; 50% volume average particle size = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was kept for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

(2) Polymerization The inside of an autoclave equipped with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, charged with 180 ml of 1-hexene and 650 g of butane as a polymerization solvent, and heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 3 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenylmethylene (concentration adjusted to 1 μmol / ml) 0.1 ml of a toluene solution of cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then 62.4 mg of the solid catalyst component obtained in (1) above was added. did. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.0758 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain an ethylene-1-hexene copolymer. The obtained copolymer was kneaded with a roll (Nisshin Kagaku Co., Ltd. test roll HR-20F type) so as to be uniform, and then the physical properties were evaluated. The kneading conditions were a front roll temperature of 150 ° C., a rear roll of 160 ° C., a roll gap of 5 mm, and a kneading time of 5 minutes (after sample melting). Table 2 shows the results of physical property evaluation of the copolymer (hereinafter referred to as PE (1)) obtained by kneading.
Using 100 parts by weight of PE (1) pellets as component (A), a foam was obtained by the following method.

(3) Molding of crosslinked foam Azodicarbonamide <ADCA> (manufactured by Sankyo Kasei Co., Ltd.), which is a thermal decomposition type foaming agent of component (B), with respect to 100 parts by weight of the pellet of PE (1). Celmic CE (decomposition temperature 208 ° C.) 20 parts by weight, zinc stearate 1.5 parts by weight, and hindered phenol antioxidant (trade name IRGANOX 1010 manufactured by Ciba Japan Co., Ltd.) 0.5 parts by weight After kneading with a Brabender at a set temperature and a rotation speed of 25 rpm, the obtained kneaded material is put into a mold on a press at 130 ° C., left to stand for 15 minutes, then pressurized and cooled, and a thickness of 2 mm is obtained. An uncrosslinked and unfoamed sheet was obtained. Next, the sheet was irradiated with an electron beam of 30 kGy by an electron beam accelerator to obtain an unfoamed crosslinked sheet. The crosslinked sheet was heated in an oven at 220 ° C. to obtain a crosslinked foam. Table 3 shows the physical properties of the obtained crosslinked foam.

[Comparative Example 1]
(1) Preparation of co-catalyst carrier Silica (Dybson Sylpol 948; 50% volume average particle size = 59 μm; pore volume = heat treated at 300 ° C. under nitrogen flow in a reactor equipped with a nitrogen-substituted stirrer 1.68 ml / g; specific surface area = 313 m ² / g) 0.36 kg and 3.5 liters of toluene were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 1,1,1,3,3,3-hexamethyldisilazane 0.15 liter and toluene 0.2 liter was kept at 5 ° C. in the reactor. The solution was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid component was washed 6 times with 2 liters of toluene. Thereafter, 2 liters of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 0.27 liter of diethyl zinc in hexane (diethyl zinc concentration: 2 mol / liter) was added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.05 kg of pentafluorophenol and 0.09 liter of toluene was added dropwise over 60 minutes while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Thereafter, the mixture was cooled to 5 ° C., and 7 g of H ₂ O was added dropwise over 1.5 hours while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours, then heated to 55 ° C. and stirred at 55 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature, and 0.63 liter of diethyl zinc in hexane solution (diethyl zinc concentration: 2 mol / liter) was added. After cooling to 5 ° C., a mixed solution of 94 g of 3,4,5-trifluorophenol and 0.2 liter of toluene was added dropwise over 60 minutes while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then cooled to 5 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O 17 g The temperature of the reactor to 5 ° C.. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, then heated to 40 ° C, stirred at 40 ° C for 2 hours, further heated to 80 ° C, and stirred at 80 ° C for 2 hours. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is seen, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. Then, 3 liters of toluene was added and stirred at 95 ° C. for 2 hours. The solid component was allowed to settle, and when the interface between the precipitated solid component layer and the upper slurry portion was seen, the upper slurry portion was removed. Next, at 95 ° C., 4 times with 3 liters of toluene and twice with 3 liters of hexane at room temperature, the mixture was stirred and allowed to stand to settle the solid component. When the interface with the slurry portion was visible, the upper slurry portion was removed. Subsequently, the remaining liquid components were removed with a filter. Then, the solid component (henceforth a promoter support (a)) was obtained by drying at room temperature under reduced pressure for 1 hour.

(2) Preparation of prepolymerization catalyst component (1) 80 liters of butane was added to an autoclave with an internal volume of 210 liters previously purged with nitrogen, and then 101 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. The autoclave was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave was lowered to 30 ° C. and the system was stabilized, 0.03 MPa of ethylene was charged at the gas phase pressure in the autoclave, and 0.7 kg of the promoter support (a) was added, followed by triisobutyl. Polymerization was started by charging 158 mmol of aluminum. After 30 minutes while continuously supplying ethylene at 0.7 kg / Hr, the temperature was raised to 50 ° C., and ethylene and hydrogen were respectively 3.5 kg / Hr and 5.5 liters (room temperature and normal pressure volume) / Hr. A total of 4 hours of prepolymerization was carried out by continuous feeding. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas, etc. are vacuum-dried at room temperature, and the prepolymerized catalyst component (1) in which 15 g of polyethylene is prepolymerized per 1 g of the promoter support (a). Got.

(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component (1) obtained above, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. As a result, polymer powder was obtained. As polymerization conditions, the polymerization temperature was 84 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.4%, the 1-butene molar ratio to the total of ethylene, 1-butene and 1-hexene was 2.3%, The 1-hexene molar ratio was 1.0%. During the polymerization, ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene-1-butene copolymer (hereinafter referred to as PE (2)) was obtained. Table 2 shows the results of physical properties evaluation of the obtained copolymer.
A crosslinked foam was obtained in the same manner as in Example 1 except that 100 parts by weight of the pellet of PE (2) was used as the component (A). Table 3 shows the physical properties of the obtained crosslinked foam.

Claims (6)

Crosslinking obtained by irradiating ionizing radiation to a resin composition containing 100 parts by weight of the following component (A) and 1 to 70 parts by weight of the following component (B) with respect to 100 parts by weight of the component (A) Foaming resin composition.
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate ( An ethylene-α-olefin copolymer having an MFR) of 0.01-100 g / 10 min, a bimodal molecular weight distribution, and a single melting peak observed by a differential scanning calorimeter (DSC) Combined component (B): Thermally decomposable foaming agent having a decomposition temperature of 120 to 240 ° C Crosslinking obtained by irradiating ionizing radiation to a resin composition containing 100 parts by weight of the following component (A) and 1 to 70 parts by weight of the following component (B) with respect to 100 parts by weight of the component (A) Foaming resin composition.
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate ( MFR) is 0.01 to 100 g / 10 min, has a bimodal molecular weight distribution, and has an ethylene-α-olefin copolymer component (B ): Pyrolytic foaming agent having a decomposition temperature of 120 to 240 ° C Crosslinking obtained by irradiating ionizing radiation to a resin composition containing 100 parts by weight of the following component (A) and 1 to 70 parts by weight of the following component (B) with respect to 100 parts by weight of the component (A) Foaming resin composition.
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density (d) of 860 to 950 kg / m ³ , and a melt flow rate ( MFR) is 0.01 to 100 g / 10 min, has a bimodal molecular weight distribution, and satisfies the following relational expression: ethylene-α-olefin copolymer 0.084 × ln (MFR) +0. 69 <k1 / k2 <0.126 × ln (MFR) +1.03
(However, k1 / k2 in the above formula is an extensional viscosity nonlinear exponential ratio)
Component (B): Thermally decomposable foaming agent having a decomposition temperature of 120 to 240 ° C The resin composition for crosslinked foaming according to claim 1 or 2, wherein the component (A) is an ethylene-α-olefin copolymer that satisfies the following relational expression.
0.084 × ln (MFR) +0.69 <k1 / k2 <0.126 × ln (MFR) +1.03
(However, k1 / k2 in the above formula is an extensional viscosity nonlinear exponential ratio)   The crosslinked foamed resin composition according to any one of claims 1 to 4 is kneaded at a temperature at which the thermally decomposable foaming agent is not decomposed to obtain a crosslinked foam original fabric, from at least one surface of the crosslinked foam original fabric A method for producing a crosslinked foamed product, which is irradiated with ionizing radiation and then heated to a temperature equal to or higher than the decomposition temperature of the thermally decomposable foaming agent to cause foaming.   A cross-linked foam obtained by the method according to claim 5.