JP4912753B2 - Propylene polymer composition and molded article comprising the composition - Google Patents

Description

  The present invention relates to a propylene polymer composition and a molded body comprising the composition.

  Polypropylene includes isotactic polypropylene, syndiotactic polypropylene, etc. Among them, isotactic polypropylene is inexpensive and is widely used in various applications because of its rigidity, heat resistance and surface gloss. Yes.

  On the other hand, syndiotactic polypropylene is known to be obtained by low-temperature polymerization in the presence of a catalyst comprising a vanadium compound, ether and organoaluminum. The polymer obtained by this method has low syndiotacticity, and it was difficult to say that the polymer exhibited the original syndiotactic properties.

  In recent years, a high tacticity polypropylene having a syndiotactic pentad fraction exceeding 0.7 can be obtained by a transition metal catalyst having an asymmetric ligand and aluminoxane by JA Ewen et al. Was first discovered (Non-Patent Document 1: J. Am. Chem. Soc., 1988, 110, 6255-6256).

  This syndiotactic polypropylene has extremely high transparency and surface gloss compared to conventional isotactic polypropylene, and also has excellent flexibility. Therefore, films, sheets and fibers known as uses of conventional isotactic polypropylene. In addition to uses such as injection-molded bodies and blow-molded bodies, new uses that could not be applied with isotactic polypropylene are expected.

  However, the syndiotactic polypropylene obtained by the method of the above-mentioned JA Ewen et al. Has a problem that the crystallization speed is still significantly higher than that of isotactic polypropylene and the degree of crystallization is low, so that the molding processability is remarkably inferior. was there.

The applicant of the present application has previously made the following proposal.
In Japanese Patent Application Laid-Open No. 3-12439 (Patent Document 1), the peak intensity of the syndiotactic pentad bond in the spectrum of methyl group measured by ¹³ C-NMR is 0.7 or more of the peak intensity of all methyl groups. A syndiotactic polypropylene resin composition consisting essentially of a propylene homopolymer and a copolymer of ethylene and propylene is proposed. The composition had high syndiotacticity and was excellent in impact resistance and transparency.

Further, in JP-A-07-247387 (Patent Document 2), 50 to 99.9 parts by weight of a resin component comprising 50 to 99 parts by weight of syndiotactic polypropylene and 1 to 50 parts by weight of isotactic polypropylene, and plasticizer 0 It proposes a syndiotactic polypropylene resin composition comprising .1 to 50 parts by weight. The composition was able to obtain a molded article excellent in transparency and flexibility with excellent molding processability, and had a high crystallization rate and excellent molding processability.

Further, in JP-A-8-59916 (Patent Document 3), syndiotactic polypropylene 97 to 99.99% by weight having a syndiotactic pentad fraction measured by ¹³ C-NMR of 0.7 or more and polyethylene A syndiotactic polypropylene resin composition comprising 0.01 to 3% by weight is proposed. The composition had a high crystallization rate and excellent moldability.

Japanese Unexamined Patent Publication No. 2000-191852 (Patent Document 4) proposes a soft transparent syndiotactic polypropylene composition comprising syndiotactic polypropylene and an amorphous propylene / α-olefin copolymer. The composition was excellent in transparency, flexibility, scratch resistance, and heat resistance.

Japanese Patent Application Laid-Open No. 2000-191858 (Patent Document 5) discloses a soft transparent syndiotactic polypropylene composition containing syndiotactic polypropylene and a propylene-ethylene copolymer having a substantially syndiotactic structure. It is disclosed. It is described that the composition is excellent in transparency, flexibility, scratch resistance, and heat resistance.

However, these compositions described in any of the above publications have room for further improvement in terms of the balance of moldability, heat resistance, transparency, low temperature impact resistance and flexibility.
Japanese Patent Laid-Open No. 3-12439 JP-A-7-247387 JP-A-8-59916 JP 2000-191852 A JP 2000-191858 A J. et al. Am. Chem. Soc. , 1988, 110, 6255-6256

  The problem to be solved by the present invention is to solve the above-mentioned points, and is a composition excellent in moldability and heat resistance, and further excellent in flexibility, transparency and low temperature impact resistance, and the composition It is in providing the molded object which consists of a thing.

The propylene polymer composition (X) of the present invention is:
Syndiotactic propylene polymer (A) 100 to 25 parts by weight Propylene / α-olefin copolymer (B) 0 to 75 parts by weight (However, (A) and (B
) Is 100 parts by weight),
For a total of 100 parts by weight of (A) and (B), ethylene / α-olefin copolymer (C)
1 to 100 parts by weight, the polymer (A) has the following requirement (a), the copolymer (B) has the following requirement (b), and the copolymer (C) has the following requirement. Each of (c) is satisfied;
(A): The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, and the melting point (Tm) determined by DSC is 145 ° C. or more, which is derived from propylene. Containing structural units in an amount exceeding 90 mol% (however, the total amount of structural units in the polymer (A) is 100 mol%).
(B): Containing structural units derived from propylene in an amount of 55 to 90 mol% (provided that the total amount of structural units in the copolymer (B) is 100 mol%), and having 2 carbon atoms 10 to 45 mol% of structural units derived from at least one olefin selected from -20 α-olefins (excluding propylene) (provided that structural units derived from propylene and α-olefins having 2 to 20 carbon atoms ( However, the total of the structural units derived from (excluding propylene) is 100 mol%), and is 230 ° C. and 2.16 k in accordance with JIS K-6721.
MFR measured by g load is in the range of 0.01 to 100 g / 10 min, and satisfies at least one of the following requirements (b-1) or (b-2);
(B-1): Syndiotactic triad fraction (rr) measured by ¹³ C-NMR method
The fraction) is 60% or more,
(B-2): Intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) satisfy the following relational expression:
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
(C): Containing structural units derived from ethylene in an amount of 50 to 99 mol% (provided that the total amount of structural units in the copolymer (C) is 100 mol%), and carbon other than ethylene 1 to 50 mol% of structural units derived from an α-olefin having 3 to 20 atoms (however, the total of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms is 100 mol) %)).

As a preferred embodiment of the propylene-based polymer composition according to the present invention,
Syndiotactic propylene polymer (A) 98 to 40 parts by weight and propylene / α-olefin copolymer (B) 2 to 60 parts by weight (however, (A) and (B
) Is 100 parts by weight),
For a total of 100 parts by weight of (A) and (B), ethylene / α-olefin copolymer (C)
1 to 100 parts by weight, the polymer (A) satisfies the following requirement (a), the copolymer (B) satisfies the following requirement (b ′), and the copolymer (C) A propylene polymer composition (X) satisfying the requirements (c ′) (hereinafter, this composition may be referred to as “composition (i)”);
(A): The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, and the melting point (Tm) determined by DSC is 145 ° C. or more, which is derived from propylene. Containing structural units in an amount exceeding 90 mol% (however, the total amount of structural units in the polymer (A) is 100 mol%).
(B ′): Containing structural units derived from propylene in an amount of 65 to 90 mol% (provided that the total amount of structural units in the copolymer (B) is 100 mol%), and the number of carbon atoms 10 to 35 mol% of structural units derived from at least one olefin selected from 2 to 20 α-olefins (excluding propylene) (provided that the structural units derived from propylene and the α-olefins having 2 to 20 carbon atoms) (However, the total amount with the structural units derived from propylene is 100 mol%), and is 230 ° C. according to JIS K-6721 and 2.16.
MFR measured by kg load is in the range of 0.01 to 100 g / 10 min and satisfies at least one of the following requirements (b-1) or (b-2);
(B-1): Syndiotactic triad fraction (rr) measured by ¹³ C-NMR method
The fraction) is 60% or more,
(B-2): The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) satisfy the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
(C ′) 60 to 95 mol% of structural units derived from ethylene (however, the total amount of the structural units in the copolymer (C) is 100 mol%), and carbon other than ethylene 5 to 40 mol% of structural units derived from an α-olefin having 3 to 20 atoms (however, the total of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms is 100 mol) %)).

As a preferred embodiment of the present invention,
100 parts by weight of syndiotactic propylene polymer (A),
1 to 100 parts by weight of an ethylene / α-olefin copolymer (C), the polymer (A) satisfies the following requirement (a), and the copolymer (C) satisfies the following requirement (c ′). And propylene-based polymer composition (X) (hereinafter, this composition may be referred to as “composition (ii)”);
(A): The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, and the melting point (Tm) determined by DSC is 145 ° C. or more, which is derived from propylene. Containing structural units in an amount exceeding 90 mol% (however, the total amount of structural units in the polymer (A) is 100 mol%).
(C ′) 60 to 95 mol% of structural units derived from ethylene (however, the total amount of the structural units in the copolymer (C) is 100 mol%), and carbon other than ethylene 5 to 40 mol% of structural units derived from an α-olefin having 3 to 20 atoms (however, the total of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms is 100 mol) %)).

The composition (X), (i), or (ii) has, for example, (1) a half crystallization time (t _1/2 ) in isothermal crystallization at 110 ° C. obtained by a differential scanning calorimeter of 1000 sec or less. It is preferable that it exists in the range.

The composition (X), (i), or (ii) preferably has, for example, (2) a needle penetration temperature of 145 ° C. or higher.
The syndiotactic propylene polymer (A) preferably has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.1 to 10 dL / g, and is determined by differential scanning calorimetry (DSC) measurement. The heat of fusion (ΔH) is preferably 40 mJ / mg or more.
The propylene · alpha-olefin copolymer polymer (B) is located an intrinsic viscosity measured at 135 ° C. in decalin [eta] is in the range of 0.1~10dL / g, molecular weight was determined by GPC distribution (Mw / Mn, It is preferable that Mn: number average molecular weight, Mw: weight average molecular weight) is 3.5 or less.

The ethylene / α-olefin copolymer (C) has an MFR measured in a load of 2.16 kg at 190 ° C. in a range of 0.01 to 100 g / 10 min in accordance with JIS K-6721, The density is preferably 0.910 to 0.850 (g / cm ³ ).

The molded product of the present invention is characterized by using the propylene-based polymer composition (X).
The sheet of the present invention is characterized by using the propylene-based polymer composition (X).
The unstretched or stretched film of the present invention is characterized by using the propylene-based polymer composition (X).
The laminate of the present invention is characterized in that at least one layer thereof is a layer containing the propylene-based polymer composition (X).
The nonwoven fabric of the present invention is characterized by using the propylene polymer composition (X).

The propylene polymer composition (X) of the present invention is excellent in moldability and heat resistance, and further excellent in transparency, flexibility and low temperature impact resistance.
The molded product of the present invention is excellent in heat resistance, and further excellent in transparency, flexibility, and low temperature impact resistance.

The present invention will be described in detail below.
The propylene-based polymer composition of the present invention comprises a specific (A) syndiotactic propylene polymer, a specific (B) propylene / α-olefin copolymer, and (C) an ethylene / α-olefin copolymer. Comprising.

(A) Syndiotactic propylene polymer The syndiotactic propylene polymer (A) used in the present invention has propylene / carbon atoms of 2 to 20 even if it is homopolypropylene, as long as it has the following characteristics. Α-olefin (except propylene) random copolymer or propylene block copolymer may be used, but preferably homopolypropylene or propylene-carbon atom number 2
˜20 α-olefin random copolymer. Particularly preferred is a copolymer of propylene and ethylene or an α-olefin having 4 to 10 carbon atoms, and a copolymer of propylene, ethylene and an α-olefin having 4 to 10 carbon atoms. Particularly preferred from the viewpoint of heat resistance.

Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene,
1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Examples include octadecene and 1-eicosene. In general, the structural unit derived from propylene is an amount exceeding 90 mol%, preferably 91 mol, based on 100 mol% of the total structural units derived from an α-olefin having 2 to 20 carbon atoms (including propylene). Contain more than%. In other words, the syndiotactic propylene polymer (AA) of the present invention usually contains propylene-derived structural units in an amount of more than 90 mol% and not more than 100 mol%, and an α-olefin having 2 to 20 carbon atoms (propylene). And a constituent unit derived from propylene and a constituent unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene). Is derived from propylene-derived structural units in an amount of 91 mol% or more and 100 mol% or less, and an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is preferable to contain the structural unit in an amount of 0 mol% to 9 mol%.

When the syndiotactic propylene polymer (A) is a propylene / α-olefin random copolymer, the structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 0.3 to It is preferably contained in an amount of 7 mol%, preferably 0.3 to 6 mol%, more preferably 0.3 to 5 mol%.

  The syndiotactic propylene polymer (A) used in the present invention has a syndiotactic pentad fraction (rrrr fraction, pentad syndiotacticity) measured by NMR method of 85% or more, preferably 90% or more. The syndiotactic propylene polymer (A) having an rrrr fraction in this range is excellent in moldability, heat resistance and transparency, and more preferably 93% or more, more preferably 94% or more. The properties as polypropylene are favorable and preferable. The upper limit of the rrrr fraction is not particularly limited, but is 100% or less, and usually 99% or less, for example.

This syndiotactic pentad fraction (rrrr fraction) is measured as follows.
The rrrr fraction is expressed as Prrrr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously syndiotactically bonded) and Pw (total methyl groups of propylene units). (Absorption intensity derived from the above) is determined by the following formula (1).

rrrr fraction (%) = 100 × Prrrr / Pw (1)
The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And ¹³ C-NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 10,000 times or more.

  The intrinsic viscosity [η] of the syndiotactic propylene polymer (A) measured in decalin at 135 ° C. is 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g. More preferably 0.50 to 8.00 dL / g, still more preferably 0.95 to 8.00 dL / g, particularly preferably 1.00 to 8.00, and still more preferably 1.40 to 8.00 dL / g. It is desirable to be in the range of 1.40 to 5.00 dL / g. The syndiotactic propylene polymer (A) having such an intrinsic viscosity [η] value exhibits good fluidity, is easy to be blended with other components, and has excellent mechanical strength from the obtained composition. There is a tendency to obtain goods.

Further, the syndiotactic propylene polymer (A) has a melting point (Tm) obtained by differential scanning calorimetry (DSC) measurement of 145 ° C. or higher, preferably 147 ° C. or higher, more preferably 150 ° C. or higher, More preferably, it is 155 degreeC or more, Most preferably, it is 156 degreeC or more. The upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower, for example.
Further, the heat of fusion (ΔH) of the syndiotactic propylene polymer (A) is 40 mJ / mg or more, preferably 45 mJ / mg or more, more preferably 50 mJ / mg or more, further preferably 52 mJ / mg or more, particularly preferably 55 mJ / mg. The above is preferable.

The measurement by the differential scanning calorimeter is performed as follows, for example. About 5.00 mg of sample is packed in a special aluminum pan, heated to 320 ° C./min from 30 ° C. to 200 ° C. using DSCPyris 1 or DSC 7 manufactured by PerkinElmer, and held at 200 ° C. for 5 minutes. The temperature is lowered to 30 ° C. at 10 ° C./min, held at 30 ° C. for 5 minutes, and then the melting point (Tm) and the heat of fusion (ΔH) are determined from the endothermic curve when the temperature is raised at 10 ° C./min. When a plurality of peaks are detected during DSC measurement, the peak detected on the highest temperature side is defined as the melting point (Tm).

  The syndiotactic propylene polymer (A) having a melting point (Tm) in this range is preferable because it is excellent in moldability, heat resistance and mechanical properties, and has good properties as crystalline polypropylene. A syndiotactic propylene polymer (A) having a melting point (Tm) in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.

In the syndiotactic propylene polymer (A), the isothermal crystallization temperature obtained by differential scanning calorimetry (DSC) measurement is T _iso , and the half crystallization time at the isothermal crystallization temperature T _iso is t _1/2 , In the range of 110 ≦ T _iso ≦ 150 (° C.), the following formula (Eq-1) is satisfied,

Preferably, the following formula (Eq-2) is satisfied,

More preferably, the following formula (Eq-3) is satisfied.

The half crystallization time (t _1/2 ) obtained by isothermal crystallization measurement is the DSC in the isothermal crystallization process
When the area between the calorie curve and the baseline is defined as the total calorific value, it is the time when the calorific value reaches 50%. [Refer to New Polymer Experiment Laboratory 8 Polymer Properties (Kyoritsu Publishing Co., Ltd.)]
The half crystallization time (t _1/2 ) is measured as follows. About 5 mg of a sample is packed in a special aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by PerkinElmer, and held at 200 ° C. for 5 minutes, then the temperature (200 ° C. ) To each isothermal crystallization temperature at a rate of 320 ° C./min, and a half crystallization time (t _1/2 ) is determined from the DSC curve obtained by maintaining the isothermal crystallization temperature. Here, the half crystallization time (t _1/2 ) is the isothermal crystallization process start time (time when the isothermal crystallization temperature is reached from 200 ° C.)
Obtained as t = 0. For the syndiotactic propylene polymer (A) used in the present invention, t _1/2 can be determined as described above, but it is convenient if it is not crystallized at a certain isothermal crystallization temperature, for example, 110 ° C. Then, several measurements are carried out at an isothermal crystallization temperature of 110 ° C. or less, and the half crystallization time (t _1/2 ) is obtained from the extrapolated value.

  The syndiotactic propylene polymer (A) satisfying the above (Eq-1) has remarkably excellent moldability as compared with existing ones. Here, excellent moldability means that when molding such as injection, inflation, blow, extrusion, or press is performed, the time from solidification to solidification is short. Moreover, such a syndiotactic propylene polymer (A) is excellent in molding cycle property, shape stability, long-term productivity, and the like.

A syndiotactic propylene polymer (A) satisfying the above (Eq-1) can be produced by setting a polymerization condition as described later using a catalyst system as described later.
As a preferable aspect of the syndiotactic propylene polymer (A) of the present invention, in addition to satisfying the preferable aspect (ΔH ≧ 40 mJ / mg) and satisfying (Eq-1), the following requirement (n -A mode in which the amount of the decane soluble part) is simultaneously satisfied.

  The amount of the n-decane soluble part of the syndiotactic propylene polymer (A) is 1 (wt%) or less, preferably 0.8 (wt%) or less, more preferably 0.6 (wt%) or less. Is desirable. The amount of the n-decane soluble part is an index closely related to the blocking property of the syndiotactic propylene polymer (A) or the molded product obtained therefrom, and the fact that the amount of the n-decane soluble part is usually small indicates low crystallinity. It means that the amount of ingredients is small. That is, the syndiotactic propylene polymer (A) that also satisfies this requirement (the amount of n-decane soluble part) has very good blocking resistance.

Accordingly, one of the most preferred embodiments of the component (A) contains a structural unit derived from propylene in an amount exceeding 90 mol%, and a syndiotactic pentad fraction (rrrr fraction measured by ¹³ C-NMR). ) Is 85% or more, the melting point (Tm) determined by DSC is 145 ° C. or more, the heat of fusion (ΔH) is 40 mJ / mg or more, further satisfies the above (Eq-1), and n-decane It is a syndiotactic propylene polymer whose soluble part amount is 1 wt% or less.

In producing the syndiotactic propylene polymer (A) used in the present invention,
(I) a bridged metallocene compound represented by the general formula [1];
(II) (II-1) organoaluminum oxy compounds,
(II-2) a polymerization catalyst (cat-) comprising: a compound that reacts with the bridged metallocene compound (A) to form an ion pair; and (II-3) at least one compound selected from organoaluminum compounds. 1), or a polymerization catalyst (cat-2) in which the catalyst (cat-1) is supported on a particulate carrier is preferably used. The polymer produced is a syndiotactic propylene polymer (A). As long as these requirements are satisfied, the catalyst used for the production of the syndiotactic polypropylene polymer (A) is not limited to the catalyst.

In the general formula [1], R ¹ , R ² , R ³ and R ⁴ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group, and R ² and R ³ are bonded to each other to form a ring. R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R ¹² are selected from hydrogen, hydrocarbon groups and silicon-containing groups, and the two groups R ⁷ and R ¹⁰ are not hydrogen atoms, Selected from a hydrocarbon group and a silicon-containing group, which may be the same or different from R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² In the combination of one or more selected adjacent groups, the adjacent groups may be bonded to each other to form a ring.

R ¹⁷ and R ¹⁸ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon atom-containing group, which may be the same or different from each other, and the substituents may be bonded to each other to form a ring. Good.

  M is Ti, Zr or Hf, Y is carbon, Q may be selected from the same or different combinations from halogen, hydrocarbon groups, anionic ligands and neutral ligands capable of coordinating with lone pairs. Often, j is an integer from 1 to 4.

(I) Bridged metallocene compound Specific examples of the bridged metallocene compound (I) represented by the general formula [1] (also referred to as “component (I)” in the present specification) are shown below.

Cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl)
Zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6
-Ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl) Fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) ) Zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n- Chirumechiren (
Cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,3 , 6,7-tetra-tert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorene Nyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) ( 2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,
Diisobutylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl (2,7-
Di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl Fluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopenta (Dienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert -Butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2, 7- (4-tert-Butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene Nyl) zirconium dichloride [otherly referred to as 1,3-diphenylisopropylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride. The following are also omitted] dibenzylmethylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) ) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, dibenzylmethylene ( Cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3 , 6-Ditert-butylfluorenyl) zirconium Chloride,
Dibenzylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,
Diphenethylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6- Ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-) Ethyl) methylene Clopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3 , 6-Ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di ( (Cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, J Tilmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (Biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
(Benzyl) (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadiene) Enyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Cyclopropylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadiene) Enyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7- Dimethyl-3, 6-di-tert-
(Butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ( 2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) Zirconium dichloride,
Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-
Dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, di-n-butyl Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di ( Trimethylsilyl) -butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di (trimethylsilyl) -butylfluorenyl) zirconium dichloride, dibenzylmethylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-diphenyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl -3,6-diphenyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (Cyclopentadienyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butyl Fluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, Di (m-chlorophenyl) methylene Lopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromo Phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7-Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl Fluorenyl) zirconium dichloride,
Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2 , 7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene Ropentajieniru) (2,7-dimethyl-3,6-di-tert- butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-
Butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3) , 6-Ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Chirufuruoreniru) zirconium dichloride, and the like can be exemplified.

  Furthermore, the compounds described above in which “zirconium” is changed to “hafnium” or “titanium”, “dichloride” is “difluoride”, “dibromide”, “diaiodide”, “dichloride” is “dimethyl” or “methyl”. Examples include metallocene compounds converted to “ethyl”.

The bridged metallocene compound (I) can be produced by a known method, and the production method is not particularly limited. As a known production method, for example, WO2001 / 27124 by the present applicant.
No. and the production method described in WO 2004/087775 pamphlet.

The above bridged metallocene compound (I) can be used alone or in combination of two or more.
(II-1) Organoaluminum oxy compound As (II-1) organoaluminum oxy compound (also referred to as “component (II-1)” in this specification) used in the production of the syndiotactic propylene polymer (A). Can use a conventionally well-known aluminoxane as it is. Specifically, the following general formula [2] and / or general formula [3]

(In the above formula [2], R is each independently a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.)
(In the above formula [3], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.)
In particular, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with some organoaluminum compounds.

In the present invention, a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can be used. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. It is insoluble or hardly soluble.

  Examples of the organoaluminum oxy compound include a modified methylaluminoxane represented by the following formula [4].

(In the formula [4], R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more.)
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [4] is generally called MMAO. Such MMAOs can be prepared by the methods listed in US4960878 and US5041584. In addition, Tosoh Finechem Co., Ltd. and the like are commercially produced under the names MMAO and TMAO where R is an isobutyl group prepared using trimethylaluminum and triisobutylaluminum. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, it is insoluble in benzene such as the compounds represented by the above formulas [2] and [3]. Unlike insoluble aluminoxane, it dissolves in aliphatic hydrocarbons and alicyclic hydrocarbons.

  Furthermore, as an organoaluminum oxy compound, an organoaluminum oxy compound containing boron represented by the following general formula [5] can be exemplified.

(In the formula [5], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and may be a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)
(II-2) A compound that reacts with the bridged metallocene compound (a) to form an ion pair. It reacts with the bridged metallocene compound (I) used in the production of the syndiotactic propylene polymer (A) to form an ion pair. Examples of the compound (II-2) (hereinafter sometimes referred to as “ionic compound” or “component (II-2)”) include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005 and JP-A-3-17900
Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-6, JP-A-3-207703, JP-A-3-207704, USP5321106 and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  An ionic compound preferably employed is a compound represented by the following general formula [6].

In the formula, R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are an organic group, preferably an aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-
Butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) Borate, tripropylammonium tetrakis (
Pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-tri Fluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, di Octadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethyl) Tilphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate And dioctadecylmethylammonium.

Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl
) Borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate and the like.

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, an ionic compound disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can be used without limitation.
The ionic compound (II-2) as described above can be used as a mixture of two or more.

(II-3) Organoaluminum compound (II-3) Organoaluminum compound (also referred to herein as “component (II-3)”) used in the production of the syndiotactic propylene polymer (A), Examples thereof include an organoaluminum compound represented by the following general formula [7], a complex alkylated product of a Group 1 metal represented by the following general formula [8] and aluminum, and the like.

R ^a _m Al (OR ^b ) _n H _p X _q ... [7]
(In the formula [7], R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.)
Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum;
Tri-branched alkyl aluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum; dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride;
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≦ 2x.) Isoprenyl represented by like Alkenyl aluminum such as aluminum;
Alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Formula Ra _2.5 Al (ORb) partially alkylaluminum which is alkoxylated with an average composition represented by like _0.5;
Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride; Examples thereof include halogenated alkylaluminum.

M ² AlR ^a ₄ ... [8]
(In the formula [8], M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

A compound similar to the compound represented by the general formula [8] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. As such a compound, specifically, (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) A
and l (C ₂ H ₅ ) ₂ .

(II-3) As the organoaluminum compound, trimethylaluminum and triisobutylaluminum are preferably used from the viewpoint of easy availability.
Moreover, each said component can also be carry | supported and used for a particulate carrier.

(III) Carrier The carrier (III) (also referred to herein as “component (III)”) used as necessary is an inorganic or organic compound, and is a granular or particulate solid.

Among these, as the inorganic compound, a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable.
Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these, eg natural or synthetic zeolite, 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, or the like can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

The inorganic oxide includes 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 , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used has a particle size of 3 to 300 μm, preferably 10 to 300 μm, more preferably 20 to 200 μm, and a specific surface area. Is 50 to 1000 m ² / g, preferably 100 to 70
Desirably, the pore volume is in the range of 0 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating the fine particles with a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained therein can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3-5 cc / g, as measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral to chemical treatment.

  As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such a bulky ion plays a role of a column supporting the layered structure and is usually called a pillar. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. As guest compounds to be intercalated, TiCl ₄ , ZrC
Cationic inorganic compounds such as l ₄ , Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (OR) ₃
Metal alkoxides (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH
) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ and other metal hydroxide ions. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolysis of metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers. Of these, clays and clay minerals are preferred, and montmorillonite, vermiculite, pectolite, teniolite and synthetic mica are particularly preferred.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  When ion exchange layered silicate is used, in addition to its function as a carrier, it can also reduce the amount of organoaluminum oxy compounds such as alkylaluminoxane by utilizing its ion exchange properties and layer structure. Is possible. The ion-exchange layered silicate is naturally produced mainly as a main component of clay mineral, but is not limited to a natural product, and may be a synthetic product. Specific examples of clay, clay mineral, and ion-exchange layered silicate include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, teniolite, synthetic mica, synthetic hectorite, and the like.

Examples of the organic compound include granular or fine particle solids having a particle size in the range of 3 to 300 μm, preferably 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene or vinylcyclohexane or styrene is used. (Co) polymer produced as the main component, or polar functional groups obtained by copolymerizing or graft polymerizing polar monomers such as acrylic acid, acrylic acid ester, maleic anhydride, etc. to these polymers Examples thereof include polymers or modified products. These particulate carriers can be used alone or in combination of two or more.

  Further, the olefin polymerization catalyst used for the production of the syndiotactic propylene polymer (A) may contain a specific organic compound component (IV) as described later together with each of the above components.

(IV) Organic Compound Component In the present invention, (IV) the organic compound component (also referred to as “component (IV)” in this specification) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. used. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

Production Method of Syndiotactic Propylene Polymer (A) In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding component (I) alone to the polymerization vessel.
(2) A method in which component (I) and component (II) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (I) supported on carrier (III) and component (II) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (II) supported on carrier (III) and component (I) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which component (I) and component (II) are supported on a carrier (III) is added to a polymerization vessel.

In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.
In each of the above methods (4) and (5) in which component (II) is supported, unsupported component (II) may be added in any order as necessary. In this case, the components (II) may be the same or different.

  In addition, the solid catalyst component in which component (I) is supported on component (III) and the solid catalyst component in which component (I) and component (II) are supported on component (III) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

The syndiotactic propylene polymer (A) comprises propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) in the presence of the olefin polymerization catalyst as described above.
It is obtained by polymerizing or copolymerizing at least one olefin selected from

  The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also.

When polymerizing propylene and at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) using the above olefin polymerization catalyst, component (I) is: The amount is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol, per liter of reaction volume.

  Component (II-1) has a molar ratio [(II-1) / M] of component (II-1) and all transition metal atoms (M) in component (I) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (II-2) has a molar ratio [(II-2) / M] of component (II-2) to transition metal atom (M) in component (I) of usually 1 to 10, preferably It is used in such an amount as to be 1-5. Component (II-3) has a molar ratio [(II-3) / M] of the aluminum atoms in component (II-3) to the total transition metals (M) in component (I) of usually 10 to 10. The amount used is 5000, preferably 20-2000.

  When component (II) is component (II-1), component (IV) has a molar ratio [(IV) / (II-1)] of usually 0.01 to 10, preferably 0.1 to 5. When the component (II) is the component (II-2), the molar ratio [(IV) / (II-2)] is usually 0.01 to 10, preferably 0.1 to 5. When the component (II) is the component (II-3), the molar ratio [(IV) / (II-3)] is usually 0.01 to 2, preferably 0.005 to It is used in such an amount that it becomes 1.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually −50 to
It is +200 degreeC, Preferably it is the range of 0-170 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (II) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

The olefin supplied to the polymerization reaction is at least one olefin selected from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). Examples of the α-olefin having 4 to 20 carbon atoms include linear or branched α-olefins having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as 1-butene, 2-butene, and 1-pentene. 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, -Octadecene, 1-eicosen, etc.

(B) Propylene / α-olefin copolymer The propylene / α-olefin copolymer (B) contains 55 structural units derived from propylene.
Included in an amount of ˜90 mol%, α-olefin having 2 to 20 carbon atoms (excluding propylene)
A propylene / α-olefin copolymer containing 10 to 45 mol% of a structural unit derived from at least one olefin selected from the group consisting of 230 ° C. and 2.16 kg in accordance with JIS K-6721. The MFR measured with a load is in the range of 0.01 to 100 g / min and satisfies any one or more of the following requirements (b-1) and (b-2).
(B-1): Syndiotactic triad fraction (rr) measured by ¹³ C-NMR method
) Is 60% or more.
(B-2): Intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and MFR (g / 10 min) measured at 230 ° C. and 2.16 kg load according to JIS K-6721 Satisfies the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
The propylene / α-olefin copolymer (B) has a constitutional unit derived from propylene in an amount of 55 to 90 mol% and a constitutional unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene). Contains an amount of ˜45 mol%.

Here, the total of structural units derived from propylene and structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol%.
Examples of the α-olefin having 2 to 20 carbon atoms (excluding propylene) include ethylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, Examples include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. Particularly preferred are ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

Among the propylene / α-olefin copolymers (B) as described above, a propylene / ethylene copolymer is one of preferred embodiments.
Among the propylene / α-olefin copolymers (B) as described above, a structural unit derived from propylene, a structural unit derived from ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene. Or a constituent unit derived from either 1-octene (sometimes referred to as HAO comonomer), and the proportion (mol%) of the constituent unit derived from ethylene is more than the proportion (mol%) of the constituent unit derived from HAO comonomer. Propylene / ethylene / HAO copolymer is also a preferred embodiment.

In the propylene / ethylene copolymer and propylene / ethylene / HAO copolymer which are polymers in these preferred ranges, it is preferable that both (b-1) and (b-2) are satisfied.

The propylene / α-olefin copolymer (B) used in the present invention is JIS K-672.
1 is preferably in the range of 0.01 to 100 g / 10 min, more preferably in the range of 0.02 to 100 g / 10 min. .

The propylene / α-olefin copolymer (B) used in the present invention satisfies at least one of the following (b-1) and (b-2).
(B-1) The syndiotactic triad fraction (rr fraction, triad syndiotacticity) measured by ¹³ C-NMR method is 60% or more.
(B-2) The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 min, 230 ° C., 2.16 kg load) satisfy the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
First, requirement (b-1) will be described.
(B-1): Syndiotactic triad fraction (rr fraction, triad syndiotacticity) measured by ¹³ C-NMR method of propylene / α-olefin copolymer (B) is 60% or more, preferably The propylene / α-olefin copolymer (B) having an rr fraction in this range of 70% or more, more preferably 75% or more, has good compatibility with the syndiotactic propylene polymer (A). preferable.

  The polymer satisfying (b-1) can be obtained, for example, by copolymerizing propylene and α-olefin with a catalyst capable of producing syndiotactic polypropylene, and can be produced using, for example, a catalyst as described later. May be.

The rr fraction is Prr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the second unit in a site where three units of propylene units are continuously syndiotactically bonded) and Pw (total methyl groups of propylene units). (Absorption intensity derived from the above) is determined by the following formula (2).

rr fraction (%) = 100 × Prr / Pw (2)
Here, mr-derived absorption (of 3 units of propylene units, absorption derived from at least both syndiotactic and isotactic bonds, used for determination of Pmr (absorption intensity)), rr-derived absorption (propylene Absorption derived from the methyl group of the second unit at the site where 3 units are continuously syndiotactically bonded, used for determination of Prr (absorption intensity)), or absorption derived from mm (3 units of propylene units are consecutive) If the absorption derived from the methyl group of the second unit at the isotactic bond site and Pmm (absorption intensity) overlap with the absorption derived from the comonomer, the contribution of the comonomer component is subtracted. Calculate as it is.

Specifically, among the descriptions of how to obtain the “syndiotacticity parameter (SP value)” described in [0018] to [0031] of JP-A-2002-097325, [00
18] to [0023], and the calculation is performed by calculating from the integrated intensity of the signals in the first region, the second region, and the third region according to the above equation (2).

In the present invention, the rr ₁ value is obtained particularly according to the method for obtaining the “syndiotacticity parameter (SP value)” described in JP-A-2002-097325, [0018] to [0031]. More preferably, the measured value is 60% or more, preferably 65% or more, more preferably 70% or more. In other words, in the calculation of the rr value, the rr ₁ value is the absorption of mr (absorption derived from at least both syndiotactic and isotactic bonds out of 3 units of propylene units, and Pmr (absorption intensity)). Used for determination), absorption derived from rr (absorption derived from the methyl group of the second unit at a site where three units of propylene units are continuously syndiotactically bonded, used for determination of Prr (absorption intensity)), or mm Absorption derived from (absorption derived from the methyl group of the second unit at a site where 3 units of propylene units are continuously isotactically bonded, intensity used for determining Pmm (absorption intensity)), and absorption derived from a comonomer In the case of overlapping, the contribution of the comonomer component is subtracted.

In the measurement of the rr value and the rr ₁ value, the NMR measurement is performed, for example, as follows. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120 ° C. using a GX-400 NMR measurement apparatus manufactured by JEOL. The number of integration is 8,000 times or more.

Next, requirement (b-2) will be described.
(B-2): The propylene / α-olefin copolymer (B) used in the present invention is 135.
The intrinsic viscosity [η] (dL / g) measured in decalin at ° C and MFR (g / 10 minutes) measured at 230 ° C and 2.16 kg load according to JIS K-6721 are expressed by the following relational expression: Fulfill.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
More preferably 1.80 × MFR ^(−0.20) ≦ [η] ≦ 2.50 × MFR ^(−0.19)
The propylene / α-olefin copolymer (B) satisfying this relational expression is preferable because it has good compatibility with the syndiotactic propylene polymer (A).

The propylene / α-olefin copolymer (B) satisfying the above formula can be obtained, for example, by copolymerizing propylene and α-olefin with a catalyst capable of producing syndiotactic propylene. You may manufacture using a catalyst. Such a material is preferable because it has good compatibility with the syndiotactic propylene polymer (A).

The propylene / α-olefin copolymer satisfying (b-2) exhibits the same [η] and a large MFR as compared with the conventional isotactic propylene-based copolymer.
As described in Macromolecules 31, 1335-1340 (1998), the molecular weight between the entanglement points of isotactic polypropylene (reported as Me = 6900 (g / mol) in the paper) and the syndiotactic polypropylene This is thought to be due to the difference in molecular weight between entanglement points (reported as Me = 2170 (g / mol) in the paper). That is, it is considered that the same [η] has a syndio structure, thereby increasing the number of entanglement points with respect to the material having an iso structure and increasing the MFR.

As described above, the propylene / α-olefin copolymer satisfying any one or more of (b-1) and (b-2) is a propylene / α-olefin copolymer having an isotactic structure. A polymer having a stereoregularity different from a coalescence is considered to have a syndiotactic structure. For this purpose, a propylene / α-olefin copolymer (B
) Is considered to have good compatibility with the component (A).

The intrinsic viscosity [η] of propylene / α-olefin copolymer (B) measured in decalin at 135 ° C. is 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g, more preferably 0.
. It is desirable to be 5 to 7.0 dL / g.

The propylene / α-olefin copolymer (B) preferably has a crystallinity measured by X-ray diffraction of 20% or less, more preferably 0 to 15%.
This propylene / α-olefin copolymer (B) has a single glass transition temperature, and the glass transition temperature (Tg) obtained by differential scanning calorimetry (DSC) measurement is usually 0 ° C. or lower. It is preferable. Glass transition temperature of propylene / α-olefin copolymer (B) (T
When g) is within the above range, the cold resistance and the low temperature characteristics are excellent.

  The differential scanning calorimeter is performed, for example, as follows. About 10.00 mg of the sample is packed in a special aluminum pan, and the temperature is increased from 30 ° C. to 200 ° C. at 200 ° C./min using a DSCRDC220 manufactured by Seiko Instruments Inc. After holding at 200 ° C. for 5 minutes, from 200 ° C. The temperature is lowered to −100 ° C. at 10 ° C./min, held at −100 ° C. for another 5 minutes, and then the glass transition temperature (Tg) is determined from the endothermic curve when the temperature is raised at 10 ° C./min.

Further, the molecular weight distribution (Mw / Mn, polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) of the propylene / α-olefin copolymer (B) measured by GPC is preferably 3.5 or less. Preferably it is 3.0 or less, More preferably, it is 2.5 or less.

The propylene / α-olefin copolymer (B) used in the present invention is:
(I ′) a bridged metallocene compound represented by the following general formula [9];
(II) (II-1) organoaluminum oxy compound,
(II-2) a compound that reacts with the bridged metallocene compound (I ′) to form an ion pair,
and
(II-3) selected from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) in the presence of an olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds Although it can manufacture by superposing | polymerizing with an at least 1 sort (s) of olefin, as long as the requirements as a propylene alpha-olefin copolymer (B) are satisfy | filled, a manufacturing method is not limited to this.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are atoms or groups selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group, and each is the same) But it can be different,
R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group,
R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group,
R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms at the same time (ie, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms at the same time);
R ² and R ³ may combine with each other to form a ring,
Adjacent groups among R ^{5 to} R ¹² may be bonded to each other to form a ring.

R ¹³ and R ¹⁴ are an aryl group having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkylaryl group having 6 to 40 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and a 7 to 40 carbon atom. Fluoroalkylaryl group, C6-C20 chloroaryl group, C7-C40 chloroalkylaryl group, C6-C20 bromoaryl group, C7-C40 bromoalkylaryl group, C6 Selected from ˜20 iodoaryl groups and C7-40 iodoalkylaryl groups, each of which may be the same or different,
At least one of R ¹³ and R ¹⁴ is an aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, a chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl group having 6 to 20 carbon atoms, A bromoalkylaryl group having 7 to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms, an iodoalkylaryl group having 7 to 40 carbon atoms and a fluoroalkylaryl group having 7 to 40 carbon atoms;
M is Ti, Zr or Hf,
Y is carbon or silicon;
Q is selected from the same or different combinations from halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or nonconjugated diene, anionic ligand, and neutral ligand capable of coordinating with a lone pair of electrons. And
j is an integer of 1-4. ).

Specific examples of the bridged metallocene compound represented by the general formula [9] (also referred to as “component (I ′)” in the present specification) are shown below, but the scope of the present invention is particularly limited thereby. It is not a thing. Here, octamethyloctahydrodibenzofluorene refers to the structure represented by the formula [10], octamethyltetrahydrodicyclopentafluorene refers to the structure represented by the formula [11], and dibenzofluorene refers to the formula [12] ] Is shown.

Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) ( 2,7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) ( 2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-di tert-Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (m-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-bromophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-bromophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-iodophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (3,6-di tert-Butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-iodophenyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-iodophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (
Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (
Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-
Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (
Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (
Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-
Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (
Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, Di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Nyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl)
Zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert -Butylfluorenyl) zirconium dichloride,
Di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (
Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m
-Trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafur Oleenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3,6-ditert-butylfluorenyl)
Zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert -Butylfluorenyl) zirconium dichloride,
Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl)
Zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydro Dibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzo Fluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) Nyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2, 7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorene Nyl) zirconium dichloride,
Di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium Dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclo Pentadienyl) (dibenzofluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopent Dienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert -Butylfluorenyl) zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) Zirconium dichloride, di (3,5-ditrifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (
Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium Dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadiene) Enyl) (dibenzofluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl)
Zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloro Methyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclo Pentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3,5-dichloromethyl-phenyl) methylene (cyclopentadienyl) (2, 3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (4-chloronaphthyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-chloronaphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (3-chloronaphthyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (3-chloronaphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (5-chloronaphthyl)
Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadiene) Enyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (5-chloronaphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride,
Phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl Fluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene ( Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethyl (Phenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylphenyl) Oreniru) zirconium dichloride,
Phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, phenyl (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) Len (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7 -Dimethyl-3,6-dite
rt-Butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoro Methyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
Naphtyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7 -Diphenyl-3,6-ditert-butylfluorenyl) zirconi Mudichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, naphthyl (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) Len (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7 -Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-di tert-butylfluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride,
(p-Tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl) ) (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zyl Nium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p- Chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) ) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6, 7-tetra-tert-butylfluorenyl) zirconium dichloride,
(p-Tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl) ) (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zyl Nium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m- Chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) ) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6, 7-tetra-tert-butylfluorenyl) zirconium dichloride,
(p-Tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) ) Methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydro (Dibenzofluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (p-tolyl) (m -Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) ) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- ( Trimethylphenyl) -3,
6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert -
(Butylfluorenyl) zirconium dichloride, (p-tolyl) (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, etc. .

  Furthermore, the compounds described above in which “zirconium” is changed to “hafnium” or “titanium”, “dichloride” is “difluoride”, “dibromide”, “diaiodide”, “dichloride” is “dimethyl” or “methyl”. Similarly, the metallocene compound represented by “ethyl” is a metallocene compound represented by the general formula [9].

The bridged metallocene compound (I ′) can be produced by referring to a known method. Examples of known production methods include the production methods described in the pamphlet of WO04 / 029062 by the present applicant.

The above metallocene compounds can be used alone or in combination of two or more.
The (II-1) organoaluminum oxy compound used in the production of the propylene / α-olefin copolymer (B) is the (II-1) organoaluminum used in the production of the syndiotactic propylene polymer (A). The same oxy compound is used.

The syndiotactic propylene polymer (A) may be used as the compound that forms an ion pair by reacting with the (II-2) bridged metallocene compound (I ′) used in the production of the propylene / α-olefin copolymer (B). (II-2) The same compound as that used to produce an ion pair by reacting with the bridged metallocene compound (I) is used.

(II-3) Organoaluminum compound used in the production of the syndiotactic propylene polymer (A) as the (II-3) organoaluminum compound used in the production of the propylene / α-olefin copolymer (B) The same is used.

  Moreover, each said component can also be carry | supported and used for a particulate carrier. The same carrier as that used in the production of the syndiotactic propylene polymer (A) is used as necessary.

Method for Producing Propylene / α-Olefin Copolymer (B) In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.

A method in which component (I ′) and component (II) are added to the polymerization vessel in any order.
In the above method, at least two or more of the catalyst components may be contacted in advance.

When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (I ′) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 1 per liter of the reaction volume.
Used in such an amount as to be 0 ^-2 mol.

Component (II-1) has a molar ratio [(II-1) / M] of component (II-1) to all transition metal atoms (M) in component (I ′) of usually 0.01-5. It is used in such an amount that it becomes 1,000, preferably 0.05 to 2,000. Component (II-2) consists of an aluminum atom in component (II-2) and component (I ′)
The molar ratio [(II-2) / M] to all transition metals (M) in the mixture is usually 1 to 1,000, preferably 1
It is used in such an amount that it becomes ˜500. Component (II-3) has a molar ratio [(II-3) / M] of component (II-3) to transition metal atom (M) in component (a) of usually 1 to 10,000, Preferably it is used in an amount of 1 to 5,000.

The propylene / α-olefin copolymer (B) is at least one selected from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) in the presence of the olefin polymerization catalyst as described above. The olefin is usually copolymerized in the liquid phase. In this case, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. Specific examples of the hydrocarbon medium include those described above. Copolymerization can be carried out by either a batch method or a continuous method.

Examples of α-olefins that can be used for polymerization include ethylene, 1-butene, 1-
Pentene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples include 1-hexadecene, 1-octadecene, and 1-eicocene. α-olefin is
These can be used singly or in combination of two or more.

  When the copolymerization is carried out by a batch method using an olefin polymerization catalyst, the concentration of the metallocene compound in the polymerization system is usually from 0.00005 to 1 mmol, preferably from 0.0001 to 0, per liter of polymerization volume. Used in an amount of 50 mmol.

The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1.
5 hours.

The propylene and at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are obtained as propylene / α-olefin copolymers (B) having the above specific composition. To the polymerization system in such amounts. In the copolymerization, a molecular weight regulator such as hydrogen can be used.

When propylene and at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are copolymerized as described above, propylene · α-
The olefin copolymer (B) is usually obtained as a polymerization solution containing the olefin copolymer (B). This polymerization solution is treated by a conventional method to obtain a propylene / α-olefin copolymer (B).

  The copolymerization reaction is usually performed at a temperature of 40 to 200 ° C., preferably 40 to 180 ° C., more preferably 50 to 150 ° C. and a pressure exceeding 0 to 10 Mpa, preferably 0.5 to 10 Mpa. More preferably, it is carried out under conditions in the range of 0.5 to 7 Mpa.

Ethylene / α-olefin random copolymer (C)
The ethylene / α-olefin random copolymer (C) used in the present invention contains a structural unit derived from ethylene in an amount of 50 to 99 mol%, and an α-olefin having 3 to 20 carbon atoms other than ethylene. An ethylene / α-olefin copolymer containing 1 to 50 mol% of the structural unit derived from (with the total of ethylene and α-olefin being 100 mol%) is desirable.

Preferably, the structural unit derived from ethylene is contained in an amount of 60 to 95 mol%, and the structural unit derived from an α-olefin having 3 to 20 carbon atoms other than ethylene is contained in an amount of 5 to 40 mol% (ethylene And α-olefin is 100 mol%), and the density is 91
0 to 850 kg / m ³ , 2.16 kg at 190 ° C. according to JIS K-6721
The MFR measured with a load of 0.01 to 100 g / 10 min.

More preferably, the structural unit derived from ethylene is contained in an amount of 80 to 95 mol%, and the structural unit derived from an α-olefin having 3 to 20 carbon atoms other than ethylene is contained in an amount of 5 to 20 mol% ( The total density of ethylene and α-olefin is 100 mol%), the density is 900 to 860 kg / m ³ , and 2.16 at 190 ° C. according to JIS K-6721.
The MFR measured with a load of kg is in the range of 0.05 to 50 g / 10 min.
The α-olefin copolymerized with ethylene is an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-
Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadodecene,
1-octadecene, 1-nonadecene, 1-eicocene, 4-methyl-1-pentene and the like can be mentioned. Among these, α-olefins having 3 to 10 carbon atoms are preferable. Particularly preferred are propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. These α-olefins may be used alone or in combination of two or more.

In addition to these units, the ethylene / α-olefin random copolymer (C) may contain units derived from other polymerizable monomers as long as the object of the present invention is not impaired.

Examples of such other polymerizable monomers include vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; butadiene Conjugated dienes such as isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7 -Methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene,
Dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropyl-2-norbornene Non-conjugated polyenes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and the like. In addition, it is one of the preferable embodiments that no non-conjugated diene or non-conjugated polyene is contained.

The ethylene / α-olefin random copolymer (C) contains units derived from such other polymerizable monomers in an amount of 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less. You may contain.

As the ethylene / α-olefin random copolymer (C), specifically,
Propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / propylene / 1-butene random copolymer, ethylene / propylene / ethylidene norbornene random copolymer, ethylene / 1-butene / 1-octene random copolymer Examples thereof include a polymer, an ethylene-4-methyl-1-pentene random copolymer, an ethylene / 1-hexene random copolymer, and an ethylene / 1-octene random copolymer. Among these, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / 1-butene / 1-octene random copolymer, ethylene / 1-hexene random copolymer, ethylene / 1 An octene random copolymer is particularly preferably used. These copolymers are
Two or more kinds may be used in combination.

The ethylene / α-olefin random copolymer (C) used in the present invention has a crystallinity measured by X-ray diffraction method of usually 40% or less, preferably 0 to 39%, more preferably 0 to 0%. 35%. The ethylene / α-olefin random copolymer (C) used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.1 to 10 dL / g, more preferably 0.5 to 5 dL. / g.

In the present invention, the balance between impact resistance and transparency is particularly improved by using the component (C).
The ethylene / α-olefin random copolymer as described above can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst. As the ethylene / α-olefin random copolymer (C), for example, a commercially available product may be used, or a trade name “Tuffmer ^™ ” manufactured by Mitsui Chemicals may be used.

Propylene polymer composition (X)
The propylene polymer composition (X) according to the present invention is:
(A) 100 to 25 parts by weight of the syndiotactic propylene polymer;
(B) 0 to 75 parts by weight of the propylene / α-olefin copolymer (provided that (A) and (
B) is 100 parts by weight), and (A) and (B) are 100 parts by weight in total.
(C) It contains 1 to 100 parts by weight of the ethylene / α-olefin copolymer.

Within this range, a propylene-based polymer composition that is particularly excellent in moldability and heat resistance and further excellent in transparency, flexibility, and low-temperature impact resistance is preferable.
If you need a material with good flexibility and excellent low-temperature impact resistance,
(A) 98 to 40 parts by weight of the syndiotactic propylene polymer;
(B) 2-60 parts by weight of the propylene / α-olefin copolymer (however, (A) and (
B) is 100 parts by weight), and (A) and (B) are 100 parts by weight in total.
(C) A composition comprising the ethylene / α-olefin copolymer 1 to 100 parts by weight (sometimes referred to as composition (i)) is preferred.

More preferably, the syndiotactic propylene polymer (A) is 10 to 49 parts by weight, more preferably 15 to 45 parts by weight, and the propylene / α-olefin copolymer (B) is preferably 51 to 90 parts by weight, more preferably. Is 55 to 85 parts by weight.

If you need a material with excellent heat resistance, relatively high rigidity, and good low temperature impact resistance,
(A) 100 parts by weight of the syndiotactic propylene polymer;
(B) 0 part by weight of the propylene / α-olefin copolymer;
(C) A composition comprising 1 to 100 parts by weight of the ethylene / α-olefin copolymer (sometimes referred to as composition (ii)) is preferred.

  In addition, the composition of the present invention is excellent in moldability and heat resistance, and further in the balance of transparency, flexibility and low temperature impact resistance. Here, excellent low temperature impact resistance means that, for example, when compared with materials having the same elastic modulus, the low temperature impact strength is higher, or for example, if the material has the same low temperature impact strength, the tensile elastic modulus is higher. Say there is.

  Here, “excellent formability” means that when molding such as injection, inflation, blow, extrusion or press is performed, the time from the molten state to solidification is short. When the moldability is good, the molding cycle performance, shape stability, long-term productivity, etc. are excellent.

Specifically, the time until solidification is preferably a half crystallization time (t _1/2 ) determined from isothermal crystallization measurement at 110 ° C. by a thermal differential calorimeter (DSC), preferably 1000 sec or less, more preferably 500 sec or less. is there. The half crystallization time (t _1/2 ) obtained from isothermal crystallization measurement at 110 ° C. with a thermal differential calorimeter (DSC) is sometimes referred to as physical property (1). Since the composition of the present invention contains specific (A) component and (B) component, t _1/2 is remarkably improved as compared with the prior art. For example, as in the case of normally used isotactic polypropylene The molding method can be used without difficulty.

The half crystallization time (t _1/2 ) obtained by isothermal crystallization measurement is the DSC in the isothermal crystallization process
When the area between the calorie curve and the baseline is defined as the total calorific value, it is the time when the calorific value reaches 50%. For more details, please refer to technical books such as New Polymer Experiment Lecture 8 Polymer Properties (Kyoritsu Publishing Co., Ltd.). The half crystallization time (t _1/2 ) is measured as follows. About 5.00 mg of sample is packed in a special aluminum pan, and DSCPyris1 or DSC7 manufactured by PerkinElmer
The temperature was raised from 30 ° C. to 200 ° C. at 320 ° C./min and held at 200 ° C. for 5 minutes, and then the temperature from 200 ° C. to isothermal crystallization temperature 110 ° C. was lowered at 320 ° C./min to 110 ° C. The half crystallization time (t _1/2 ) is determined from the DSC curve obtained while maintaining the temperature. Here, the half crystallization time (t _1/2 ) is obtained as an isothermal crystallization process start time of 110 ° C. (time when the temperature reaches 110 ° C. from 200 ° C.) t = 0. The composition of the present invention can determine t _1/2 as described above. However, when it does not crystallize at 110 ° C., several measurements are carried out at an isothermal crystallization temperature of 110 ° C. or lower for convenience. The half crystallization time (t _1/2 ) is determined from the extrapolated value.

  The needle penetration temperature measured for the propylene polymer composition (X) (softening temperature determined by TMA measurement, hereinafter sometimes referred to as physical property (2)) is preferably 145 ° C. or more, more preferably 150 ° C. That's it.

The softening temperature calculated | required by TMA measurement can be measured as follows.
Thickness 1mm using Seiko SS-120 or TA Instrument Q-400
A pressure of ² kgf / cm ² is applied to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min using a press sheet test piece, and the needle entry temperature (° C.) is obtained from the TMA curve.

  In addition, methods for measuring Izod impact strength (sometimes referred to as physical property (3)), tensile modulus (sometimes referred to as physical property (4)), and haze (sometimes referred to as physical property (5)) are shown below.

  The Izod impact strength was measured at 0 ° C by punching out a test piece of 12.7 mm (width) x 3.2 mm (thickness) x 64 mm (length) from a 3 mm thick press sheet, inserting a notch for machining, The average value of three measurements is adopted.

  The tensile elastic modulus is punched from a 1 mm thick press sheet in accordance with JIS K6301 with a JIS No. 3 dumbbell order bell and used as an evaluation sample. For example, using an Instron tensile tester Inston 1123, measurement is performed at 23 ° C. with a span interval of 30 mm and a tensile speed of 30 mm / min, and an average value of three measurements is employed.

As a haze, an internal haze is measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd. using a 1 mm thick press sheet test piece, and an average value of two measurements. Is adopted.

  In each of the above tests, after preheating at 200 ° C. for 5 minutes to 10 minutes with a press molding machine and molding in 1 to 2 minutes under 10 MPa pressure, cooling is performed at 20 ° C. under 10 MPa pressure. A test piece is obtained by producing a sheet having a thickness.

The propylene polymer composition (X) of the present invention is
(2) Needle penetration temperature is 145 ° C. or higher, preferably 147 ° C. or higher (3) Izod impact strength is 50 J / m or higher, preferably 100 J / m
(4) The tensile elastic modulus is in the range of 1 MPa to 2000 MPa, preferably in the range of 1 MPa to 1500 MPa. (5) The internal haze value is preferably 50% or less, preferably 40% or less.

In the case of the composition (i), the α-olefin of the propylene / α-olefin copolymer (B) is ethylene or a combination of ethylene and the above-described HAO monomer, and ethylene is particularly preferable. The structural unit derived from α-olefin is preferably 10
More preferably, it is mol%-40 mol%, and it is especially preferable that it is 15-35 mol%. If it is this range, it will become a composition excellent in especially heat resistance, transparency, a softness | flexibility, and impact resistance.

In the case of composition (i), the half-crystallization time (1) is preferably 1000 sec or less, more preferably 500 sec or less;
The needle penetration temperature (2) is preferably 145 ° C. or higher, more preferably 147 ° C. or higher, further preferably 150 ° C. or higher;
Izod impact strength (3) is preferably 50 J / m or more, more preferably 100 J / m or more;
The tensile modulus (4) is preferably in the range of 1 MPa to 2000 MPa, more preferably in the range of 1 MPa to 1000 MPa, and even more preferably in the range of 1 MPa to 800 MPa;
The internal haze (5) is preferably 50% or less, more preferably 40% or less.

  In the case of the composition (i), it is preferable that at least one of the physical properties (1) to (5) satisfies a preferable range, and (1), (3), and (4) are simultaneously satisfied. 2), (3), and (4) are simultaneously satisfied, or (3), (4), and (5) are preferably satisfied at the same time. (1), (3), and (4) ) And (5) are satisfied simultaneously, or (2), (3), (4) and (5) are more preferably satisfied, and (1), (2), (3), (4) and (4) It is particularly preferable to satisfy all 5).

In the case of the composition (ii), 1-butene and 1-octene are particularly preferable as the α-olefin of the ethylene / α-olefin copolymer (C). The structural unit derived from α-olefin is preferably 5 mol% to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 5 to 20 mol%. . If it is this range, it will become a composition excellent in especially heat resistance, transparency, low temperature impact resistance, and rigidity.

In the case of composition (ii), the half crystallization time (1) is preferably 1000 sec or less, more preferably 500 sec or less;
The needle penetration temperature (2) is preferably 145 ° C. or higher, more preferably 147 ° C. or higher, further preferably 150 ° C. or higher;
Izod impact strength (3) is preferably 100 J / m or more, more preferably 200 J / m;
The tensile modulus (4) is preferably in the range of 100 MPa to 2000 MPa, more preferably in the range of 100 MPa to 1000 MPa, and still more preferably in the range of 100 MPa to 800 MPa;
The internal haze (5) is preferably 50% or less, more preferably 40% or less.

In the case of the composition (ii), it is preferable that at least one physical property of (1), (2), (3), (4), and (5) satisfies the preferred range, and (1) and ( 3) and (4) must be satisfied at the same time, (2), (3) and (4) must be satisfied at the same time, or (3), (4) and (5) must be satisfied at the same time. Preferably, (1), (3), (4) and (5)
Or (2), (3), (4) and (5) are preferably satisfied at the same time, and all of (1), (2), (3), (4) and (5) are satisfied. It is particularly preferable to satisfy it.

The propylene polymer composition (X) of the present invention is composed of 99.0 to 35.0 mol% of structural units derived from propylene and α-olefin having 2 to 20 carbon atoms (excluding propylene). 1.0 to 65 mol% (wherein the structural unit derived from an α-olefin having 2 to 20 carbon atoms (including propylene) is 100 mol%)
It is preferable. In addition, it is more preferable that ethylene is included as a C2-C20 alpha olefin (except propylene).

  The propylene-based polymer composition (X) according to the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, and a nucleus within a range not impairing the object of the invention. Additives such as agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants may be blended as necessary.

The propylene-based polymer composition (X) according to the present invention may contain other polymers such as elastomers and resins within a range not impairing the object of the present invention.
Graft modification At least a part or all of the propylene polymer composition (X) of the present invention may be graft-modified with a polar monomer.

  For example, part or all of the component (A) may be graft-modified, part or all of the component (B) may be graft-modified, and part or all of the component (C) may be graft-modified. Part or all of each of the component (A) and the component (B) may be graft-modified, and part or all of the component (B) and the component (C) may be graft-modified. Part or all of each of the component (A) and the component (C) may be graft-modified, and part of each of the component (A), the component (B), and the component (C). Alternatively, all may be graft-modified.

  Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, chlorides. Examples thereof include vinyl and carbodiimide compounds.

  As the polar monomer, an unsaturated carboxylic acid or a derivative thereof is particularly preferable. Examples of the unsaturated carboxylic acid or a derivative thereof include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.

Specific examples of the compound include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocis-bicyclo [2.2.1] hept Unsaturated carboxylic acids such as -5-ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters and the like. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

These unsaturated carboxylic acids and / or derivatives thereof can be used singly or in combination of two or more. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used.

  The modification is obtained by graft polymerizing a polar monomer to the object to be modified. When grafting such a polar monomer as described above to the object to be modified, the polar monomer is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight per 100 parts by weight of the object to be modified. used. This graft polymerization is usually carried out in the presence of a radical initiator.

As the radical initiator, an organic peroxide or an azo compound can be used.
The radical initiator can be used as it is mixed with the modified substance and the polar monomer, but can also be used after being dissolved in a small amount of an organic solvent. Any organic solvent that can dissolve the radical initiator can be used without particular limitation.

Further, when the polar monomer is graft-polymerized on the object to be modified, a reducing substance may be used. When a reducing substance is used, the graft amount of the polar monomer can be improved.
Graft modification of the object to be modified with a polar monomer can be performed by a conventionally known method. For example, the object to be modified is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution. The reaction can be carried out preferably by reacting at a temperature of 80 to 190 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours.

  In addition, a modified propylene polymer composition can also be produced by reacting an object to be modified with a polar monomer using an extruder or the like. This reaction is usually at a temperature equal to or higher than the melting point of the object to be modified, specifically, for example, when the component (B) is modified, for example, 120 to 300 ° C., preferably 120 to 250 ° C., usually 0.5 to 10 minutes. It is desirable to be done. Moreover, when modifying the to-be-modified | denatured body containing (A) component, it is desirable to carry out for 0.5 to 10 minutes normally at the temperature of 160-300 degreeC, Preferably it is 180 degreeC-250 degreeC.

  The modified amount of the modified product thus obtained (the graft amount of the polar monomer) is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight, with the modified product being 100% by weight, The content is preferably 0.2 to 10% by weight.

  In the present invention, these modified products are used and, if necessary, further kneaded with one or more unmodified products selected from the component (A), the component (B) and the component (C). A coalescence composition (X) can be obtained.

  For example, the propylene-based polymer composition (Y) of the present invention, which will be described later, or a pellet of the propylene-based polymer composition (Y) is modified to prepare a modified product, and this modified product and a necessary amount of unmodified The propylene polymer (X) may be produced by melt-kneading a polymer (1 or more selected from the component (A), the component (B) or the component (C)).

  And the content with respect to 100 weight% of propylene polymer composition (X) by which at least one part obtained by the said method of the polar monomer was graft-modified by the polar monomer is 0.001 to 50 weight% normally, Preferably It is 0.001 to 10 weight%, More preferably, it is 0.001 to 5 weight%, More preferably, it is 0.01 to 3 weight%. The content of the polar monomer can be easily controlled, for example, by appropriately selecting the grafting conditions.

When at least a part of the propylene-based polymer composition of the present invention is graft-modified with a polar monomer, it is excellent in adhesion and compatibility with other resins, and obtained from the propylene-based polymer composition. The wettability of the surface of the molded body may be improved.

  Further, by making at least a part of the composition graft-modified, the propylene-based polymer composition of the present invention has transparency, low temperature impact resistance, mechanical properties (rigidity or flexibility), heat resistance, etc. In some cases, it is possible to add compatibility or adhesiveness to other materials while maintaining the above performance.

  In addition, since the content of polar monomers such as unsaturated carboxylic acids and / or derivatives thereof is within the above range, the polyolefin composition of the present invention can contain polar group-containing resins (for example, polyester, polyvinyl alcohol, ethylene / vinyl alcohol). Polymer, polyamide, PMMA, polycarbonate, etc.).

  In addition, the propylene-based polymer composition in which at least a part of the present invention is graft-modified is blended with another polymer, such as a thermoplastic resin or an elastomer, within a range that does not impair the properties of the modified product. Can do. Their blending may be in the graft modification step or after modification.

In order to further improve the moldability of the propylene polymer composition according to the present invention, that is, to increase the crystallization temperature and increase the crystallization speed, a nucleating agent which is a specific optional component may be included. In this case, for example, the nucleating agent is dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4
, 6-ditert-butylphenyl) sodium phosphate, pimelic acid and its salts, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, etc., and the amount is not particularly limited, but for propylene polymer compositions There is preferably about 0.1 to 1 part by weight. There is no restriction | limiting in particular in a mixing | blending timing, It can add during superposition | polymerization, after superposition | polymerization, or a shaping | molding process.

Production Method of Propylene Polymer Composition (X) The propylene polymer composition as described above is prepared by various known methods such as slurry phase, solution phase or gas phase within the above ranges. Continuous or batch multi-stage polymerization method, Henschel mixer, V-blender, riboblender, tumbler blender, etc. or after mixing, melt kneading with single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. Then, it can manufacture by employ | adopting the method of granulating or grind | pulverizing.

In producing the propylene-based polymer composition (X) of the present invention, for example, pellets made of the following propylene-based polymer composition (Y) can be used as a raw material. This propylene-based polymer composition (Y)
1 to 65 parts by weight of syndiotactic propylene polymer (A1);
Propylene / α-olefin copolymer (B1) 99 to 35 parts by weight (however, (A1)
And (B1) is 100 parts by weight), the polymer (A1) satisfies the following requirement (a1), and the copolymer (B1) satisfies the following requirement (b ′). Do;
(A1): The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more and the melting point (Tm) determined by DSC is 145 ° C. or more, which is derived from propylene. The structural unit is contained in an amount exceeding 90 mol% (however, the total amount of the structural units in the polymer (A1) is 100 mol%).
(B1): Containing structural units derived from propylene in an amount of 55 to 90 mol% (provided that the total amount of structural units in the copolymer (B1) is 100 mol%), and having 2 carbon atoms It contains a structural unit derived from at least one olefin selected from -20 α-olefins (excluding propylene) in an amount of 10 to 45 mol%, and is 230 ° C and 2.16 kg according to JIS K-6721. The MFR measured under load is in the range of 0.01 to 100 g / 10 min and satisfies at least one of the following requirements (b1-1) or (b1-2);
(B1-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B1-2) The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) satisfy the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
Examples of the (A1) syndiotactic propylene polymer used in the pellet include the same propylene polymer as used in the propylene polymer composition (X). Preferred modes such as bonding mode, types of structural units derived from α-olefins other than structural units derived from propylene, abundance, syndiotactic pentad fraction, Tm, ΔH, [η], etc., production method, etc. Are all the same as the syndiotactic propylene polymer (A) used in the propylene polymer composition (X).

Examples of the (B1) propylene / α-olefin copolymer used in the pellets of the present invention include the same as the propylene / α-olefin copolymer (B) used in the propylene polymer composition (X). It is done.

In the present invention, the propylene-based polymer is also suitable for all of the preferred embodiments such as the type, ratio, rr value, rr ₁ value, [η], crystallinity, Tg, Mw / Mn, etc. This is the same as the propylene / α-olefin copolymer (B) used in the coalescence composition (X).

  In the pellet, the component (A1) is 1 to 65 parts by weight, preferably 1 to 40 parts by weight, and the component (B1) is 99 to 35 parts by weight, preferably 99 to 60 parts by weight (here, the component (A1) and ( B1) a propylene polymer composition (Y) that is 100 parts by weight in total).

  Examples of the shape of the pellet made of the propylene-based polymer composition (Y) include a spherical shape, a cylindrical shape, a lens shape, and a cubic shape. These can be produced by a known pelletization method. For example, the components (A1) and (B1) are uniformly melt-mixed and extruded by an extruder, and then hot cut or strand cut to obtain a spherical shape, a cylindrical shape, Lenticular pellets are obtained. In this case, the cutting may be performed either in water or in an air stream such as air. Moreover, if an extruder having an apparatus that can form the outer layer and the inner layer with different polymers is used, a double-structured strand in which the component (A1) is arranged in the outer layer and the component (B1) is arranged in the inner layer is cut. Therefore, it is possible to further suppress mutual attachment and is effective. The cubic pellets can be obtained by, for example, uniformly mixing, forming into a sheet shape with a roll or the like, and using a sheet pelletizing machine. As the size, the length of the longest part of the pellet is preferably 3 cm or less. In the case of pellets larger than this, the weighing error may increase.

  The pellet made of the propylene-based polymer composition (Y) is one in which one or more of calcium carbonate, barium sulfate, silica, talc, stearic acid and polyolefin powder are dusted on the surface of the pellet. There may be. In this case, it is preferable from the viewpoint of suppressing the bridging phenomenon of the pellets when further pressing the mutual attachment or taking out from the silo or the like. The required amount of dusting may be added depending on the size and shape of the pellet, but it is usually added in an amount of 0.05 to 3 parts by weight based on the resin composition pellet.

In addition, a weather resistance stabilizer, a heat stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, a nucleating agent, a lubricant, a pigment, a dye, a plasticizer, and an anti-aging agent as long as the object of the present invention is not impaired. Additives such as an agent, hydrochloric acid absorbent, and antioxidant may be blended as necessary. The propylene-based polymer composition (Y) according to the present invention includes other polymers ((A1) propylene-based polymer, (B1) propylene / α-olefin copolymer within the range not impairing the object of the present invention. And an ethylene / α-olefin copolymer (C)) may be included.

  As a preferred method for obtaining propylene-based polymer composition (Y) pellets, the (A1) component and the (B1) component are equal to or higher than the maximum peak temperature (Tm) in the differential scanning calorimetry (DSC) of the (A1) component. For example, a method of kneading at a temperature of 280 ° C. or lower can be mentioned.

  In order to obtain the propylene-based polymer composition (X) from the propylene-based polymer composition (Y), the polymer to be modified, for example, the polyolefin-based polymer, the polyolefin-based modifier of the present invention, and as necessary. Then, the additive described in the section of the propylene polymer composition (X) may be kneaded. As a kneading method, it is preferable to melt knead the pellet of the present invention and the polymer to be modified. The blending amount of the modifier is 3 to 95% by weight, preferably 10 to 80% by weight, more preferably 30 to 70% by weight. If the amount is within this range, a modified polymer composition having sufficient reforming effect, good fluidity, excellent moldability and strength, and excellent heat resistance can be obtained.

Since the pellets are excellent in blocking resistance, other polymers can be modified with high productivity.
Therefore, the composition (X) of the present invention is mixed with the above pellets, the required amount of the component (A), the required amount of the (C) ethylene / α-olefin copolymer, and another polymer (( A) Syndiotactic propylene polymer, (B) Propylene / C2-C20 α-olefin (
However, it can also be obtained by blending and kneading the above-mentioned additives as necessary, except for copolymers (excluding propylene), (C) excluding ethylene / α-olefin copolymers having 3 to 20 carbon atoms). It is.

Molded product using propylene-based polymer composition (X) The propylene-based polymer composition (X) according to the present invention as described above is excellent in moldability and heat resistance, and has flexibility and low-temperature impact resistance. In addition, since it is possible to obtain a molded article having excellent transparency, it has been practically difficult to use syndiotactic polypropylene, and it can be widely used for conventionally known polyolefin applications. For example, the product can be used by forming it into a sheet, an unstretched or stretched film, a filament, and other various shapes. Moreover, the molded object using propylene-type polymer composition (X) should just contain propylene-type polymer composition (X) in a part of molded object, ie, a propylene-type in a part of molded object. The polymer composition (X) only needs to be used, and the propylene-based polymer composition (X) may be used for the entire molded body. As an example in which the propylene-based polymer composition (X) is used in a part of the molded body, a multilayer laminate can be mentioned. Specifically, the multilayer laminate is a laminate in which at least one layer thereof contains the propylene polymer composition (X), and is a multilayer film and sheet, multilayer container, multilayer tube, water-based paint A multilayer coating film laminate included as a constituent component of

  Specific examples of the molded body include known thermoforming such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding, and powder slush molding. The molded object obtained by a method is mentioned. Hereinafter, the molded body will be described with several examples.

  When the molded body according to the present invention is, for example, an extruded molded body, the shape and product type are not particularly limited, and examples thereof include a sheet, a film (unstretched), a pipe, a hose, an electric wire coating, a tube, and the like. (Skin material), film, tube, catheter, monofilament (nonwoven fabric) and the like are preferable.

  When extruding the propylene-based polymer composition (X), conventionally known extruding equipment and molding conditions can be employed. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder The molten propylene polymer composition can be molded into a desired shape by extruding from a specific die or the like.

  The stretched film is obtained by stretching an extruded sheet or extruded film (unstretched) as described above by a known stretching method such as a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method, or the like. Obtainable.

  The stretching ratio when stretching the sheet or unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 μm by stretching.

Moreover, an inflation film can also be manufactured as a film-shaped molded object. Drawdown is less likely to occur during inflation molding.
Sheets and film molded articles using the propylene polymer composition (X) are hardly charged, and have mechanical properties, heat resistance, stretchability, impact resistance, aging resistance, transparency, transparency, gloss, rigidity. It is excellent in moisture resistance and gas barrier properties, and can be widely used as a packaging film.

  In this case, the sheet and film molded body using the propylene-based polymer composition (X) may be a multilayer molded body, and a multilayer laminate containing at least one layer of the propylene-based polymer composition (X). Used as a body.

  The filament molded body can be produced, for example, by extruding a molten propylene polymer composition through a spinneret. Specifically, a spunbond method or a melt bron method is preferably used. The filament thus obtained may be further stretched. This stretching may be performed to such an extent that at least one uniaxial direction of the filament is molecularly oriented, and it is usually desirable to perform the stretching at a magnification of about 5 to 10 times. Filaments made of the propylene-based polymer composition (X) are not easily charged, and are excellent in transparency, flexibility, heat resistance, impact resistance, and stretchability.

  The injection-molded body can be produced by injection-molding the propylene-based polymer composition into various shapes using a known condition using a conventionally known injection molding apparatus. An injection molded article using the propylene-based polymer composition is hardly charged and has excellent transparency, rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc. It can be used in a wide range of trim materials for automobiles, exterior materials for automobiles, housings for home appliances, containers and the like.

  The blow molded article can be produced by blow molding a propylene-based polymer composition using a known blow molding apparatus under known conditions. In this case, the blow molded article made of the propylene polymer composition may be a multilayer molded article, and contains at least one layer of the propylene polymer composition.

  For example, in extrusion blow molding, the propylene polymer composition (X) is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is held in a mold having a desired shape. A hollow molded body can be manufactured by blowing after-air and mounting the mold at a resin temperature of 130 ° C to 300 ° C. The stretching (blowing) magnification is desirably about 1.5 to 5 times in the lateral direction.

In injection blow molding, the propylene-based polymer composition is resin temperature 100 ° C. to 300 ° C.
A parison is molded by injecting into a parison mold, and then the parison is held in a mold having a desired shape, then air is blown into the mold, and a hollow molded body is manufactured by wearing the mold at a resin temperature of 120 ° C to 300 ° C. can do. The draw (blow) magnification is desirably 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.5 times in the transverse direction.

A blow molded article using a propylene-based polymer composition is excellent in transparency, rigidity or flexibility, heat resistance and impact resistance, and also in moisture resistance.
Examples of the press-molded body include a mold stamping molded body. For example, when a base material and a skin material are press-molded at the same time and both are integrally formed (mold stamping molding), the base material is a propylene-based polymer composition ( X).

  Specific examples of such a mold stamping molded body include automotive interior materials such as door rims, rear package trims, seat back garnishes, and instrument panels.

  A press-molded product using the propylene-based polymer composition (X) is hardly charged, and has rigidity or flexibility, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, and abrasion resistance. Excellent in properties.

A foamed molded article using the propylene-based polymer composition (X) is obtained at a high expansion ratio, has good injection moldability, and has high rigidity and material strength.
The propylene-based polymer composition (X) can produce vacuum molded bodies such as interior skin materials such as automobile instrument panels and door trims. The molded body is hardly charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance, and the like.

  The propylene-based polymer composition (X) can produce powder slush moldings such as automobile parts, home appliance parts, toys, and miscellaneous goods. The molded body is hardly charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance, and the like.

Moreover, as a molded object which concerns on this invention, the laminated body which has at least one layer which consists of propylene polymer composition (X) can be mentioned.
The propylene-based polymer composition (X) according to the present invention is suitable for a container or a nonwoven fabric, for example. Examples of the container include a food container such as a frozen storage container and a retort pouch, and a bottle container. Moreover, a medical container, an infusion bag, etc. can be illustrated.

  As described above, the propylene-based polymer composition (X) of the present invention includes, for example, an infusion bag, a medical container, an automobile interior / exterior material, a beverage bottle, a clothing case, a food container, a food packaging, a retort container, a PET substitute, Pipes, transparent substrates, sealants, transparent sealants, porous films, masking films, film for capacitors, laminates (including glass), foams, reflective films, dicing films, electric cables, soundproofing materials, damping materials, damping materials, Sound absorbing material, sound insulating material, foam material, building material, building material skin material, automotive skin material, solar cell sealing material, radiation resistant film, gamma ray film, flow mark modifier, non-woven fabric, modifier, shape memory material, Laminated glass film, bulletproof material, bulletproof glass film, protective film, adhesive, compatibilizer (for example, graft-modified), Interview link the film, resistant Chiippingu material, resistant Chiippingu resistance improver, oriented films, weld modifiers, wrap film, it can be widely used for applications such as capacitor films.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the examples, each physical property was measured as follows.

Physical property measurement method [Intrinsic viscosity [η]]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of polymer powder, pellets, or resin mass was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).

[Η] = lim (ηsp / C) (C → 0)
[Amount of soluble part of n-decane]
200 ml of n-decane was added to 5 g of a sample of syndiotactic propylene polymer, and the polymer was dissolved by heating at 145 ° C. for 30 minutes. The resulting solution was allowed to cool to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (n-decane insoluble part) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate was filtered off from acetone and then dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following equation.

n-decane soluble part amount (wt%) = [precipitate weight / sample weight] × 100
[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. Separation column is TSKg
Two el GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o-dichlorobenzene ( Wako Pure Chemical Industries) and BHT (antioxidant)
Takeda) 0.025% by weight, moved at 1.0ml / min, sample concentration 15mg /
The sample injection volume was 500 microliters, and a differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[Ethylene, propylene, α-olefin content in polymer]
Quantification of ethylene, propylene, and α-olefin content was measured as follows using a JNM GX-400 NMR measuring apparatus manufactured by JEOL Ltd. A sample of 0.35 g was dissolved by heating in 2.0 ml of hexachlorobutadiene. This solution was filtered through a glass filter (G2), 0.5 ml of deuterated benzene was added, and the solution was charged into an NMR tube having an inner diameter of 10 mm and subjected to ¹³ C-NMR measurement at 120 ° C. The number of integrations was 8,000 times or more. The composition of ethylene, propylene, and α-olefin was quantified by the obtained ¹³ C-NMR spectrum.

[Melting point (Tm), heat of fusion (ΔH)]
Using a DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20 ml / min), a sample of about 5 mg was heated to 200 ° C. and held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 5 minutes, the melting point was calculated from the peak of the crystal melting peak when the temperature was raised to 200 ° C. at 10 ° C./min, and the heat of fusion was calculated from the integrated value of the peaks.

[Semi-isothermal crystallization time (t _1/2 )]
About 5mg of sample is packed in a special aluminum pan, heated from 30 ° C to 200 ° C at 320 ° C / min using DSCPyris 1 or DSC7 manufactured by PerkinElmer, and held at 200 ° C for 5 minutes, then isothermal crystal from 200 ° C From the DSC curve obtained by lowering the crystallization temperature up to 110 ° C. at 320 ° C./min and holding at each isothermal crystallization temperature, the semi-isothermal crystallization time (t _1/2 )
Asked. Here, the half crystallization time (t _1/2 ) was determined as t = 0 when the isothermal crystallization process start time (time when the isothermal crystallization temperature was reached from 200 ° C.) The composition of the present invention can determine t _1/2 as described above. For example, when it does not crystallize at a certain isothermal crystallization temperature, for example, 110 ° C., isothermal crystallization of 110 ° C. or less for convenience. Several measurements were carried out at temperature, and the half crystallization time (t _1/2 ) was determined from the extrapolated value.

[Glass point transfer (Tg)]
Using a DSC manufactured by Seiko Instruments Inc., a sample of about 5 mg was packed in an aluminum pan for measurement, heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 5 minutes, and then −150 ° C. at 10 ° C./min. The glass point transfer (Tg) was determined from an endothermic curve where the temperature was lowered to 200 ° C. at 10 ° C./min.

[MFR]
The MFR of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B) was measured at 230 ° C. under a load of 2.16 kg according to JIS K-6721.

The MFR of the ethylene / butene copolymer (C) is 19 in accordance with JIS K-6721.
Measurement was performed at 0 ° C. with a load of 2.16 kg.
[Manufacturing method of various press sheets]
A 10 MPa pressure sheet was formed using a hydraulic hot press machine manufactured by Shindo Metal Industry Co., Ltd. set at 200 ° C. In the case of a 0.5-3 mm thick sheet (spacer shape; 80 × 80 × 0.5-3 mm, 4 pieces on a 240 × 240 × 2 mm thick plate), the remaining heat is about 5-7 minutes and 10 MP
After pressurizing with a for 1 to 2 minutes, a measurement sample was prepared by compressing at 10 MPa using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set at 20 ° C. and cooling for about 5 minutes. A 5 mm thick brass plate was used as the hot plate. The samples prepared by the above method were used for various physical property evaluation samples.

[Tensile modulus]
From a 1 mm-thick press sheet, it was punched out using an JIS No. 3 dumbbell custom-made bell according to JIS K6301, and used as an evaluation sample. The sample was measured at 23 ° C. with a span interval of 30 mm and a tensile speed of 30 mm / min.

[Izod impact strength]
In accordance with ASTM D-256, from a 3 mm thick press sheet, 12.7 mm (width) x 3
. A test piece of 2 mm (thickness) × 64 mm (length) was punched out, a notch for machining was added, and measurement was performed at 0 ° C.

[Softening temperature by TMA measurement]
In accordance with JIS K7196, using a test piece with a thickness of 1 mm, a pressure of ² kgf / cm ² was applied to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min, and the softening temperature (
° C).

[Internal haze (%)]
Using a test piece having a thickness of 1 mm, a digital turbidimeter “NDH-20” manufactured by Nippon Denshoku Industries Co., Ltd.
D ".

Catalyst synthesis example [Synthesis Example 1]
Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride was produced by the method described in Synthesis Example 3 of JP-A No. 2004-189666.
[Synthesis Example 2]
Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was prepared as follows.
((Step 1) Synthesis of 2,7-Dibromo-3,6-di-tert-butyl-fluorene Under a nitrogen stream, 170 mL of propylene carbonate was added to 15.22 g (54.7 mmol) of 3,6-di-tert-butylfluorene To this solution, 20.52 g (115 mmol) of N-bromosuccinimide was added, followed by heating and stirring for 5 hours at 80 ° C. After allowing to cool naturally, the reaction solution was added to 800 mL of water. The resulting white yellow powder was washed 5 times with 10 mL of ethanol, and a mixed solution of hexane and a small amount of dichloromethane was added to the white yellow powder. All were dissolved by heating, and allowed to stand overnight at −20 ° C. The precipitated crystals were washed 3 times with 5 mL of hexane to obtain the desired product as a white yellow powder (yield 21.16 g, yield 76%). .

¹ H NMR (270 MHz, CDCl ₃ ): δ 1.60 (s, tBu (Flu), 18H), 3.75 (s, Flu-9H, 2H), 7.73 (s, Flu, 2H), 7.81 (s, Flu, 2H).
MS (FD): M / z 436 (M ⁺ ).
(Step 2) Synthesis of 3,6-Di-tert-butyl-2,7-diphenyl-fluorene Under a nitrogen stream, 2,15-dibromo-3,6-di-tert-butylfluorene 8.15 g (18.7 mmol) ), 120 mL of anhydrous DME was added to 1.08 g (0.93 mmol) of Pd (PPh3), and the mixture was stirred at room temperature for 20 minutes. To this solution, a solution of 5.01 g (41.1 mmol) of phenylboric acid in 20 mL of ethanol was added. The flask containing phenylboric acid was washed twice with 4 mL of ethanol and added. After stirring at room temperature for 20 minutes, 37.4 mL (74.8 mmol) of a 2.0 mol / L sodium carbonate aqueous solution was added. Heating under reflux was performed for 18 hours. After naturally cooling, the reaction was terminated with 1N hydrochloric acid in an ice bath. Ether was added for liquid separation, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off and separation by silica gel chromatography was performed. A mixed solution of hexane and a small amount of dichloromethane was added to the obtained white yellow powder, and heated to 60 ° C. to completely dissolve it. After leaving still at room temperature for 1 hour, it left still at -20 degreeC for 13 hours. The precipitated crystals were washed 3 times with 10 mL of hexane to obtain the desired product as a white powder (yield 4.36 g, yield 54%).

¹ H NMR (270 MHz, CDCl ₃ ): δ 1.29 (s, tBu (Flu), 18H), 3.78 (s, Flu-9H, 2H), 7.16 (s, Flu, 2H), 7.34 (br, PhFlu, 10H), 7.97 (s, Flu, 2H).
MS (FD): M / z 430 (M ⁺ ).
(Step 3) Synthesis of 6,6-dibenzylfulvene 8.0 g (121.0 mm) of cyclopentadiene in a 500 mL 3-neck flask under a nitrogen atmosphere
ol) and 100 mL of dehydrated THF were added and stirred. This mixed solution was cooled in an ice bath, and 80 mL (125.6 mmol) of a hexane solution of n-butyllithium having a concentration of 1.57 mol / L.
l) was added. Thereafter, the mixture was stirred at room temperature for 3 hours, and the resulting white slurry was cooled in an ice bath, and then a solution of 25.0 g (118.0 mmol) of 1,3-diphenyl-2-propanone in 50 ml of dehydrated THF was added. The mixture was then stirred at room temperature for 12 hours, and the resulting yellow solution was quenched with saturated aqueous NH 4 Cl. Hexane 100mL was added and the soluble part was extracted, and this organic phase was dried with magnesium sulfate after washing | cleaning with water and a saturated salt solution. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a yellow solid (yield 3.7 g, yield 12%).

¹ H NMR (270 MHz, CDCl ₃ ): δ 3.69 (s, PhCH ₂ , 4H), 6.60-6.72 (m, Cp, 4H), 7.13-7.32 (m, PhCH ₂ , 10H).
(Step 4) Synthesis of (Ph CH ₂ ) ₂ C (Cp) (3,6-tBu ₂ -2,7-Ph ₂ -Flu) 3,6-Di-tert-butyl-2,7- under nitrogen flow To 1.60 g (3.71 mmol) of diphenyl-fluorene, 40 mL of anhydrous THF was added and stirred. The solution was cooled in an ice bath and 1.56M
2.65 mL (4.13 mmol) of n-butyllithium in hexane was added. Stir at room temperature for 2 hours. The obtained red solution was cooled to −78 ° C. with a dry ice-methanol bath, and 2 solutions of 1.06 g (4.10 mmol) of 6,6-dibenzylfulvene in 20 mL of THF were added.
Added dropwise over 0 minutes. Thereafter, the mixture was stirred for 18 hours while gradually warming to room temperature. To the resulting black-red solution, 60 mL of 1N hydrochloric acid was added to terminate the reaction. 80 mL of ether was added to carry out liquid separation, and a soluble part was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The target product was obtained as a white yellow powder by evaporating the solvent and purifying by silica gel chromatography (yield 0.59 g, yield 23%).

¹ H NMR (270 MHz, CDCl ₃ ): δ 1.25 (s, tBu (Flu), 18H), 2.66 (br, CpH, 1H), 3.22
(br, CH ₂ Ph, 4H), 4.41 (br, Flu-9H, 1H), 5.85-6.51 (m, Cp, 4H), 6.82-7.40 (m, Ph (Flu) and CH ₂ Ph and Flu, 22H ), 7.67 (s, Flu, 2H).
MS (FD): M / z 688 (M ⁺ ).
(Step 5) Synthesis of (PhCH ₂ ) ₂ C (Cp) (3,6-tBu ₂ -2,7-Ph ₂ -Flu) ZrCl ₂ (PhCH ₂ ) ₂ C (Cp) into a 100 mL Schlenk tube under a nitrogen atmosphere ) (3,6-tBu ₂ -2,7-Ph ₂ -Flu) 0.59 g (0.855 mmol) and anhydrous diethyl ether 40 mL were added and stirred. This mixed slurry solution was cooled in an ice bath, 1.21 mL (1.88 mmol) of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L was added, and the mixture was stirred for 45 hours while gradually warming to room temperature. The red reaction solution was cooled (−78 ° C.) with a dry ice / methanol bath, and 0.200 g (0.858 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 42 hours while gradually warming to room temperature to obtain a red-orange suspension.

  The solvent was dried under reduced pressure, dissolved in hexane in a glove box, washed with hexane through a glass filter packed with celite, and the orange powder not dissolved in hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off, washed with diethyl ether / cold pentane, and dried to obtain the desired product as an orange powder (yield 515 mg, 71%).

¹ H NMR (270 MHz, CDCl ₃ ): δ 1.30 (s, tBu (Flu), 18H), 3.82 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 3.93 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 5.80 (t, J = 2.6 Hz, Cp, 2H), 6.25 (t, J = 2.6 Hz, Cp, 2H), 6.97-7.34 (m, Ph (Flu) and CH ₂ Ph, 20H ), 7.37 (s, Flu, 2H), 8.32 (s, Flu, 2H).
MS (FD): M / z 848 (M ⁺ ).
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was prepared by the following method.

[Synthesis Example 3]
Synthesis of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (i) Synthesis of 6,6-di (p-chlorophenyl) fulvene Reaction vessel equipped with a dropping funnel Under nitrogen atmosphere, 40 ml of dehydrated tetrahydrofuran and 2.15 ml (25.9 mmol) of cyclopentadiene were added, and 18.0 ml (28.5 mmol) of a hexane solution of 1.58 mol / L n-butyllithium was cooled while cooling this solution to 0 ° C.
Was slowly added dropwise and stirred. Thereafter, a solution obtained by dissolving 5.00 g (19.9 mmol) of 4,4′-dichlorobenzophenone in 30 ml of dehydrated tetrahydrofuran was added to the dropping funnel, and the solution was slowly added dropwise while cooling to 0 ° C., followed by returning to room temperature and stirring for one day. This reaction solution was extracted with diethyl ether, the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the separated organic phase was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered off. The solvent of the filtrate was distilled off under reduced pressure using a rotary evaporator. Purification was performed on a silica gel column to obtain the desired product (yield 3.37 g, yield 57%). The target product was identified by ¹ H-NMR.

¹ H NMR spectrum (270 MHz, CDCl ₃ , TMS): δ 6.21-6.24 (m, 2H), 6.60-6.63 (m, 2H), 7.23 (d, 2H, J = 8.1 Hz), 7.37 (d, 2H , J = 8.6 Hz).
(Ii) Synthesis of octamethyloctahydrodibenzofluorene In a 500 ml three-necked flask equipped with a nitrogen-filled three-way cock, dropping funnel and magnetic stirrer, 9.72 g (58.6 mmol) of fluorene and 2,5-dimethyl were added. -19.6 g (134 mmol) of -2,5-hexanediol was added at room temperature. After adding 85 ml of dehydrated dichloromethane and stirring with a magnetic stirrer, the mixture was cooled to −8 ° C. with an ice bath. To this, 38.9 g (292 mmol) of crushed anhydrous aluminum chloride was added over 70 minutes, followed by stirring at 0 ° C. for 2 hours, further removing the ice bath and stirring at room temperature for 19 hours. After confirming disappearance of fluorene by GC, the black brown solution was quenched by pouring into 150 ml of ice water. After extraction of soluble components with 500 ml of diethyl ether, the organic layer was neutralized with a saturated aqueous solution of sodium bicarbonate and washed with water. The separated organic phase was dried over anhydrous magnesium sulfate, the magnesium sulfate was filtered off, and the solvent of the filtrate was distilled off under reduced pressure using a rotary evaporator. The residue was transferred onto a Kiriyama funnel, washed with hexane 10 ml × 6 times, and dried under reduced pressure to obtain the desired product (yield 12.0 g, yield 53%). The object was identified by ¹ H-NMR and FD-MS spectra.

¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ / ppm 1.3 (s, 12H), 1.4 (s, 12H), 1.7 (s, 8H), 3.8 (s, 2H), 7.4 (s, 2H ), 7.6 (s, 2H).
MS (FD): M / z 386 (M ⁺ ).
(Iii) Synthesis of di (p-chlorophenyl) cyclopentadienyl (octamethyloctahydrodibenzofluorenyl) methane In a reaction vessel equipped with a dropping funnel, 40 ml of dehydrated tetrahydrofuran and the octamethyloctahydrodibenzofluorene were added in a nitrogen atmosphere. 2.35 g (6.08 mmol) was added, and while cooling this solution to 0 ° C., 4.62 ml (7.30 mmol) of a 1.58 mol / L n-butyllithium hexane solution was slowly added dropwise and stirred. To this solution, 1,3-dimethyl-
After adding 0.86 ml (7.90 mmol) of 2-imidazolidinone and stirring for 30 minutes, 2.00 g (6.68 mmol) of 6,6-di (p-chlorophenyl) fulvene was dissolved in 30 ml of dehydrated tetrahydrofuran in a dropping funnel. The solution was added dropwise slowly while cooling to -78 ° C., and stirred for one day while slowly returning to room temperature. This reaction solution was extracted with diethyl ether, the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the separated organic phase was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered off. The solvent of the filtrate was distilled off under reduced pressure using a rotary evaporator. After purification with a silica gel column, recrystallization was performed with toluene to obtain the desired product (yield 0.714 g, yield 17%). The target product was identified by ¹ H-NMR and FD-MS spectra.

¹ H NMR spectrum (270 MHz, CDCl ₃ , TMS): δ 0.94 (s, 6H), 1.14 (s, 6H), 1.27 (s,
12H), 1.62 (s, 8H), 3.06 (b, 2H), 5.30 (s, 1H), 6.38-6.50 (b, 3H), 7.00-7.29 (m, 8H)
FD-MS spectrum: m / z 684 (M ⁺ ).
(Iv) Synthesis of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride In 15 ml of dehydrated diethyl ether under nitrogen atmosphere, di (p-chlorophenyl) cyclopentadienyl ( 428 mg (0.62 mmol) octamethyloctahydrodibenzofluorenyl) methane
The solution was cooled slowly to 0 ° C., and 0.88 ml (1.37 mmol) of a 1.58 mol / L hexane solution of n-butyllithium was slowly added dropwise and stirred overnight. Then -78
While cooling at 0 ° C., 224 mg (0.59 mmol) of zirconium tetrachloride / tetrahydrofuran complex (1: 2) was added and stirred overnight. After distilling off the volatile components of this slurry under reduced pressure, the residue was washed with 40 ml of dehydrated hexane, and the washing solution was separated by filtration. The hexane-dissolved portion of the filtrate was concentrated, and dehydrated hexane was added to the resulting solid and recrystallized to obtain the desired product (yield 90 mg, 18%). The target product was identified by ¹ H-NMR and FD-MS spectra.

¹ H NMR (Spectrum 270 MHz, CDCl ₃ ): δ 0.87 (s, 6H), 0.99 (s, 6H), 1.42 (s, 6H), 1.49 (s, 6H), 1.64-1.71 (m, 8H), 5.51-5.53 (m, 2H), 6.17 (s, 2H), 6.29-6.31 (m, 2H), 7.33 (dd, 2H, J = 2.16 Hz, 8.37 Hz), 7.46 (dd, 2H, J = 1.89 Hz , 8.64 Hz), 7.74 (dd, 2H, J = 2.43 Hz, 8.1 Hz), 7.88 (dd, 2H, J = 2.16 Hz, 8.37 Hz), 8.08 (s, 2H)
FD-MS spectrum: m / z 844 (M ⁺ ).
[Synthesis Example 4]
Synthesis of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride (i) Preparation of 1-ethyl-3-tert-butylcyclopentadiene Synthesis Under a nitrogen atmosphere, a 300 ml three-necked flask equipped with a magnetic stirrer and a three-way cock was charged with 200 ml of dehydrated diethyl ether and 52 ml (154 mmol) of a 3.0M ethylmagnesium bromide diethyl ether solution. In an ice water bath, 17.8 g (129 mmol) of 3-tert-butylcyclopentenone was added dropwise over 1 hour. After stirring at room temperature for 20 hours, the reaction solution was poured into 100 ml of 2N hydrochloric acid. The organic layer was separated and the aqueous layer was extracted twice with 50 ml of ether. The obtained organic layers were combined and washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, and twice with saturated brine. It dried with magnesium sulfate and the solvent was distilled off. Thereafter, purification by column chromatography gave 20.2 g (GC purity 75%) of a pale yellow transparent liquid. The yield was 78%. Identification was performed by ¹ H-NMR spectrum. The measurement results are shown below.

¹ H-NMR spectrum (270 MHz, CDCl ₃ , TMS standard): δ / ppm 6.19 + 6.05 + 5.81 + 5.77 (m + m + m + m, 2H), 2.91 + 2.85 (m + m, 2H), 2.48− 2.27 (m, 2H), 1.15−1.08 (s + s + m, 12H)
(Ii) Synthesis of 3-tert-butyl-1-ethyl-6,6-diphenylfulvene In a 300 ml three-necked flask equipped with a magnetic stirrer and a three-way cock in a nitrogen atmosphere, 1-ethyl-3-tert-butylcyclo Pentadiene 5.11 g (23.9 mmol) (GC purity 75%) and THF 150 ml were charged. In a dry ice / methanol bath, 16 ml (25.2 mmol) of a 1.56 Mn-butyllithium hexane solution was slowly added dropwise, and then stirred at room temperature for 20 hours. To the resulting reaction solution, 3.1 ml (28.8 mmol) of 1,3-dimethyl-2-imidazolidinone was added, followed by charging with 5.3 g (28.8 mmol) of benzophenone and refluxing for 48 hours. Stir. The reaction solution was poured into 100 ml of 2N hydrochloric acid. The organic layer was separated and the aqueous layer was extracted twice with 50 ml of hexane. The organic layer was combined and washed with a saturated aqueous sodium hydrogen carbonate solution, water, and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. Thereafter, the product was purified by column chromatography to obtain 4.2 g of an orange solid. The yield was 56%. Identification was performed by ¹ H-NMR spectrum. The measurement results are shown below.

¹ H-NMR spectrum (270 MHz, CDCl ₃ , TMS standard): δ / ppm 7.2−7.4 (m, 10H), 6.3 (m, 1H), 5.7 (m, 1H), 1.70 + 1.85 (q, 2H) , 1.15 (s, 9H), 0.85 (t, 3H)
(Iii) Synthesis of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) A 200 ml three-necked flask equipped with a magnetic stirring bar and a three-way cock was used. The gas was thoroughly purged with nitrogen, and 3.8 g of 2,7-di-tert-butylfluorene (13.7 mmol) under a nitrogen atmosphere.
) Was dissolved in 80 ml of dehydrated diethyl ether. Under an ice-water bath, 9.2 ml of n-butyllithium / hexane solution (1.56M: 14.3 mmol) was gradually added dropwise to this solution, and then stirred at room temperature for 100 hours. To this reaction solution, 4.5 g of 3-tert-butyl-1-ethyl-6,6-
Diphenylfulvene (14.3 mmol) was added and stirred under reflux for 30 hours. The reaction solution was poured into 100 ml of 2N aqueous hydrochloric acid solution in an ice bath, diethyl ether was added to separate the organic layer, and the aqueous layer was extracted twice with 50 ml of diethyl ether. The organic layer was combined and washed with a saturated aqueous sodium hydrogen carbonate solution, water, and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. Thereafter, the residue was purified by column chromatography to obtain 4.2 g of a white solid. The yield was 53%. Identification was performed by FD-mass spectrometry spectrum (FD-MS). The measurement results are shown below.

FD-MS: m / z = 592 (M ⁺ )
(Iv) Synthesis of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride 100 ml with a magnetic stirrer tip and a three-way cock The Schlenk flask was thoroughly purged with nitrogen, and 1.0 g of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) (1 .68 mmol) was dissolved in 40 ml of dehydrated diethyl ether. To this solution, 2.2 ml (3.4 mmol) of a 1.56 M n-butyllithium hexane solution was gradually added dropwise in an ice bath, followed by stirring at room temperature for 28 hours. The reaction solution was sufficiently cooled in a dry ice / methanol bath, and 0.39 g of zirconium tetrachloride (1.68 mmol) was added. After stirring for 48 hours while gradually returning to room temperature, the solvent was distilled off under reduced pressure. The slurry was reslurried with hexane and filtered through a glass filter filled with diatomaceous earth. The brown solid on the filter was extracted with a small amount of dichloromethane and filtered. The solvent was distilled off under reduced pressure for each of the obtained hexane solution and dichloromethane solution. The dark orange solid was washed with a small amount of pentane and diethyl ether, respectively, and dried under reduced pressure to obtain 140 mg (0.186 mmol) of the target compound as an orange solid. Identification was performed by ¹ H-NMR spectrum and FD-mass spectrometry spectrum.
The measurement results are shown below.

¹ H-NMR spectrum (270 MHz, CDCl ₃ , TMS standard): δ / ppm 7.90-8.07 (m, 5H), 7.75 (m,
1H), 7.15-7.60 (m, 8H), 6.93 (m, 1H), 6.15-6.25 (m, 2H), 5.6 (d, 1H), 2.05 + 2.25 (q,
2H), 0.95−1.15 (s + t + s, 30H)
FD-MS: m / z = 752 (M ⁺ )
[Polymerization example]
[Polymerization Example (A-1)]
(Synthesis of syndiotactic propylene polymer (A-1))
To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branched flask with sufficient nitrogen substitution, to which was added 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), followed by dibenzylmethylene (cyclopentadiene). Enyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride in toluene 5.0 μmo
was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated to initiate polymerization. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. under normal pressure for 45 minutes, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 2.38 g of polymer was obtained. The polymerization activity is 0.63 kg-PP / mmol-Zr · hr, and the obtained polymer [η] is 1.9 dl / g, Tm = 158 ° C. (Tm ₁ = 152 ° C., Tm ₂ = 158 ° C.). Yes, rrrr fraction = 93.5%. This operation was repeated to obtain the required amount of polymer and used in the examples.

[Polymerization Example (A-2)]
(Synthesis of syndiotactic propylene polymer (A-2))
To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branched flask with sufficient nitrogen substitution, 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), and then dibenzylmethylene (cyclopentadiene). Enil) (2,
Toluene solution of 7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride (5.0 μmol) was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated to initiate polymerization. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. for 10 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 6.95 g of polymer was obtained. The polymerization activity is 7.58 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer is 2.9 dl / g, Tm = 162.0 ° C., rrrr fraction = 95.3%. there were. This operation was repeated to obtain the required amount of polymer and used in the examples.
(Syndiotactic propylene polymer (A-3)
Total syndiotactic polypropylene (trade name: Finaplas 1471, MFR = 5.0 g / 10 min) was used in the examples. The physical properties are shown in Table 1.
[Polymerization Example A-4]
(Synthesis of syndiotactic propylene polymer (A-4))
Except that hydrogen was further supplied to the polymerization system, it had the same TMA softening temperature, rrrr fraction, and Mw / Mn as the polymer (A-1) according to the production method of Polymerization Example A-1, and [η ] = 1.
A syndiotactic propylene polymer (A-4) (propylene homopolymer) of 4 dl / g was produced. Table 3 shows the physical properties of the polymer (A-4).
[Polymerization Example A-5]
(Synthesis of syndiotactic propylene polymer (A-5))
Except that hydrogen was further supplied to the polymerization system, it had the same TMA softening temperature, rrrr, Mw / Mn as the polymer (A-1) according to the production method of Polymerization Example A-1, and [η] = 1 .2 dl / g
Syndiotactic propylene polymer (A-5) (propylene homopolymer) was used. Table 3 shows the physical properties of the polymer (A-5).
(Syndiotactic propylene polymer (A-6)
Syndiotactic polypropylene (trade name: Finaplas1571, MFR = 9.1 g / 10 min) manufactured by Total was used in the examples. Table 3 shows the physical properties of the polymer (A-6).

[Polymerization Example (B-1)]
(Synthesis of propylene / α-olefin copolymer (B-1))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.66 MPa, the system internal pressure was adjusted to 1.36 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 15 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.36 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 105 g, [η] measured in decalin at 135 ° C. was 2.5 (dL / g), and MFR was 0.7 (g / 1).
0 min). Table 1 shows the measured physical properties of the obtained polymer. Rr ₁
The value was 78%.

[Polymerization Example (B-2)]
(Synthesis of propylene / α-olefin copolymer (B-2))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.64 MPa, the system internal pressure was adjusted to 1.34 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 15 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.34 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 109 g, [η] measured in decalin at 135 ° C. was 2.6 (dL / g), and MFR was 0.6 (g / 1
0 min). Table 1 shows the measured physical properties of the obtained polymer. Rr ₁
The value was 76%.

[Polymerization Example (B-3)]
(Synthesis of propylene / α-olefin copolymer (B-3))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and the pressure inside the system was adjusted with propylene. After pressurizing to 0.67 MPa, the system pressure was adjusted to 1.37 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 10 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.37 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 90 g, [η] measured in decalin at 135 ° C. was 2.3 (dL / g), and MFR was 1.0 (g / 10).
min). Table 1 shows the measured physical properties of the obtained polymer. The rr ₁ value was 75%.

[Polymerization Example (B-4)]
(Synthesis of propylene / α-olefin copolymer (B-4))
In a 4000 ml polymerization apparatus sufficiently purged with nitrogen, 1834 ml of dry hexane, 20 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, and then the temperature inside the polymerization apparatus was raised to 70 ° C. with propylene. After pressurizing the system pressure to 0.63 MPa, the system pressure was adjusted to 1.33 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 10 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.33 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 102 g, [η] measured in decalin at 135 ° C. was 2.3 (dL / g), MFR
Was 1.0 (g / 10 min). Table 1 shows the measured physical properties of the obtained polymer. The rr ₁ value was 75%.

[Polymerization Example B-5]
(Synthesis of propylene / α-olefin copolymer (B-5))
After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) in a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 50 ° C., and the pressure inside the system was adjusted with propylene. After pressurizing to 0.67 MPa, the system pressure was adjusted to 1.37 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel, polymerized for 10 minutes while maintaining the internal temperature at 50 ° C. and the internal pressure at 1.37 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 78 g, [η] = 3.5 (dL / g) measured in decalin at 135 ° C., and the ethylene content measured by ¹³ C-NMR was 18 mol%. Table 3 shows the measured physical properties of the obtained polymer.

Details of the ethylene / butene copolymer (C) and the propylene polymers (D-1) to (D-8) are as follows.
(Ethylene / Butene Copolymer (C))
Table 1 shows the physical properties of the ethylene / butene-1 random copolymers (C-1) to (C-3). (Propylene polymer (D-1))
PP manufactured by Prime Polymer Co., Ltd. (trade name F102W, MFR = 2.1 g / 10 min)
(Propylene polymer (D-2))
PP manufactured by Prime Polymer Co., Ltd. (trade name J104W, MFR = 5.2g / 10min)
(Propylene polymer (D-3))
PP made by Prime Polymer (trade name B101, MFR = 0.7 g / 10 min)
(Propylene polymer (D-4))
PP manufactured by Prime Polymer Co., Ltd. (trade name J106G, MFR = 15.0 g / 10 min)
(Propylene polymer (D-5))
PP manufactured by Prime Polymer Co., Ltd. (trade name J107G, MFR = 30.0 g / 10 min)
(Propylene polymer (D-6))
PP manufactured by Prime Polymer Co., Ltd. (trade name J108M, MFR = 45.0g / 10min)
(Propylene polymer (D-7))
(Synthesis of propylene / ethylene / butene copolymer)
After charging 1834 ml of dry hexane, 1-butene and 110 g of triisobutylaluminum (1.0 mmol) into a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 55 ° C. After pressurizing the system pressure to 0.58 MPa, the system pressure was adjusted to 0.75 MPa with ethylene. Subsequently, diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride synthesized in Synthesis Example 2 was 0.001 mmol and 0 in terms of aluminum. A toluene solution contacted with 3 mmol of methylaluminoxane (manufactured by Tosoh Finechem) was added to the polymerization vessel, and polymerization was performed for 25 minutes while maintaining the internal temperature at 55 ° C. and the internal pressure at 0.75 MPa with ethylene. Methanol was added to stop the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 120.2 g and MFR was 0.7 (g / 10 min). Table 4 shows the measured physical properties of the obtained polymer.
(Propylene polymer (D-8))
Except for setting the polymerization temperature to 40 ° C., the same ethylene content and butene content as the polymer (D-7) produced according to the production conditions of the propylene polymer (D-7), [η] = 4.0
A polymer with Mw / Mn = 2.1 was used in the examples. Table 4 shows the physical properties.

Table 4 shows the physical properties of the propylene polymers (D-1) to (D-8).
Isotactic propylene polymers (D-1) to (D-8), and (B-1) to (B-5), (A-1), (A-3), (A- A plot of MFR and [η] of 4), (A-5), and (A-6) is shown in FIG. It can be seen that the isotactic polymer and the polymer of the present invention are distinguished by the formula (b-2).

[Example 1]
Syndiotactic polypropylene (A-1) 10 obtained in [Polymerization Example (A-1)]
0 part by weight, ethylene / 1-butene random copolymer (C-1) (MFR (190 ° C.) = 4
. 0, 1-butene content 12 mol%) 25 parts by weight, and 0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant with respect to the composition, 0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer and 0.1 weight of calcium stearate as a hydrochloric acid absorbent Part mix. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge of 40 g (apparatus batch volume = 60 cm ³ ), 50 rpm
After melt-kneading for 5 minutes, it was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Excellent moldability and heat resistance, as well as excellent transparency and low temperature impact resistance.

[Example 2]
Syndiotactic polypropylene (A-1) 10 obtained in [Polymerization Example (A-1)]
0 part by weight, ethylene / 1-butene random copolymer (C-1) (MFR (190 ° C.) = 4
. 0, 1-butene content 12 mol%) 66.7 parts by weight, and 0.1 weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant with respect to the composition 0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer, and 0. 1 part by weight is blended. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge of 40 g (apparatus batch volume = 60 cm ³ ), 50 r.
After melting and kneading at pm for 5 minutes, the sheet was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Excellent moldability and heat resistance, as well as transparency, flexibility, and low temperature impact resistance.

[Example 3]
Syndiotactic polypropylene (A-1) 75 obtained in [Polymerization Example (A-1)]
Parts by weight, 25 parts by weight of the propylene / ethylene copolymer (B-1) obtained in [Polymerization Example (B-1)], ethylene / 1-butene random copolymer (C-3) (MFR ( 190 ° C.) = 4.0, 1-butene content: 15 mol%) and 25 parts by weight of the composition and 0% tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant. .1 part by weight, 0.1 part by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer, calcium stearate as a hydrochloric acid absorbent Is blended by 0.1 part by weight. Thereafter, a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd. was used, and the amount of resin charged was 40 g (apparatus batch volume = 60 cm ³ ), 50 rpm, 5 at a set temperature of 200 ° C.
After melt-kneading for a minute, it was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Excellent moldability and heat resistance, as well as transparency, flexibility, and low temperature impact resistance.

[Example 4]
Syndiotactic polypropylene (A-1) 66 obtained in [Polymerization Example (A-1)]
. 7 parts by weight and the propylene / ethylene copolymer (B-3) obtained in [Polymerization Example (B-3)]
) 33.4 parts by weight, ethylene / 1-butene random copolymer (C-2) (MFR (190 ° C.) = 0.5, 1-butene content 12 mol%) 66.7 parts by weight and In contrast, 0.1 part by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant,
0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer and 0.1 weight of calcium stearate as a hydrochloric acid absorbent Part mix. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge of 40 g (apparatus batch volume = 60 cm ³ ),
After melt-kneading at 50 rpm for 5 minutes, the sample was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Excellent moldability and heat resistance, as well as transparency, flexibility and impact resistance.

[Example 5]
Syndiotactic polypropylene (A-2) 50 obtained in [Polymerization Example (A-2)]
Parts by weight, and propylene / ethylene copolymer (B-4) 5 obtained in [Polymerization Example (B-4)] 5
0 parts by weight, 25 parts by weight of ethylene / 1-butene random copolymer (C-3) (MFR (190 ° C.) = 4.0, 1-butene content 15 mol%) and the composition 0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as an antioxidant and n-octadecyl-3- (4'-hydroxy-3 ', 5'- as a heat stabilizer 0.1 part by weight of di-t-butylphenyl) propinate and 0.1 part by weight of calcium stearate as a hydrochloric acid absorbent are blended. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge amount of 40 g (device batch volume = 60 cm ³ ), 50 rpm,
After melt-kneading for 5 minutes, it was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Excellent moldability and heat resistance, as well as transparency, flexibility and impact resistance.

[Reference Example 1]
Syndiotactic polypropylene (A-1) 10 obtained in [Polymerization Example (A-1)]
0 parts by weight, 150 parts by weight of ethylene / 1-butene random copolymer (C-1) (MFR (190 ° C.) = 4.0, 1-butene content 12 mol%) and the composition 0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as an antioxidant and n-octadecyl-3- (4'-hydroxy-3 ', 5'- as a heat stabilizer 0.1 part by weight of di-t-butylphenyl) propinate and 0.1 part by weight of calcium stearate as a hydrochloric acid absorbent are blended. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge of 40 g (apparatus batch volume = 60 cm ³ ), 50 rpm
After melt-kneading for 5 minutes, it was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties.

[Comparative Example 2]
Total Syndiotactic Polypropylene (A-3) (trade name: Finaplas1471, MFR = 5.0 g / 10 min, rrrr fraction = 69%) 100 parts by weight, ethylene / 1-butene random copolymer ( C-1) (MFR (190 ° C.) = 4.0, 1-butene content 12 mol%) 25 parts by weight, and tri (2,4-di-t as a secondary antioxidant) with respect to the composition -Butylphenyl) phosphate 0.1 parts by weight, and 0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer Then, 0.1 part by weight of calcium stearate as a hydrochloric acid absorbent is blended. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge amount of 40 g (device batch volume = 60 cm ³ ), 50 rpm, melt for 5 minutes, and then taken out 20 It was made into a sheet with a cooling press set at 0 ° C., and cut into an appropriate size to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. It is inferior to moldability and heat resistance as compared to the examples.

[Comparative Example 3]
60 parts by weight of Total Syndiotactic Polypropylene (A-3) (trade name: Finaplas 1471, MFR = 5.0 g / 10 min, rrrr fraction = 69%), [Polymerization Example (B-3
)] And 40 parts by weight of the propylene / ethylene copolymer (B-3) obtained as described above and tri (2,4-di-t-butylphenyl) phosphine as a secondary antioxidant with respect to the composition. Fate 0.1
Parts by weight, 0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer, and 0 of calcium stearate as a hydrochloric acid absorbent Mix 1 part by weight. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge amount of 40 g (device batch volume = 60 cm ³ ), 50 rpm, melt for 5 minutes, and then taken out 20 It was made into a sheet with a cooling press set at 0 ° C., and cut into an appropriate size to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. It is inferior in moldability, heat resistance and impact resistance compared to the examples.

FIG. 7 is a graph plotting the relationship between a specific isothermal crystallization temperature (T _iso ) and a half crystallization time (t _1/2 ) at the temperature for the syndiotactic propylene polymers described in the examples and comparative examples of the present invention. is there. A portion surrounded by a thick line indicates a region of inequality (Eq-1) which is a preferable property of the syndiotactic propylene polymer (A) of the present invention. It is the figure which plotted the relationship between MFR and [(eta)] about the polymer applicable to the (A) component or (B) component of this invention, and an isotactic propylene-type polymer. In addition, the part enclosed with the thick line shows the area | region of (b-2) which is one of the preferable characteristics of (B) component of this invention, and a broken line shows the preferable range of (b-2).

Claims (12)

Syndiotactic propylene polymer (A) 100-25 parts by weight and propylene / α-olefin copolymer (B) 0-75 parts by weight (provided that the total of (A) and (B) is 100 parts by weight) When,
It comprises 1 to 100 parts by weight of an ethylene / α-olefin copolymer (C) with respect to a total of 100 parts by weight of (A) and (B), and the polymer (A) satisfies the following requirement (a): The propylene-based polymer composition (X) in which the copolymer (B) satisfies the following requirement (b) and the copolymer (C) satisfies the following requirement (c).
(A): The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, and the melting point (Tm) determined by DSC is 156 ° C. or more, which is derived from propylene. Containing structural units in an amount exceeding 90 mol% (however, the total amount of structural units in the polymer (A) is 100 mol%).
(B): Containing structural units derived from propylene in an amount of 55 to 90 mol% (provided that the total amount of structural units in the copolymer (B) is 100 mol%), and having 2 carbon atoms 10 to 45 mol% of structural units derived from at least one olefin selected from -20 α-olefins (excluding propylene) (provided that structural units derived from propylene and α-olefins having 2 to 20 carbon atoms ( However, the MFR measured at 230 ° C. and a 2.16 kg load in accordance with JIS K-6721 is 0.01. In the range of ˜100 g / 10 min and satisfy any one or more of the following requirements (b-1) or (b-2);
(B-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B-2): Intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) satisfy the following relational expression:
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
(C): 50 to 99 mol% of structural units derived from ethylene (provided that the total amount of structural units in the copolymer (C) is 100 mol%), and carbon atoms other than ethylene 1 to 50 mol% of structural units derived from an α-olefin having 3 to 20 (however, the total of structural units derived from ethylene and an α-olefin having 3 to 20 carbon atoms is 100 mol%) MFR measured in accordance with JIS K-6721 and measured at 190 ° C. under a load of 2.16 kg is in the range of 0.01 to 100 g / 10 min, and the density = 0. It is 910-0.850 (g / cm < ³ >). Syndiotactic propylene polymer (A) 98-40 parts by weight and propylene / α-olefin copolymer (B) 2-60 parts by weight (however, the sum of (A) and (B) is 100 parts by weight) When,
It comprises 1 to 100 parts by weight of an ethylene / α-olefin copolymer (C) with respect to a total of 100 parts by weight of (A) and (B), and the polymer (A) satisfies the following requirement (a): The propylene-based polymer composition (X) according to claim 1, wherein the copolymer (B) satisfies the following requirement (b ') and the copolymer (C) satisfies the following requirement (c'). ;
(A): The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, and the melting point (Tm) determined by DSC is 156 ° C. or more, which is derived from propylene. Containing structural units in an amount exceeding 90 mol% (however, the total amount of structural units in the polymer (A) is 100 mol%).
(B ′): Containing structural units derived from propylene in an amount of 65 to 90 mol% (provided that the total amount of structural units in the copolymer (B) is 100 mol%), and the number of carbon atoms 10 to 35 mol% of structural units derived from at least one olefin selected from 2 to 20 α-olefins (excluding propylene) (provided that the structural units derived from propylene and the α-olefins having 2 to 20 carbon atoms) MFR measured at 230 ° C. and 2.16 kg load in accordance with JIS K-6721 is 0.00. In the range of 01 to 100 g / 10 min and satisfy any one or more of the following requirements (b-1) or (b-2);
(B-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B-2): The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) satisfy the following relational expression.
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
(C ′) 60 to 95 mol% of structural units derived from ethylene (however, the total amount of the structural units in the copolymer (C) is 100 mol%), and carbon other than ethylene 5 to 40 mol% of structural units derived from an α-olefin having 3 to 20 atoms (however, the total of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms is 100 mol) The MFR measured with a load of 2.16 kg at 190 ° C. in the range of 0.01 to 100 g / 10 min in accordance with JIS K-6721, and the density = 0 910 to 0.850 (g / cm ³ ). 100 parts by weight of syndiotactic propylene polymer (A),
1 to 100 parts by weight of an ethylene / α-olefin copolymer (C), the polymer (A) satisfies the following requirement (a), and the copolymer (C) satisfies the following requirement (c ′). Each of the propylene-based polymer composition (X) according to claim 1;
(A): The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, and the melting point (Tm) determined by DSC is 156 ° C. or more, which is derived from propylene. Containing structural units in an amount exceeding 90 mol% (however, the total amount of structural units in the polymer (A) is 100 mol%).
(C ′) 60 to 95 mol% of structural units derived from ethylene (however, the total amount of the structural units in the copolymer (C) is 100 mol%), and carbon other than ethylene 5 to 40 mol% of structural units derived from an α-olefin having 3 to 20 atoms (however, the total of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms is 100 mol) The MFR measured with a load of 2.16 kg at 190 ° C. in the range of 0.01 to 100 g / 10 min in accordance with JIS K-6721, and the density = 0 910 to 0.850 (g / cm ³ ). (1) The propylene-based weight according to any one of claims 1 to 3, wherein the half crystallization time (t _1/2 ) in isothermal crystallization at 110 ° C. determined by a differential scanning calorimeter is in the range of 1000 sec or less. Combined composition (X). (2) The propylene-based polymer composition (X) according to any one of claims 1 to 3, which has a needle penetration temperature of 145 ° C or higher.   The syndiotactic propylene polymer (A) has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.1 to 10 dL / g, and a heat of fusion determined by differential scanning calorimetry (DSC) measurement. The propylene-based polymer composition (X) according to any one of claims 1 to 3, wherein (ΔH) is 40 mJ / mg or more.   3. The propylene / α-olefin copolymer (B) has a molecular weight distribution (Mw / Mn, Mn: number average molecular weight, Mw: weight average molecular weight) determined by GPC of 3.5 or less. The propylene-based polymer composition (X) described.   The molded object formed using the propylene-type polymer composition (X) in any one of Claims 1-7.   The sheet | seat formed using the propylene-type polymer composition (X) in any one of Claims 1-7.   The unstretched or stretched film which uses the propylene polymer composition (X) in any one of Claims 1-7.   A laminate in which at least one layer is a layer containing the propylene polymer composition (X) according to any one of claims 1 to 7.   The nonwoven fabric which uses the propylene-type polymer composition (X) in any one of Claims 1-7.

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