JP4979987B2 - PROPYLENE POLYMER COMPOSITION AND MOLDED BODY USING THE COMPOSITION - Google Patents

Description

  The present invention relates to a propylene-based polymer composition and a molded body using 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 (J. Am. Chem. Soc., 1988, 110, 6255-6256: Non-Patent Document 1).

  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.

In addition, in JP-A-8-59916 (Patent Document 3), syndiotactic polypropylene having a syndiotactic pentad fraction measured by ¹³ C-NMR of 97 to 99.99% by weight 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, flexibility, scratch resistance, wear resistance and vibration damping properties.
Japanese Patent Laid-Open No. 3-12439 Japanese Patent Laid-Open No. 07-247387 JP-A-8-59916 JP 2000-191852 A JP 2000-191858 A J. Am. Chem. Soc., 1988, 110, 6255-6256

  The problem to be solved by the present invention is to solve the above points, and the present invention provides a propylene-based polymer composition excellent in moldability and heat resistance, moldability and heat resistance. Propylene-based polymer composition with excellent properties, scratch resistance, wear resistance, and vibration damping properties, and flexibility in addition to moldability, heat resistance, scratch resistance, wear resistance, and vibration damping properties Propylene-based polymer composition excellent in moldability and heat resistance, as well as a propylene-based polymer composition excellent in scratch resistance, abrasion resistance, flexibility, and low-temperature impact resistance For the purpose.

The propylene polymer composition (X) of the present invention comprises 10 to 95 parts by weight of a syndiotactic propylene polymer (A),
90-5 parts by weight of propylene / α-olefin copolymer (B) (However, (A) and (B
)), The polymer (A) satisfies the following requirement (a), and the copolymer (B) satisfies the following requirement (b): Features
(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 30 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 70 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): 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)
As a preferred embodiment of the propylene-based polymer composition (X) of the present invention (hereinafter also simply referred to as “composition (X)”),
From a total of 100 parts by weight of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B), further from (C-1) rosin resin, terpene resin and petroleum resin And a propylene polymer composition containing 0.1 to 100 parts by weight of one or more resins selected from the group (hereinafter, this composition may be referred to as “composition (i)”).

Preferred forms of the composition (X) and the composition (i) are the propylene / α-olefin copolymer (B),
Containing a structural unit derived from propylene in an amount of 30 to 90 mol%, a total of 10 structural units derived from ethylene and structural units derived from an α-olefin having 4 to 20 carbon atoms.
Propylene / ethylene contained in an amount of ˜70 mol% (here, the total of the structural unit derived from propylene, the structural unit derived from ethylene, and the structural unit derived from α-olefin having 4 to 20 carbon atoms is 100 mol%) -It is an α-olefin copolymer having 4 to 20 carbon atoms, and the proportion of structural units derived from ethylene is P _E (mol%), and the proportion of structural units derived from α-olefins having 4 to 20 carbon atoms is P _HAO. In the case of (mol%), a propylene-based polymer composition (X) where P _E ≦ P _HAO is mentioned.

As a preferable aspect of the propylene polymer composition (X) of the present invention,
Non-crosslinked or partially crosslinked olefinic thermoplastic elastomer with respect to a total of 100 parts by weight of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B) The propylene polymer composition according to claim 1 comprising 0.1 to 500 parts by weight of (C-2) (hereinafter, this composition may be referred to as “composition (ii)”). .

  In the composition (X), 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 differential scanning calorimeter ( The heat of fusion (ΔH) determined by DSC measurement is preferably 40 mJ / mg or more.

In the composition (X), GPC of the propylene · alpha-olefin copolymer polymer (B)
It is preferable that the molecular weight distribution (Mw / Mn, Mn: number average molecular weight, Mw: weight average molecular weight) calculated | required by (3) is 3.5 or less.

The molded product of the present invention comprises the composition (X).
The sheet | seat of this invention uses the said composition (X).
The unstretched or stretched film of the present invention comprises the composition (X).
The laminate of the present invention is a laminate in which at least one layer thereof is a layer comprising the composition (X).
The nonwoven fabric of this invention uses the said composition (X).

The propylene polymer composition (X) of the present invention is excellent in moldability and heat resistance.
Further, in the propylene-based polymer composition (X) of the present invention, the propylene / α-olefin copolymer (B) has an ethylene-derived constituent unit ratio of P _E (mol%) and 4 to 20 carbon atoms. When the proportion of α-olefin-derived structural units is P _HAO (mol%), if P _E ≦ P _HAO is satisfied, the moldability, heat resistance, scratch resistance, wear resistance, and vibration damping properties are excellent. ing.

  The propylene polymer composition (X) of the present invention has moldability and heat resistance when one or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins are added. Excellent in scratch resistance, wear resistance, vibration control and flexibility.

  The propylene polymer composition (X) of the present invention is excellent in moldability, heat resistance, scratch resistance, abrasion resistance flexibility, and low temperature impact resistance when a thermoplastic elastomer is added. Yes.

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

(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, 3-methyl-1-butene, 1-pentene, 1-hexene, 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). More than% is included. 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). 0 mol% of structural units derived from
It is contained in an amount of less than 10 mol% (herein, the total of the structural units derived from propylene and the structural units derived from α-olefins having 2 to 20 carbon atoms (excluding propylene) is 100 mol%), A constituent unit derived from propylene in an amount of 91 mol% or more and 100 mol% or less, and a constituent unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 0 mol% or more and 9 mol% or less. It is preferable to contain by quantity.

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. , More preferably 93% or more, still more preferably 94% or more, the syndiotactic propylene polymer (A) having an rrrr fraction in this range is excellent in moldability, heat resistance and transparency, Good properties as crystalline polypropylene are preferred. 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 in terms of Prrrr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the third unit in a site where five 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, Especially 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) 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, and particularly preferably 55 mJ / mg or more.

  The differential scanning calorimetry is performed, for example, as follows. 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 Perkin Elmer, 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 is obtained from a DSC curve obtained by lowering the temperature at 320 ° C./min and maintaining the isothermal crystallization temperature. Here, the half crystallization time (t _1/2 ) is obtained as isothermal crystallization process start time (time when the isothermal crystallization temperature is reached from 200 ° C.) 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 superior 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 preferred embodiment of the syndiotactic propylene polymer (A), in addition to the preferred embodiment (satisfying ΔH ≧ 40 mJ / mg and satisfying (Eq-1)), the following requirement (n-decane acceptable) The aspect which satisfy | fills the amount of melt | dissolution part) simultaneously is mentioned.

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. It is desirable to be. The amount of the n-decane soluble part is an index closely related to the blocking property of the syndiotactic propylene polymer (A) or a 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, this requirement (n
The syndiotactic propylene polymer (A) that also satisfies (the amount of decane-soluble part) has very good anti-blocking properties.

Accordingly, one of the most preferred embodiments of the syndiotactic propylene polymer (A) contains a structural unit derived from propylene in an amount exceeding 90 mol%, and ¹³ C-NM.
The syndiotactic pentad fraction (rrrr fraction) measured by R is 85% or more, the melting point (Tm) determined by DSC is 145 ° C. or more, and the heat of fusion (ΔH) is 40 mJ / mg or more. Yes, it is a syndiotactic propylene polymer satisfying the formula (Eq-1) and having an n-decane soluble part amount of 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 in 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, a hydrocarbon group and a silicon-containing group, and the two groups R ⁷ and R ¹⁰ are selected from a hydrocarbon group and a silicon-containing group, not a hydrogen atom, R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹¹ may be the same or different.
And one or more adjacent group combinations selected from R ¹² , 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 and 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 is selected from halogen, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair in the same or different combinations However, j is an integer of 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. Examples of known production methods include the production methods described in WO 2001/27124 and WO 2004/087775 by the present applicant.

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, a 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. An organoaluminum oxy compound that is insoluble or sparingly soluble.

  In addition, examples of the organoaluminum oxy compound include 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 carbon atom having 1 to 10 carbon atoms. Indicates a hydrogen 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. As compound (II-2) (hereinafter sometimes referred to as “ionic compound” or “component (II-2)”), JP-A-1-501950,
JP-A-1-502036, JP-A-3-179005, JP-A-3-179006
And Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-3-207703, JP-A-3-207704, USP5321106, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  The ionic compound preferably employed in the present invention is a compound represented by the following general formula [6].

In the formula [6], examples of R ^{e +} include H ⁺ , a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal. R ^{f to} R ⁱ may be the same as or different from each other, and are organic groups, preferably aryl groups.

  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, etc. .

  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, 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 include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

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 a compound 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, more preferably 10 to 300 μm, and even more preferably 20 to 200 μm. Surface area of 50 to 1000 m ² / g, preferably 100
It is desirable that the pore volume be in the range of -700 m ² / g and the pore volume be in the range of 0.3-3.0 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.
The clay and clay mineral are also preferably subjected 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 which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using 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. Guest compounds that intercalate include TiCl4, Z
Cationic inorganic compounds such as rCl4, Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (O
Metal alkoxides such as R) ₃ (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 metal hydroxide ions such as ⁺ . 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-eikosen.

Propylene / α-olefin copolymer (B)
The propylene / α-olefin copolymer (B) contains 30 to 90 mol% of structural units derived from propylene (provided that the total amount of the structural units in the copolymer (B) is 100 mol%). Containing a structural unit derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) in an amount of 10 to 70 mol%, in accordance with JIS K-6721 The MFR measured at 230 ° C. and a 2.16 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) and (b-2) It is characterized by that.
(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 decalin at 135 ° C. and MFR (g / 10 min) measured at 230 ° C. 2.16 kgf load according to JIS K-6721 Satisfies the following relational expression.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20)
In the present invention, the propylene / α-olefin copolymer (B) having various physical properties within the above-mentioned range is used without any particular limitation. As the propylene / α-olefin copolymer (B),
Containing structural units derived from propylene in an amount of 30 to 90 mol%, preferably 40 to 90 mol%, more preferably 50 to 90 mol%, still more preferably 51 to 90 mol%,
The structural unit derived from ethylene and the structural unit derived from an α-olefin having 4 to 20 carbon atoms are combined in a total of 10 to 70 mol% (wherein the structural unit derived from propylene, the structural unit derived from ethylene, and the carbon number of 4 to 20). Of the α-olefin-derived structural unit is 100 mol%), preferably 10 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 10 to 49 mol%. The copolymer (B) contained in an amount of 1 is one of preferred embodiments from the viewpoint of vibration damping properties, scratch resistance, and abrasion resistance.

Furthermore, the propylene / α-olefin copolymer (B) is a propylene / ethylene / α-olefin copolymer having 4 to 20 carbon atoms, and the proportion of the structural unit derived from ethylene is P _E (
Mol%), the proportion of the constituent unit derived from α- olefin having 4 to 20 carbon atoms in the case of a P _HAO, and more preferably a copolymer which is a P _E ≦ P _HAO. More specifically, P _E / P _HAO is 0.01 to 1.00, preferably 0.05 to 0.80, more preferably 0.06 to 0.60, and still more preferably 0.10. It is desirable that it is ˜0.50.

The propylene polymer composition (X) of the present invention is further described below with respect to a total of 100 parts by weight of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B). In the case of a composition (composition (i)) containing 0.1 to 100 parts by weight of the hydrocarbon resin (C-1), the propylene / α-olefin copolymer (B) is:
Containing structural units derived from propylene in an amount of 30 to 90 mol%, preferably 40 to 90 mol%, more preferably 50 to 90 mol%, still more preferably 51 to 90 mol%,
A total of 10 to 70 mol% of structural units derived from ethylene and structural units derived from α-olefins having 4 to 20 carbon atoms (where propylene-derived structural units, ethylene-derived structural units and carbon numbers of 4 to 20 carbon atoms are used). The total amount of structural units derived from α-olefin is 100 mol%), preferably 10 to 60 mol%, more preferably 10 to 50 mol%, and still more preferably 10 to 49 mol%. in containing and P _E (mol%) the amount of the structural unit derived from ethylene, the amount of the structural unit derived from α- olefin having 4 to 20 carbon atoms in the case of a P _HAO, is P _E ≦ P _HAO ,
A propylene / ethylene / α-olefin copolymer having 4 to 20 carbon atoms is preferable.

More specifically, P _E / P _HAO is preferably 0.01 to 1.00, more preferably 0.05 to 0.80, and further preferably 0.06 to 0.60. , 0
. Particularly preferred is 10 to 0.50.

The propylene-based polymer composition (X) of the present invention is further non-crosslinked with respect to a total of 100 parts by weight of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B). In the case of a composition containing 0.1 to 500 parts by weight of a crosslinked olefinic thermoplastic elastomer (C-2) (“composition (ii)”), the propylene / α-olefin copolymer (B )
Containing structural units derived from propylene in an amount of 30 to 90 mol%, preferably 50 to 90 mol%, more preferably 55 to 90 mol%, still more preferably 60 to 90 mol%,
The structural unit derived from ethylene and the structural unit derived from an α-olefin having 4 to 20 carbon atoms are combined in a total of 10 to 70 mol% (wherein the structural unit derived from propylene, the structural unit derived from ethylene, and the carbon number of 4 to 20 Of the α-olefin-derived structural unit is 100 mol%), preferably 10 to 50 mol%, more preferably 10 to 40 mol%. preferable.

Here, the total of the structural unit derived from propylene and the structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol%. Here, of course, as in the composition (i), in the composition (ii), the propylene / α-olefin copolymer (B) has a proportion of ethylene-derived structural units of P _E (mol%), carbon the proportion of the constituent unit derived from the number 4 to 20 of the α- olefin when the P _HAO, a P _E ≦ P _HAO, even α- olefin copolymer propylene-ethylene-4 to 20 carbon atoms good. In that case, the preferable range of P _E / P _HAO can be the same as the preferable range of P _E / P _{HAO in} the composition (i).

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, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned, especially ethylene, 1-butene, 1-hexene,
4-Methyl-1-pentene and 1-octene are preferred.

JIS K-672 of the propylene / α-olefin copolymer (B) used in the present invention.
MFR measured at 230 ° C. and 2.16 kg load in accordance with 1 is preferably in the range of 0.01 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 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 (r) measured by ¹³ C-NMR method
a propylene / α-olefin copolymer having an r fraction (triad syndiotacticity) of 60% or more, preferably 70% or more, more preferably 75% or more, and an rr fraction within this range ( B) is preferable because it has good compatibility with the syndiotactic propylene polymer (A).

  The polymer satisfying (b-1) can be obtained, for example, by copolymerizing propylene and α-olefin in the presence of a catalyst capable of producing syndiotactic polypropylene. May be manufactured.

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] measured in decalin at 230 ° C and 230 ° C in accordance with JIS K-6721.
The MFR measured with a 16 kg load satisfies the following relational expression.

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 propylene (reported as Me = 6900 (g / mol) in the paper) and the syndiotactic propylene This is 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 reason, the propylene / α-olefin copolymer (B) is considered to have good compatibility with the component (A).

The intrinsic viscosity [η] measured in 135 ° C. decalin of the propylene / α-olefin copolymer (B) is 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g, more preferably 0.5. It is desirable to be -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. The propylene / α-olefin copolymer (B) is excellent in cold resistance and low temperature characteristics when the glass transition temperature (Tg) is within the above range.

  The differential scanning calorimetry 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 7-40 carbon atoms iodoalkylaryl groups, 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 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 electron pair in the same or different combinations. ,
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) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-trichloromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Nyl) 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-butylfluorenyl) zirconi Mudichloride, 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- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, phenyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) 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-ditert-butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-di tert-Butylfluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, phenyl (m-trifluoromethyl-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-dite
rt-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) methylene (cyclopentadienyl) (2, 7-diphenyl-3,6-ditert-butylfluorenyl) zirco Um 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-ditert-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) (octamethylocta Hydrodibenzofluorenyl) 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 (cyclohexane) Ntadienyl) (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-di-tert-
(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 (a) bridged metallocene compound 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 singly 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) includes component (II-3) and component (I ′)
The molar ratio [(II-3) / M] with the transition metal atom (M) is usually 1 to 10,000, preferably 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-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. α-olefin is a single type,
Or it can use in combination of 2 or more types.

  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).

  In this copolymerization reaction, the temperature is usually 40 to 200 ° C., preferably 40 ° C. to 180 ° C., more preferably 50 ° C. to 150 ° C., and the pressure exceeds 0 to 10 MPa, preferably 0.5 to It is carried out under the condition of 10 Mpa, more preferably 0.5-7 Mpa.

[(C-1) one or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins]
Of one or more resins (C-1) selected from the group consisting of rosin resins, terpene resins and petroleum resins used in the present invention, rosin resins include natural rosin, polymerized rosin, maleic acid, fumarate. Examples thereof include modified rosin and rosin derivatives modified with acid, (meth) acrylic acid, and the like. Examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof. Furthermore, these hydrogenated substances can also be mentioned.

  Examples of the terpene resin include α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, and the like. Α-pinene, β-pinene, limonene, dipentene, An aromatic modified terpene resin obtained by polymerizing an aromatic monomer such as Moreover, these hydrogenated substances can also be mentioned.

  The petroleum resin includes, for example, an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and a copolymer petroleum resin thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And a co-polymer of C9 fraction), a coumarone indene resin containing styrenes, indenes, coumarone, other dicyclopentadiene, etc. of the tar naphtha fraction, p-tert-butylphenol and Examples thereof include alkylphenol resins typified by condensates of acetylene, xylene resins obtained by reacting o-xylene, p-xylene or m-xylene with formalin.

  In addition, one or more resins (C-1) selected from the group consisting of rosin resins, terpene resins and petroleum resins that may be used in the present invention are excellent in weather resistance and discoloration resistance. Hydrogenated derivatives are preferred. The softening point of the resin (C-1) by the ring and ball method is preferably in the range of 40 to 180 ° C. Moreover, it is preferable that the number average molecular weight (Mn) molecular weight measured by GPC of the said resin (C-1) exists in the range of about 100-10,000.

A commercially available product may be used as one or more resins (C-1) selected from the group consisting of rosin resins, terpene resins and petroleum resins, which may be used in the present invention.
[Non-crosslinked or partially crosslinked olefinic thermoplastic elastomer (C-2)]
Below, (C-2) component used by this invention is demonstrated concretely.

  The non-crosslinked or partially crosslinked olefinic thermoplastic elastomer (C-2) that may be used in the present invention comprises polypropylene and an ethylene / α-olefin random copolymer containing a nonconjugated diene. Although it is desirable to contain, it is not restricted to this, For example, even if it is a non-crosslinked or partially crosslinked olefinic thermoplastic elastomer containing polypropylene and ethylene / α-olefin random copolymer Often, the α-olefin is preferably propylene or butene.

  The MFR measured at 230 ° C. and a load of 10 kg of the non-crosslinked or partially crosslinked olefinic thermoplastic elastomer (C-2) is preferably 0.001 to 100, more preferably 0.01 to 80.

Of the uncrosslinked or partially crosslinked olefinic thermoplastic elastomer (C-2),
The melting point (Tm) obtained from the DSC endothermic curve is preferably 120 to 165 ° C, more preferably 130 to 160 ° C. The non-crosslinked or partially crosslinked olefinic thermoplastic elastomer (C-2) is a non-crosslinked thermoplastic elastomer composition or a partially crosslinked thermoplastic elastomer composition, preferably a crystalline polyolefin resin. (C-2-1) and α-olefin copolymer rubber (C-2-2).

[Crystalline polyolefin resin (C-2-1)]
The crystalline polyolefin resin (C-2-1) that may be used in the present invention is a crystalline high molecular weight obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method. It is a solid product. Such resins include, for example, isotactic and syndiotactic monoolefin polymer resins, but these representative resins are commercially available.

  Specific examples of suitable raw material olefins for the crystalline polyolefin resin (C-2-1) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3 -Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-octene, 1-decene and mixed olefins obtained by mixing two or more of these olefins.

  As the crystalline polyolefin resin (C-2-1), in particular, an isotactic polypropylene having a propylene content of 70 mol% or more, preferably a propylene content of 80 mol% or more is suitably used.

  The polymerization mode may be random type or block type, and any polymerization mode can be adopted as long as a resinous material is obtained. The MFR (A-1STM A-4 1238-65T, 230 ° C.) of the crystalline polyolefin resin (C-2-1) is usually in the range of 0.01 to 100 g / 10 minutes, particularly 0.05 to 50 g / 10 minutes. It is preferable that it exists in.

  Moreover, it is preferable that melting | fusing point (Tm) calculated | required from the endothermic curve of DSC of the crystalline polyolefin resin (C-2-1) used for the said thermoplastic elastomer (C-2) is 120-165 degreeC, 130 degreeC More preferably, it is in the range of ~ 160. The crystalline polyolefin resin (C-2-1) may be polypropylene mentioned as the above-mentioned syndiotactic polypropylene (A), or may be a crystalline polyolefin other than the above (A).

  The crystalline polyolefin resin (C-2-1) has a role of improving the fluidity and heat resistance of the composition. In the present invention, the crystalline polyolefin resin (C-2-1) is a total amount of 100 weight of the crystalline polyolefin resin (C-2-1) and the α-olefin copolymer rubber (C-2-2). In the part, it is used in a proportion of 10 to 60 parts by weight, preferably 20 to 55 parts by weight.

  When the crystalline polyolefin resin (C-2-1) is used in the above proportion, an olefinic thermoplastic elastomer composition having excellent rubber elasticity and excellent molding processing can be obtained.

[Α-Olefin Copolymer Rubber (C-2-2)]
The α-olefin polymer rubber (C-2-2) used in the present invention is an α-olefin having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and if necessary, a non-conjugated polyene, For example, a rubber obtained by copolymerization with a non-conjugated diene.

  Specific examples of the α-olefin include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-decene, Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene, Examples thereof include 12-ethyl-1-tetradecene.

  In the present invention, the above α-olefins may be used singly or as a mixture of two or more. When 4-methyl-1-pentene and other α-olefin are used as a mixture, the molar ratio of 4-methyl-1-pentene to other α-olefin (other α-olefin / 4-methyl- 1-pentene) is preferably in the range of 10/90 to 95/5.

Of the α-olefins, ethylene, propylene, and 1-butene are particularly preferably used.
Examples of the α-olefin copolymer rubber (C-2-2) include a copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms. Examples thereof include ethylene / alpha-olefins having 3 or more carbon atoms (molar ratio) of 40 / 60-95 / 5, which is the ratio of the structural units derived from α-olefins having 3 or more carbon atoms. .

  Specific examples of the non-conjugated polyene used as necessary in the present invention include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl- , 5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 4-methyl-1 , 4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1 , 5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1 , 6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1 , 4-Decadier 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene , 8-ethyl-1,8-decadiene, 9-methyl-1,8-undecadiene and the like. Among them, in particular, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), 4-ethylidene-8-methyl-1, 7-nonadiene (EMND) is preferred.

  In the present invention, when the non-conjugated polyene as described above, for example, a non-conjugated diene is used, it may be used alone or as a mixture of two or more. Furthermore, in addition to the non-conjugated polyene as described above, other copolymerizable monomers may be used as long as the object of the present invention is not impaired.

  In the α-olefin polymer rubber (C-2-2), when a non-conjugated polyene is copolymerized, the content of the structural unit derived from the non-conjugated polyene in the copolymer is: 0.01 to 30 mol%, preferably 0.1 to 20 mol%, particularly preferably 0.1 to 10 mol% (provided that the α-olefin copolymer rubber (C-2-2)) The total amount of the structural units in the mixture is 100 mol%.)

  The α-olefin copolymer rubber (C-2-2) is preferably a copolymer of α-olefin and non-conjugated polyene. In particular, an ethylene / C3 or higher α-olefin / non-conjugated polyene copolymer, which is a ratio of ethylene and C3 or higher α-olefin, ethylene / C3 or higher α-olefin (molar ratio). ) Is 40/60 to 95/5, and preferably contains 0.01 to 30 mol% of a structural unit derived from non-conjugated polyene.

  The intrinsic viscosity [η] measured in a 135 ° C. decalin solvent of the α-olefin copolymer rubber (C-2-2) is 1.0 to 10.0 dl / g, preferably 1.5 to 7 dl / g. It is in the range of g. Further, although there is no particular limitation, the melting point (Tm) obtained from the DSC endothermic curve of the α-olefin copolymer rubber (C-2-2) does not exist or may exist below 120 ° C. preferable.

  In the present invention, the α-olefin copolymer rubber (C-2-2) is composed of a crystalline polyolefin resin (C-2-1) and an α-olefin copolymer rubber (C-2-2). It is used in a proportion of 90 to 40 parts by weight, preferably 80 to 45 parts by weight in a total amount of 100 parts by weight.

  The α-olefin copolymer rubber (C-2-2) as described above can be produced by the following method. The α-olefin copolymer rubber (C-2-2) is a copolymer of an α-olefin having 2 to 20 carbon atoms and, if necessary, a non-conjugated diene in the presence of an olefin polymerization catalyst. Is obtained.

  The non-crosslinked or partially crosslinked olefinic thermoplastic elastomer composition (C-2) includes crystalline polyolefin resin (C-2-1) and α-olefin copolymer rubber (C-2). In addition to -2), a softener (C-2-3) and / or an inorganic filler (C-2-4) can be included as optional components.

  As the softener (C-2-3), softeners usually used for rubber can be used. Specifically, petroleum such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly. Coal tars such as coal tar and coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; ricinoleic acid Fatty acids such as palmitic acid, stearic acid, barium stearate, calcium stearate or metal salts thereof; synthetic polymer materials such as petroleum resin, coumarone indene resin, atactic polypropylene; dioctyl phthalate, dioctyl adipate, dioctyl sebacate, etc. Ester plasticizer; other microcrystalline wax, sub Factice), liquid polybutadiene, modified liquid polybutadiene, etc. liquid Thiokol and the like.

  In the present invention, the softener (C-2-3) is added to 100 parts by weight of the total amount of the crystalline polyolefin resin (C-2-1) and the α-olefin copolymer rubber (C-2-2). On the other hand, it is usually used in a proportion of 200 parts by weight or less, preferably 2 to 100 parts by weight.

  Specific examples of the inorganic filler (C-2-4) include calcium carbonate, calcium silicate, clay, carion, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, Examples thereof include calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, and shirasu balloon.

  In the present invention, the inorganic filler (C-2-4) is 100 parts by weight of the total amount of the crystalline polyolefin resin (C-2-1) and the α-olefin copolymer rubber (C-2-2). The amount is usually 100 parts by weight or less, preferably 2 to 50 parts by weight. In this invention, when the usage-amount of an inorganic filler (C-2-4) exceeds 100 weight part, it exists in the tendency for the rubber elasticity of a thermoplastic elastomer composition obtained and a moldability to fall.

  The partially cross-linked olefinic thermoplastic elastomer composition comprises the above-described crystalline polyolefin resin (C-2-1), α-olefin copolymer rubber (C-2-2), The softener (C-2-3) and / or inorganic filler (C-2-4) blended as necessary is dynamically mixed in the presence of an organic peroxide as described below. It is obtained by heat treatment and partial crosslinking.

  Here, “dynamically heat-treating” means kneading in a molten state. Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5- Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3 , 5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate , Tert-butylperoxyisopropyl carbonate, diacetylperoxa De, lauroyl peroxide, etc. tert- butyl cumyl peroxide and the like.

  Such an organic peroxide is based on 100 parts by weight of the total amount of the object to be treated, that is, the total amount of the crystalline polyolefin resin (C-2-1) and the α-olefin copolymer rubber (C-2-2). The amount used is 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight. If the blending amount is less than the above range, the resulting thermoplastic elastomer composition has a low degree of cross-linking, and therefore has insufficient heat resistance, tensile properties, elastic recovery, rebound resilience, and the like. Moreover, when there are more compounding quantities than the said range, the thermoplastic elastomer composition obtained may have a too high bridge | crosslinking degree, and may cause a moldability fall.

  In the present invention, in the partial crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, N′-m-phenylenedimaleimide, etc. Peroxy crosslinking aids such as polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, acrylic methacrylate, vinyl butyrate or vinyl stearate You may mix | blend a polyfunctional vinyl monomer.

By using a compound such as the above-mentioned crosslinking aid, a uniform and mild crosslinking reaction can be expected. Such a crosslinking aid or a compound such as a polyfunctional vinyl monomer is usually 2 parts by weight or less, more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the whole object to be treated. Used.

  In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese Decomposition accelerators such as naphthenates such as magnesium, lead, and mercury may also be used.

The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature ranges from the melting point of the crystalline polyolefin resin (C-2-1) to 300 ° C., and is usually 150 to 250 ° C., preferably 170 to 225 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is, 10～100,000Sec ^-1 as the shear rate is preferably 100~50,000sec ^-1.

  As a kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single-screw or twin-screw extruder can be used, and a non-open type apparatus is preferable.

  Olefin-based thermoplastic elastomer comprising crystalline polyolefin resin (C-2-1) and α-olefin copolymer rubber (C-2-2) or partially crosslinked by the above-mentioned dynamic heat treatment A composition is obtained.

  In the present invention, that the thermoplastic elastomer composition is partially crosslinked means that the gel content measured by the following method is 20% or more, preferably 20 to 99.5%, particularly preferably 45 to 98%. When it is within range. The gel content was measured by weighing 100 mg of a sample of the thermoplastic elastomer composition and cutting it into 0.5 mm × 0.5 mm × 0.5 mm strips into 30 ml of cyclohexane in a sealed container. After immersing at 23 ° C. for 48 hours, the sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained.

  From the weight of this dry residue, the weight of all cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component, and the crystalline polyolefin resin (C-2-1) in the sample before cyclohexane immersion The weight reduced is defined as “corrected final weight [y]”.

On the other hand, the weight of the α-olefin copolymer (C-2-2) in the sample is defined as “corrected initial weight [x]”. Here, the gel content is determined by the following formula.
Gel content [wt%] = (corrected final weight [y] / corrected initial weight [x]) × 100.

Propylene polymer composition (X)
The propylene polymer composition (X) according to the present invention is:
(A) 10 to 95 parts by weight of the syndiotactic propylene polymer, preferably 15 to 90 parts by weight;
(B) 90-5 parts by weight of the propylene / α-olefin copolymer, preferably 85-10
Parts by weight (however, the sum of (A) and (B) is 100 parts by weight).

The composition (X) in which the blending ratio of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer is in this range is excellent in moldability and heat resistance, and has flexibility and scratch resistance. It is preferable because of its excellent properties and wear resistance.

In addition, as a material with high heat resistance, excellent flexibility, abrasion resistance, scratch resistance, vibration damping, and adhesiveness,
(A) 10 to 95 parts by weight of the syndiotactic propylene polymer, preferably 15 to 90 parts by weight;
(B) 90-5 parts by weight of the propylene / α-olefin copolymer, preferably 85-10
Parts by weight (provided that the total of (A) and (B) is 100 parts by weight),
The propylene polymer composition (X) (composition) further comprising a total of 0.1 to 100 parts by weight of one or more resins (C-1) selected from the group consisting of rosin resins, terpene resins and petroleum resins. A thing (i)) can be mentioned preferably.

  One or more resins (C-1) selected from the group consisting of rosin resins, terpene resins and petroleum resins are preferably 1 to 90 parts by weight, more preferably 1 to 80 parts by weight, and still more preferably 2 to 2 parts by weight. An amount of 70 parts by weight is used. When (C-1) is included in the above range, the propylene-based polymer composition (X) is also excellent in adhesiveness. The composition (i) can also be a composition having excellent transparency.

In addition, as a material with high heat resistance, excellent wear resistance, scratch resistance, and low temperature impact resistance,
(A) 10 to 95 parts by weight of the syndiotactic propylene polymer, preferably 15 to 90 parts by weight;
(B) 90-5 parts by weight of the propylene / α-olefin copolymer, preferably 85-10
Parts by weight (provided that the total of (A) and (B) is 100 parts by weight),
Furthermore, a propylene polymer composition (X) comprising 0.1 to 500 parts by weight of an uncrosslinked or crosslinked olefinic thermoplastic elastomer (C-2) is preferably mentioned (composition (ii)). it can. The content of the elastomer (C-2) is more preferably 1 to 500 parts by weight, and further preferably 50 to 400 parts by weight.

The composition of the present invention is particularly excellent in moldability and heat resistance, and can also be a material excellent in flexibility, scratch resistance, and abrasion resistance.
Here, “excellent formability” means that it takes time to solidify from a molten state when molding such as injection, inflation, blow, extrusion, foaming or pressing. 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). The composition of the present invention contains a specific component (A) and component (B), whereby t _1/2
However, it can be molded without difficulty by a molding method similar to that of normally used isotactic polypropylene or the like.

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 DSCPyris 1 or DSC 7 manufactured by PerkinElmer is used.
The temperature was raised from 320 ° 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 and the temperature was kept at 110 ° C. It was obtained from the DSC curve obtained. Here, the half crystallization time (t _1/2 ) is 110
The isothermal crystallization process start time (° C. from 110 ° C. to 110 ° C.) t = 0 is obtained. The t _1/2 of the composition of the present invention can be determined as described above, but when crystallization does not occur at 110 ° C., for convenience, several measurements are performed at an isothermal crystallization temperature of 110 ° C. or less. The half crystallization time (t _1/2 ) is determined from the extrapolated value.

The propylene-based polymer composition (X) of the present invention preferably satisfies either of the following (1) and (2), and (1) and (2) are more preferably in their preferred ranges. preferable;
(1) The half crystallization time (t _1/2 ) is preferably 1000 sec or less, more preferably 500 sec or less.
(2) The softening temperature measured by the TMA method is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher.

The composition (i) which is a preferred embodiment of the present invention preferably satisfies at least one of the following (i-1) to (i-3), more preferably (i-1) and ( i-3) or (i-2) and (i-3) are satisfied, and (i-1) to (i-3) are more preferably satisfied.
(I-1) The half crystallization time (t _1/2 ) is preferably 1000 sec or less, more preferably 500 sec or less.
(I-2) The softening temperature measured by the TMA method is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher.
(I-3) The rebound resilience measured according to JISK6255 is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.

More preferably, the composition (i) further satisfies the following (i-7).
(I-7) The internal haze is preferably 50% or less, more preferably 30% or less.
The composition (i) particularly preferably satisfies the following (i-6).
(I-6) The tensile elastic modulus is in the range of 1 MPa to 1000 MPa, preferably 1 to 800 MPa, more preferably 10 MPa to 500 MPa.

The composition (ii), which is a preferred embodiment of the present invention, preferably contains at least one of the following (ii-1), (ii-2), (ii-4), and (ii-5). More preferably (ii-1) and (ii-5) or (ii-2) and (ii-5), more preferably (ii-1) and (ii-5) ( ii-4) or (ii-2), (ii-5) and (ii-4), more preferably (ii-1), (ii-2), (ii-4), (ii) Satisfy all of ii-5).
(Ii-1) The half crystallization time (t _1/2 ) is preferably 1000 sec or less, more preferably 500 sec or less.
(Ii-2) The softening temperature measured by the TMA method is preferably 145 ° C. or higher, more preferably 147 ° C. or higher.
(Ii-4) The Izod impact strength is preferably 50 J / m or more, more preferably 100 J / m.
(Ii-5) The gross change rate before and after the Gakushoku abrasion test is preferably 40 (%) or less, and more preferably 30 (%) or less.

Furthermore, the composition (ii) of the present invention more preferably satisfies the following (ii-6).
(Ii-6) The tensile modulus is preferably in the range of 1 MPa to 1000 MPa, more preferably in the range of 1 MPa to 500 MPa, and still more preferably in the range of 1 MPa to 200 MPa.

The softening point (sometimes referred to as physical property (2) or needle penetration temperature) measured by the TMA method can be measured as follows.
Thickness 1mm using Seiko SS-120 or TA Instrument Q-400
A press intrusion temperature (° C.) is obtained from a TMA curve by applying a pressure of ² kgf / cm ² to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min.

Also, rebound resilience (sometimes referred to as physical property (3)), Izod impact strength (sometimes referred to as physical property (4)), gloss change rate (sometimes referred to as physical property (5)), tensile modulus (property ( 6)), haze (sometimes referred to as physical property (7)) and the like.
(3) Rebound resilience The rebound resilience measured in accordance with JISK6255 is preferably 40% or less, more preferably 35% or less, and particularly preferably 30% or less.
(4) Izod impact strength A test piece of 12.7 mm (width) x 3.2 mm (thickness) x 64 mm (length) was punched out of a 3 mm thick press sheet, and a machined notch was added. The average value of three measurements is obtained.
(5) Gloss change rate The gloss change rate before and after the Gakushoku abrasion test is preferably 40 (%) or less, and more preferably 30 (%) or less.
(6) Tensile elastic modulus From a 1 mm thick press sheet, it was punched out using a JIS No. 3 dumbbell order bell in accordance with JIS K6301, 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 obtained.
(7) Haze Using a press sheet test piece with a thickness of 1 mm, the internal haze was measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd., and the average value of the two measurements was obtained. Ask.

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

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, a part or all of the component (A) may be graft-modified, a part or all of the component (B) may be graft-modified, one for each of the component (A) and the component (B). Part or 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 bodies are used, and if necessary, at least a part of the present invention is graft-modified by kneading with one or more unmodified bodies selected from the components (A) and (B). Propylene polymer composition (X) can be obtained.

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

  Further, by making at least a part of the composition graft-modified, the propylene-based polymer composition (X) of the present invention has 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 the polar monomer, for example, unsaturated carboxylic acid and / or derivative thereof is in the above range, the polyolefin composition (X) of the present invention has a polar group-containing resin (for example, polyester, polyvinyl alcohol, ethylene. High adhesion strength to vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, etc.).

  In addition, the propylene polymer composition (X) in which at least a part of the present invention is graft-modified is provided with another polymer such as a thermoplastic resin or an elastomer as long as the properties of the modified product are not impaired. Can be blended. Their blending may be in the graft modification step or after modification.

  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, and antioxidants may be blended as necessary.

  The propylene polymer composition (X) according to the present invention may contain polyethylene, isotactic polypropylene, or styrene elastomer, but may also contain polyethylene, isotactic polypropylene, or styrene elastomer in one embodiment. is there.

In order to further improve the moldability of the propylene polymer composition (X) 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-di-). tert-butylphenyl) sodium phosphate, pimelic acid and salts thereof, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, etc., and the amount is not particularly limited, but is 0.1 to 0.1% relative to the propylene polymer composition. There is preferably about 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 (X) as described above may be prepared by various known methods such as slurry phase, solution phase or A method of multistage polymerization in the gas phase in a continuous or batch manner, a method of mixing with a Henschel mixer, V-blender, riboblender, tumbler blender, etc., or after mixing, a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. Then, after melt-kneading, it can be produced by employing a method of granulating or pulverizing.

[Molded body using propylene polymer composition (X)]
The propylene-based polymer composition (X) according to the present invention as described above provides a molded product having excellent moldability and heat resistance, and excellent flexibility, scratch resistance, vibration damping properties, and low-temperature impact properties. Therefore, it is difficult to use syndiotactic polypropylene in the past, and it can be widely used in conventionally known polyolefin applications. In particular, the propylene-based polymer composition (X) can be used for, for example, a sheet, unstretched Or it can shape | mold and use for a stretched film, a filament, and other various-shaped molded objects. 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-based polymer composition (X) can be formed 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 (X) 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 manufactured by injection-molding the propylene-based polymer composition (X) into various shapes using a known injection molding apparatus under known conditions. The injection molded product using the propylene polymer composition (X) is hardly charged and has excellent transparency, rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, and the like. It can be widely used for automobile interior trim materials, automotive exterior materials, housings and containers for home appliances.

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

  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 the injection blow molding, after the propylene polymer composition (X) is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C., the parison is molded, and then the parison is held in a mold having a desired shape. A hollow molded body can be manufactured by blowing air and mounting it on a mold at a resin temperature of 120 ° C to 300 ° C. 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 the propylene-based polymer composition (X) 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 foam 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 is 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 0.35 g sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. The solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is placed in an NMR tube having an inner diameter of 10 mm, and ¹³ C-NMR measurement is performed at 120 ° C. The number of integration is 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) of component (A), heat of fusion (ΔH)]
Using a DSCPyris 1 or 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 half-isothermal crystallization time (t _1/2
) 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.) T _1/2 can be obtained as described above. For example, when crystallization is not performed at a certain isothermal crystallization temperature, for example, 110 ° C., several measurements are made at an isothermal crystallization temperature of 110 ° C. or less for convenience. The semi-crystallization time (t _1/2 ) was determined from the extrapolated value.

[Glass point transfer (Tg) of component (B), melting point (Tm)]
Using a Seiko Instruments DSC, 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 at 10 ° C./min. The temperature was determined from an endothermic curve that was lowered to 200 ° C. and then heated 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. and a load of 2.16 kgf in accordance with JIS K-6721.

The MFR of the ethylene / butene copolymer (C) is 19 in accordance with JIS K-6721.
The measurement was performed at 0 ° C. with a load of 2.16 kgf.
[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 0.5 to 3 mm thick sheet (spacer shape; 240 x 240 x 2 mm thick plate 80 x 80 x 0.5 to 3 mm, 4 pieces), the remaining heat is about 5-7 minutes and 10MP
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 having 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 with a thickness of 1 mm, a digital turbidimeter “NDH-2” manufactured by Nippon Denshoku Industries Co., Ltd.
0D ".

[Gloss change rate after academic wear (%)]
Using a Toyo Seiki, Gakushin Abrasion Tester, using a 2 mm-thick test piece, the tip of a 470 g wear indenter made of 45R, SUS is covered with cotton canvas # 10, and this is 23 ° C. and the number of reciprocations is 100 times. The sample was worn at a reciprocating speed of 33 times / min and a stroke of 100 mm, and the gloss change rate ΔGloss before and after that was determined as follows.

ΔGloss = (Gloss before wear-Gloss after wear) / Gloss before wear × 100
[Rebound resilience (%)]
Measured with a rebound elastic modulus device manufactured by Ueshima Seisakusho Co., Ltd. using a test piece having a thickness of 15 mm (5 sheets of 3 mm thick press sheets are stacked) in accordance with the Dupke method (Dupke method) described in JIS K6255. did.

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]
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 object 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) of octamethyloctahydrodibenzofluorenyl) methane was added, and 0.87 ml (1.37 mmol) of a 1.58 mol / L n-butyllithium hexane solution was slowly added dropwise while cooling the solution to 0 ° C. 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 3]
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 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): δ7.2−7.4 (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. After sufficiently purging with nitrogen, 3.8 g of 2,7-di-tert-butylfluorene (13.7 mmol) was dissolved in 80 ml of dehydrated diethyl ether under a nitrogen atmosphere. 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): δ7.90−8.07 (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). Enil) (3,6-
Di-tert-butylfluorenyl) zirconium dichloride in toluene solution 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. [Η] of the obtained polymer is 1.9 dl / g, Tm1 = 152 ° C., Tm2 = 158 ° C., rrrr = 93.5% Met. This operation was repeated to obtain the required amount of polymer and used in the examples.

(Syndiotactic propylene polymer (A-2))
Total syndiotactic polypropylene (trade name: Finaplas 1471, MFR = 5.0 g / 10 min) was used in the examples.
[Polymerization Example A-3]
(Synthesis of syndiotactic propylene polymer (A-3))
According to the production method of Polymerization Example A-1, except that hydrogen was further supplied to the polymerization system, it had the same TMA softening temperature, rrrr fraction, Mw / Mn as the polymer (A-1), [η] A syndiotactic propylene polymer (A-3) (propylene homopolymer) with = 1.4 dl / g was used. Table 4 shows the physical properties of the polymer (A-3).
[Polymerization Example A-4]
(Synthesis of syndiotactic propylene polymer (A-4))
According to the production method of Polymerization Example A-1, except that hydrogen was further supplied to the polymerization system, it had the same TMA softening temperature, rrrr fraction, Mw / Mn as the polymer (A-1), [η] A propylene homopolymer with = 1.2 dl / g was used. Table 4 shows the physical properties of the polymer (A-3).
(Syndiotactic propylene polymer (A-5))
Syndiotactic polypropylene (trade name: Finaplas1571, MFR = 9.1 g / 10 min) manufactured by Total was used. Table 4 shows the physical properties.

[Polymerization Example B-1]
(Synthesis of propylene / α-olefin copolymer (B-1))
After charging 8.3 ml of dry hexane, 1-butene and 120 g of triisobutylaluminum (1.0 mmol) into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, the temperature inside the polymerization apparatus was raised to 60 ° C. and propylene was used. After the pressure in the system was increased to 0.33 MPa, the system pressure was adjusted to 0.62 MPa with ethylene. Next, 0.002 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem Co.) in terms of aluminum are brought into contact with each other. The toluene solution was added to the polymerization vessel and polymerized for 20 minutes while maintaining the internal temperature at 60 ° C. and the internal pressure at 0.62 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 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 73 g and [η] = 2.1 (dL / g) measured in 135 ° C. decalin. Table 1 shows the measured physical properties of the obtained polymer.

[Polymerization Example B-2]
(Propylene / α-olefin copolymer (B-2))
After charging 8.3 ml of dry hexane, 1-butene and 120 g of triisobutylaluminum (1.0 mmol) into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, the temperature inside the polymerization apparatus was raised to 60 ° C. and propylene was used. After the pressure in the system was increased to 0.33 MPa, the system pressure was adjusted to 0.63 MPa with ethylene. Next, 0.002 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem Co.) in terms of aluminum are brought into contact with each other. The toluene solution was added to the polymerization vessel and polymerized for 20 minutes while maintaining the internal temperature at 60 ° C. and the internal pressure at 0.63 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 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The resulting polymer is
It was 97 g and [η] = 2.3 (dL / g) measured in 135 ° C. decalin. Table 1 shows the measured physical properties of the obtained polymer.

[Polymerization Example B-3]
(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 and [η] = 2.2 (dL / g) measured in 135 ° C. decalin. Table 1 shows the measured physical properties of the obtained polymer.

[Polymerization Example B-4]
(Synthesis of propylene / α-olefin copolymer (B-4))
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 4 shows the measured physical properties of the obtained polymer.

[Polymerization Example (BB-1)]
(Synthesis of propylene / α-olefin copolymer (BB-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, MFR was 0.7 (g / 10 min), and [η] = 2.5 (dL / g) measured in 135 ° C. decalin. Table 5 shows the measured physical properties of the obtained polymer. R
The r ₁ value was 78%.

[Polymerization example (BB-2)]
(Synthesis of propylene / α-olefin copolymer (BB-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, the MFR was 0.6 (g / 10 min), and [η] = 2.6 (dL / g) measured in decalin at 135 ° C. Table 5 shows the measured physical properties of the obtained polymer. R
The r ₁ value was 76%.

[Polymerization example (BB-3)]
(Synthesis of propylene / α-olefin copolymer (BB-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, MFR was 1.0 (g / 10 min), and [η] = 2.3 (dL / g) measured in 135 ° C. decalin. Table 5 shows the measured physical properties of the obtained polymer. The rr ₁ value was 75%.

[Polymerization example (BB-4)]
(Synthesis of propylene / α-olefin copolymer (BB-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, the MFR was 1.0 (g / 10 min), and [η] = 2.3 (dL / g) measured in 135 ° C. decalin. Table 5 shows the measured physical properties of the obtained polymer. The rr ₁ value was 75%.

Details of the other components are as follows.
Hydrocarbon resin (C-1) Hydrogenated terpene resin P150 manufactured by Yasuhara Chemicals
Thermoplastic elastomer (C-2) Miralastomer 7030B manufactured by Mitsui Chemicals (MFR = 25.0 g / 10 min)
Ethylene / Butene Copolymer (C-3) Ethylene / Butene Copolymer (C) manufactured by Mitsui Chemicals (trade name: Toughmer A4070, MFR = 4.0 g / 10 min)
(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 3 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 6 shows the physical properties of the obtained polymer.
(Propylene polymer (D-8))
Except for setting the polymerization temperature to 40 ° C., the ethylene content and the butene content were the same as those of the (D-7) produced according to the production conditions of the propylene polymer (D-7), and [η] = 4 A polymer having 0.0, Mw / Mn = 2.1 was used.

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

[Example 1]
Syndiotactic polypropylene (A-1) 20 obtained in [Polymerization Example (A-1)]
Parts by weight, propylene / ethylene / 1-butene random copolymer (B-1) (MFR (230 ° C.) = 1.2, [η] = 2.1, ethylene content 5 mol%, 1-butene content 29 mol%
) Tri (2,4-di-t-) as a secondary antioxidant for a total of 100 parts by weight with 80 parts by weight
0.1 part by weight of butylphenyl) phosphate, 0.1 part by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer, 0.1 parts by weight of calcium stearate as a hydrochloric acid absorbent was 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. Excellent heat resistance, transparency, abrasion resistance, and resilience.

[Example 2]
Syndiotactic polypropylene (A-1) 20 obtained in [Polymerization Example (A-1)]
Parts by weight and a propylene / ethylene / 1-butene random copolymer (B-2) (MFR (23
0 ° C.) = 0.9, [η] = 2.3, ethylene content 10 mol%, 1-butene content 28 mo
l%) 20 parts by weight of hydrogenated terpene resin P150 manufactured by Yasuhara Chemicals Co., Ltd. with respect to 100 parts by weight as a total of 80 parts by weight, and tri (2,4-disulfide) as a secondary antioxidant. -t-butylphenyl) phosphate, 0.1 parts by weight, n-octadecyl-3- (
0.1 part by weight of 4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate and 0.1 part by weight of calcium stearate as a hydrochloric acid absorbent were 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 2
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. Excellent heat resistance, transparency and wear resistance, especially rebound resilience.

[Example 3]
Syndiotactic polypropylene (A-1) 60 obtained in [Polymerization Example (A-1)]
Resin (C-1) (hydrogenated terpene resin P150 manufactured by Yashara Chemicals Co., Ltd.) with respect to 100 parts by weight in total of parts by weight and 40 parts by weight of the propylene / ethylene / 1-butene random copolymer (B-2). ) 20 parts by weight, 0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant, and n-octadecyl-3- (4′- 0.1 part by weight of hydroxy-3 ', 5'-di-t-butylphenyl) propinate and 0.1 part by weight of calcium stearate as a hydrochloric acid absorbent are blended. Thereafter, a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd. was used to make a sheet in the same manner as in Example 2, 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.

[Comparative Example 1]
In Example 1, instead of 20 parts by weight of syndiotactic polypropylene (A-1), 20 parts by weight of syndiotactic polypropylene (A-2) and a propylene / ethylene / 1-butene random copolymer (B-1) Instead of 80 parts by weight, 80 parts by weight of propylene / ethylene / 1-butene random copolymer (B-3) is used, and with respect to a total of 100 parts by weight of (A-2) and (B-3), 0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- (4′-hydroxy-3 ′, 5 as a heat stabilizer 0.1 parts by weight of '-di-t-butylphenyl) propinate and 0.1 parts by weight of calcium stearate as a hydrochloric acid absorbent were blended. Thereafter, a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd. was used to make a sheet in the same manner as in Example 1, 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.

[Comparative Example 2]
In Example 1, instead of 20 parts by weight of syndiotactic polypropylene (A-1), 20 parts by weight of syndiotactic polypropylene (A-2) and a propylene / ethylene / 1-butene random copolymer (B-1) Instead of 80 parts by weight, 80 parts by weight of ethylene / 1-butene random copolymer (C-3) is used, and the total of 100 parts by weight of (A-2) and (C-3) is secondary. 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 were blended. Thereafter, a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd. was used to make a sheet in the same manner as in Example 1, 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.

[Example 4]
Syndiotactic polypropylene (A-1) 20 obtained in [Polymerization Example (A-1)]
100 parts by weight in total of 80 parts by weight of propylene / ethylene random copolymer (B-3) (MFR (230 ° C.) = 1.1, [η] = 2.2, ethylene content 18 mol%) In contrast, 200 parts by weight of Miralastomer ^™ (trade name) 7030B manufactured by Mitsui Chemicals, Inc. as the thermoplastic elastomer (C-2), and tri (2,4-di-t-butylphenyl) as the secondary antioxidant 0.1 parts by weight of phosphate, 0.1 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer, hydrochloric acid absorbent 0.1 parts by weight of calcium stearate was added. 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, melted and kneaded for 5 minutes, and taken out at 20 ° C. A sheet was formed with a set cooling press, 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 heat resistance, impact strength, wear resistance, etc.

[Example 5]
Syndiotactic polypropylene (A-1) 20 obtained in [Polymerization Example (A-1)]
Parts by weight and the propylene / ethylene / 1-butene random copolymer (B-2) obtained in Polymerization Example (B-2) (MFR = 0.9 g / 10 min, [η] = 2.3 dL / g) , An elastomer content of 10 mol%, a 1-butene content of 28 mol%) and a total of 100 parts by weight, as a thermoplastic elastomer (C-2), Miralastomer ^TM (trade name) 7030B manufactured by Mitsui Chemicals, Inc. 100 parts by weight, 0.1 part by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant, and n-octadecyl-3- (4′-hydroxy) as a heat-resistant stabilizer 0.1 part by weight of 3 ', 5'-di-t-butylphenyl) propinate and 0.1 part by weight of calcium stearate as a hydrochloric acid absorbent were blended. Thereafter, a sheet was prepared in the same manner as in Example 4, 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 3 shows the results of various physical properties. Excellent heat resistance, impact strength, wear resistance, etc.

[Comparative Example 3]
100 parts by weight of Miralastomer ^™ (trade name) 7030B manufactured by Mitsui Chemicals, Inc. as the thermoplastic elastomer (C-2) and tri (2,4-di-t-butylphenyl) phosphate as the secondary antioxidant 0.1 part by weight, 0.1 part by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as heat stabilizer, steer as hydrochloric acid absorbent 0.1 part by weight of calcium phosphate was blended. Thereafter, a sheet was prepared in the same manner as in Example 4, 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 3 shows the results of various physical properties.

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. The portion surrounded by a thick line indicates a region of inequality (Eq-1) which is a preferable property of the syndiotactic propylene polymer (A) used in the present invention. It is the figure which plotted the relationship between MFR and [(eta)] about the polymer applicable to (A) component or (B) component used for 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 the (B) component used for this invention, and a broken line shows the preferable range of (b-2). .

Claims (10)

10 to 95 parts by weight of syndiotactic propylene polymer (A);
90 to 5 parts by weight of a propylene / α-olefin copolymer (B) (provided that the total of (A) and (B) is 100 parts by weight), and the polymer (A) is: Propylene-based polymer composition (X) that satisfies the requirement (a) and the copolymer (B) is an α-olefin copolymer having 4 to 20 carbon atoms that satisfies the following requirement (b) );
(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 30 to 90 mol% (provided that the total amount of structural units in the copolymer (B) is 100 mol%), and derived from ethylene. 10 to 70 mol% in total of the structural unit and the structural unit derived from the α-olefin having 4 to 20 carbon atoms (however, the structural unit derived from propylene, the structural unit derived from ethylene, and the α-carbon having 4 to 20 carbon atoms) The total amount with the structural unit derived from olefin is 100 mol%),
When the proportion of the structural unit derived from ethylene is P _E (mol%) and the proportion of the structural unit derived from an α-olefin having 4 to 20 carbon atoms is P _HAO (mol%), P _E / P _HAO = 0. 01-0.80,
MFR measured at 230 ° C. and 2.16 kg load in accordance with JIS K-6721 is in the range of 0.01 to 100 g / 10 minutes, and any of the following requirements (b-1) or (b-2) Satisfy one or more;
(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)   From a total of 100 parts by weight of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B), (C-1) from rosin resin, terpene resin and petroleum resin The propylene polymer composition (X) according to claim 1, comprising 0.1 to 100 parts by weight of one or more resins selected from the group consisting of:   Non-crosslinked or partially crosslinked olefinic thermoplastic elastomer with respect to a total of 100 parts by weight of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B) The propylene polymer composition (X) according to claim 1, comprising 0.1 to 500 parts by weight of (C-2).   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.   The molecular weight distribution (Mw / Mn, Mn: number average molecular weight, Mw: weight average molecular weight) determined by GPC of the propylene / α-olefin copolymer (B) is 3.5 or less. The propylene polymer composition (X) according to any one of the above.   The molded object which uses the propylene-type polymer composition (X) in any one of Claims 1-5.   The sheet | seat formed using the propylene-type polymer composition (X) in any one of Claims 1-5.   An unstretched or stretched film using the propylene-based polymer composition (X) according to any one of claims 1 to 5.   A laminate in which at least one layer contains the propylene-based polymer composition (X) according to any one of claims 1 to 5.   The nonwoven fabric which uses the propylene polymer composition (X) in any one of Claims 1-5.

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