JP2008045008A - Propylenic resin compositioh for packaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylenic resin composition for packaging materials, excellent in the balance of high transparency, rigidity, low temperature impact resistance and blocking resistance, to provide a film for retorts, a film for protect, and a film for packaging medical treatment containers, obtained from the same, and to provide a sheet therefor. <P>SOLUTION: This propylenic resin composition for the packaging materials comprises a propylene polymer (A) satisfying specific requirements and propylene-ethylene copolymer (B) satisfying specific requirements, wherein D<SB>insol</SB>and D<SB>sol</SB>satisfy specific requirements. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a propylene resin composition for packaging materials having specific properties. More specifically, the present invention relates to a propylene-based resin composition for packaging materials having excellent rigidity, transparency, impact resistance, and blocking resistance.

  Propylene-based resin compositions are used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, and automobile parts. In particular, in the field of packaging films, propylene-based resin compositions corresponding to the required functions have been proposed. However, many film fields are emerging that cannot be handled by existing propylene resin compositions alone. Specifically, a retort film or a protective film can be used.

  In recent years, retort foods have begun to spread rapidly from general households to business fields, and there is a demand for packaging materials that can package a larger amount of retort foods at a time than the amount used in general households. Retort food is generally stored at room temperature or low temperature for a long period of time, so that the package will not break or the package will break from the heat seal part of the package, and the contents will not leak. There is a need for films for packaging materials that have high heat seal strength and low temperature impact resistance. Moreover, when using the said film for packaging materials for a retort food, after filling and sealing a content, a retort sterilization process is performed using a high-pressure kettle at about 100-140 degreeC high temperature. Therefore, the film for packaging material is required to be a film that retains the heat resistance and heat seal strength of the heat seal part that can withstand the processing from the viewpoint of quality control of food.

  The packaging material film used in such retort foods is a blend film of polypropylene and ethylene / α-olefin copolymer rubber, a polypropylene block copolymer film, or the polypropylene block copolymer and ethylene / α-olefin. Films obtained from blend resin compositions with copolymer rubber are widely used. However, it is difficult to say that these films have an excellent balance of main performance as a film for packaging materials such as heat resistance, low temperature impact strength, blocking resistance and heat sealability. There is a big problem in the balance with the sealing property. For example, in order to prevent any decrease in heat seal strength after retorting, Patent Document 1 discloses a propylene / α-olefin block composed of 95 to 70% by weight of a polypropylene block and 5 to 30% by weight of an elastomer block. Proposals have been made to use polymers for heat seal layers. However, the film specifically disclosed in the publication obtains a propylene / α-olefin block copolymer containing an elastomer block having a propylene content of 30 to 70 mol% by using a Ziegler-Natta catalyst system, It is a film to be molded from now on, and its low-temperature impact strength is not sufficient.

  On the other hand, Patent Document 2 proposes a polypropylene sheet and film made of a propylene-based block copolymer produced with a metallocene catalyst system. Since these sheets and films are obtained from a propylene-based block copolymer having a uniform elastomer block composition, the impact resistance is improved. Patent Document 2 discloses a propylene-based polymer in which the content of structural units derived from ethylene in the n-decane soluble part is 30% by weight (39 mol%) or more. In recent years, as environmental problems have become more important, it is required to reduce the amount of film for packaging materials. Therefore, a film having high rigidity while maintaining impact resistance is desired even for a thin film. ing.

  Further, in recent years, as a retort packaging material, there is a case where it is required to have transparency enough to allow the packaged object to be seen through. In order to improve transparency, Patent Document 3 discloses a resin composition comprising a propylene-based homopolymer produced using a metallocene catalyst and an ethylene / propylene / 1-butene copolymer produced in the presence of the metallocene catalyst. Has been proposed. However, although the film specifically described in the publication is excellent in transparency, there is still room for improvement in low temperature impact resistance and rigidity required as a retort film.

  On the other hand, a protective film made of a propylene-based resin composition is conventionally used for the purpose of preventing scratches on the surface when the automobile is transported domestically or exported. As the required properties of the protective film, moderate adhesiveness when the film is attached to the metal surface, ease of peeling work, and strength such as tearing are required. For example, Patent Document 3 discloses a protective film made of a propylene-based block copolymer produced with a Ziegler-Natta catalyst, and describes that the film is suitable for protecting a metal surface. However, since the propylene block copolymer specifically described in the publication has a wide molecular weight distribution of the rubber component, the low molecular weight rubber may bleed and the adhesive force may change over time. In recent years, with the expansion of the liquid crystal display market, surface protection films for various optical sheets used in liquid crystal displays have been growing. The protective film for optical sheets is required to have high transparency with little fish eye in order to suppress the change in adhesive force with time and facilitate visual inspection.

In addition, materials for medical containers such as infusion preparation containers are changing from glass materials to plastic materials. As a material for infusion preparation containers, polyethylene has been used in many cases so far, but in recent years, polypropylene having a good balance of flexibility, moisture resistance, water resistance, chemical resistance and the like tends to increase. In particular, since sterilization at 121 ° C. is required overseas, polypropylene is more advantageous than polyethylene from the viewpoint of heat resistance. However, since polypropylene is inferior in low-temperature impact resistance compared to polyethylene, there is a possibility that the container may break if the infusion preparation container is accidentally dropped in a cold region. As a method for improving the low-temperature impact resistance of polypropylene, a method using a propylene-based block copolymer can be considered, but the existing propylene-based block copolymer is inferior in the balance between transparency, impact resistance and heat resistance. There is a point.
JP 2000-255012 A JP 2006-152068 A JP 2001-172402 A JP 2000-168006 A

  The present invention relates to a retort film excellent in balance of high transparency, rigidity, low-temperature impact resistance, and blocking resistance, a propylene-based resin composition for packaging materials suitable for obtaining a protective film, and a retort obtained from such a composition. The present invention relates to medical films, protective films, medical container packaging films, and sheets thereof.

That is, the present invention is a propylene-based copolymer (A) satisfying the following requirements (a1) to (a2): 60 to 90% by weight and a propylene-ethylene copolymer (B) satisfying the following requirements (b1) to (b4): A propylene-based resin composition for packaging materials, characterized by comprising 40 to 10% by weight (provided that (A) + (B) = 100% by weight) and a sheet or film obtained from such a composition.

Propylene polymer (A);
(A1) Melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) is 0.1 to 10 (g / 10 min).

(A2) Melting point (Tm) measured with a differential scanning calorimeter (DSC) is 145 ° C to 170 ° C.
Propylene-ethylene copolymer (B);
(B1) Content of the structural unit derived from ethylene is 15 mol% to 25 mol%.

(B2) Decalin solvent, intrinsic viscosity [η] at 135 ° C. is 1.8 dl / g to 3.5 dl / g.
(B3) Molecular weight distribution (Mw / Mn) is 3.5 or less.
(B4) The n-decane soluble part at 23 ° C. is 95% by weight or more.

The present invention also satisfies the following requirements (a1 ′) to (a2 ′), the n-decane insoluble part (D _insol ) at 23 ° C. is 60 to 90% by weight, and the following requirements (b1 ′) to (b3 ′): The n-decane soluble part (D _sol ) at 23 ° C. is 40 to 10% by weight, and the melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) is 0.1 to 20 ( g / 10 min), a propylene-based resin composition for packaging materials, and a sheet or film obtained from the composition.

n-decane insoluble part (D _insol );
(A1 ′) The content of structural units derived from ethylene is 2% by weight or less.
(A2 ′) The melting point (Tm) measured with a differential scanning calorimeter (DSC) is 145 ° C. to 170 ° C.
n-decane soluble part (D _sol );
(B1 ′) The content of structural units derived from ethylene is 15 mol% to 25 mol%.

(B2 ′) Decalin solvent, intrinsic viscosity [η] at 135 ° C. is 1.8 dl / g to 3.5 dl / g.
(B3 ′) Molecular weight distribution (Mw / Mn) is 3.5 or less.

  The sheet or film obtained by molding the propylene-based resin composition of the present invention is more transparent than a sheet or film obtained from a propylene-based block copolymer produced using an existing Ziegler-Natta catalyst. Excellent balance between low temperature impact resistance and rigidity.

Propylene polymer (A)
The propylene polymer (A) which is one of the components forming the propylene resin composition for packaging materials of the present invention,
(A1) Melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) is 0.1 to 10 (g / 10 min), preferably 0.5 to 7 (g / 10 min), more preferably 1. It is in the range of 0-5 (g / 10min),
(A2) The melting point (Tm) measured with a differential scanning calorimeter (DSC) is in the range of 145 ° C to 170 ° C, preferably 150 ° C to 170 ° C, more preferably 155 ° C to 170 ° C.

A propylene polymer having an MFR of less than 0.1 (g / 10 min) may deteriorate the extrusion moldability of the propylene-based resin composition for packaging materials obtained by mixing with the propylene-ethylene copolymer (B). Yes, if it exceeds 10 (g / 10 min), the low-temperature impact property of the obtained sheet or film tends to deteriorate.

  A propylene polymer having a melting point of less than 145 ° C. is inferior in heat resistance and the resulting sheet or film may be softened during retort treatment, and may not be particularly suitable as a high retort film. In addition, the resulting film is weak and may wrinkle when affixed to the product surface, which may not be suitable as a protective film.

  The propylene polymer (A) according to the present invention is a propylene homopolymer or a copolymer of propylene and a small amount of other α-olefin, for example, 5 mol% or less. As the α-olefin, ethylene, 1-butene, 1-hexene and 1-octene are preferably used.

  The molecular weight distribution (Mw / Mn) of the propylene polymer (A) according to the present invention is preferably 3.5 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. From the propylene-based resin composition for packaging materials comprising the propylene-based polymer (A) having such a molecular weight distribution, a sheet or film that is further excellent in transparency, impact resistance, blocking resistance and the like is obtained.

  The propylene-ethylene copolymer (A) according to the present invention is preferably produced in the presence of a metallocene catalyst. As described later, the metallocene catalyst used for the production of the propylene-ethylene copolymer (A) can react with a metallocene compound, an organometallic compound, an organoaluminum oxy compound, and a metallocene compound to form an ion pair. A metallocene catalyst comprising at least one compound selected from compounds that can be selected and, if necessary, a particulate carrier, and has already been disclosed in the above-mentioned publication (WO01 / 27124) or JP-A-11-315109 by the present applicant. The crosslinkable metallocene compound used is preferably used.

Propylene-ethylene copolymer (B)
The propylene-ethylene copolymer (B), which is another component forming the propylene-based resin composition for packaging materials of the present invention,
(B1) The content of structural units derived from ethylene is in the range of 15 mol% to 25 mol%, preferably 17 mol% to 25 mol%, more preferably 18 to 23 mol%.
(B2) Decalin solvent, intrinsic viscosity [η] at 135 ° C. of 1.8 dl / g to 3.5 dl / g, preferably 1.9 dl / g to 3.0 dl / g, more preferably 2.0 dl / g It is in the range of 2.5 dl / g.
(B3) The molecular weight distribution (Mw / Mn) is in the range of 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less.
(B4) The n-decane soluble part at 23 ° C. is in the range of 95% by weight or more, preferably 98% by weight or more, more preferably 99% by weight or more.

  A copolymer having a content of structural units derived from ethylene of less than 15 mol% may deteriorate the blocking resistance of the resulting sheet or film, and a copolymer exceeding 25 mol% may be used in the resulting sheet or film. Since impact resistance tends to decrease, it may not be suitable as a retort film or a protective film.

  A copolymer having an intrinsic viscosity [η] of less than 1.8 dl / g may reduce the impact resistance of the resulting sheet or film, while a copolymer having an intrinsic viscosity [η] of more than 3.5 dl / g. Since a polymer tends to generate fish eyes in the obtained sheet or film, the polymer may not be suitable as a retort film or a protective film.

A copolymer having a molecular weight distribution (Mw / Mn) of more than 3.5 has a low molecular weight component, which may reduce the impact resistance and tear strength of the resulting sheet or film. Since it may bleed out, it may not be suitable as a retort film or a protective film.

  A copolymer having an n-decane-soluble part of less than 95% by weight at 23 ° C. has a wide composition distribution of the propylene-ethylene copolymer, and the rigidity or impact resistance of the resulting sheet or film is lowered. May not be suitable as a protective film or protective film.

  The propylene-ethylene copolymer (B) according to the present invention is preferably produced in the presence of a metallocene catalyst. As described later, the metallocene catalyst used for the production of the propylene-ethylene copolymer (B) can react with a metallocene compound, an organometallic compound, an organoaluminum oxy compound, and a metallocene compound to form an ion pair. A metallocene catalyst comprising at least one compound selected from compounds that can be selected and, if necessary, a particulate carrier, and has already been disclosed in the above-mentioned publication (WO01 / 27124) or JP-A-11-315109 by the present applicant. The crosslinkable metallocene compound used is preferably used.

Propylene-based resin composition The propylene-based resin composition for packaging materials of the present invention is a propylene-based polymer (A) of 60 to 90% by weight, preferably 70%, in a total of 100% by weight of (A) and (B). -85 wt%, more preferably 80-85 wt% and the propylene-ethylene copolymer (B) in the range of 40-10 wt%, preferably 30-15 wt%, more preferably 20-15 wt%. This is a propylene-based resin composition for packaging materials (hereinafter also referred to as “composition C1”).

  A composition having an amount of the propylene-based polymer (A) of less than 60% by weight tends not to be suitable as a retort film because the rigidity of the resulting sheet or film tends to be low. On the other hand, a composition exceeding 90% by weight may not be suitable as a film for retort because the impact resistance of the resulting sheet or film tends to decrease.

  The propylene resin composition for packaging materials of the present invention preferably has a melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) usually in the range of 0.1 to 20 g / 10 min.

The propylene-based resin composition for packaging materials of the present invention also satisfies the following requirements (a1 ′) to (a2 ′), and has an n-decane insoluble part (D _insol ) at 23 ° C. of 60 to 90% by weight, preferably 70-85% by weight, more preferably 80-85% by weight and the following requirements (b1 ′) to (b3 ′) satisfying the following requirements (b1 ′)-(b3 ′): n-decane soluble part (D _sol ) at 23 ° C. 30 to 15% by weight, more preferably 20 to 15% by weight, and the melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) is in the range of 0.1 to 20 (g / 10 min). A propylene-based resin composition for packaging materials (hereinafter also referred to as “composition C2”).

n-decane insoluble part (D _insol );
(A1 ′) The content of structural units derived from ethylene is 2% by weight or less.
(A2 ′) The melting point (Tm) measured with a differential scanning calorimeter (DSC) is in the range of 145 ° C. to 170 ° C., preferably 150 ° C. to 170 ° C., more preferably 155 ° C. to 170 ° C.

n-decane soluble part (D _sol );
(B1 ′) The content of structural units derived from ethylene is in the range of 15 mol% to 25 mol%, preferably 17 mol% to 25 mol%, more preferably 18 to 23 mol%.

(B2 ′) Decalin solvent, intrinsic viscosity [η] at 135 ° C. of 1.8 dl / g to 3.5 dl / g
, Preferably 1.9 dl / g to 3.0 dl / g, more preferably 2.0 dl / g to 2.5 dl / g.
(B3 ′) The molecular weight distribution (Mw / Mn) is in the range of 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less.

In addition to the propylene-based polymer (A) and the propylene-ethylene copolymer (B), the propylene-based resin composition for packaging materials of the present invention (including the composition C1 and the composition C2), As other polymers, for example, the following ethylene-α-olefin copolymer (D), ethylene-propylene copolymer (B ′), propylene-based polymer (I ′) and the like may be included.

Ethylene-α-olefin copolymer (D)
The propylene-based resin composition for packaging materials of the present invention may contain an ethylene-α-olefin copolymer (D) for the purpose of further improving functions such as impact resistance of the obtained sheet or film. . Examples of the α-olefin in the ethylene-α-olefin copolymer (D) include α-olefins having 4 to 20 carbon atoms, preferably 1-butene, 1-hexene, 1-octene and the like. The density of the ethylene-α-olefin copolymer (D) is usually 0.850 to 0.910 g / cm ³ , preferably 0.860 to 0.890 g / cm ³ .

A copolymer having a density of less than 0.850 g / cm ³ tends to deteriorate the transparency or blocking resistance of the obtained sheet or film, and may not be suitable as a film for retort. On the other hand, when the density is higher than 0.910 g / cm ^{3, the} impact resistance of the obtained sheet or film may be lowered, and fish eyes tend to be generated. Therefore, it is suitable as a film for retort. There may not be. The addition amount of the ethylene-α-olefin copolymer (D) is 0 to 15% by weight, preferably 0 to 10% by weight, more preferably 0, in the propylene-based resin composition for packaging materials (100% by weight). It is in the range of ˜5% by weight.

Ethylene-propylene copolymer (B ')
The propylene-based resin composition for packaging materials of the present invention is derived from less ethylene than the propylene-ethylene copolymer (B) for the purpose of further improving functions such as impact resistance of the obtained sheet or film. An ethylene-propylene copolymer (B ′) having an amount smaller than the content of structural units or the content of structural units derived from ethylene contained in the n-decane soluble part (D _sol ) of the composition C2. It may be added.

  The content of the structural unit derived from ethylene in the ethylene-propylene copolymer (B ′) is preferably in the range of 25 to 85 mol%, more preferably 30 to 70 mol%, and still more preferably 30 to 55 mol%.

  The ethylene-propylene copolymer (B ′) was produced in the presence of a metallocene catalyst from the viewpoint of improving the impact resistance and blocking resistance of a sheet or film obtained from the propylene-based resin composition for packaging materials. It is desirable to be a thing. The addition amount of the ethylene-propylene copolymer (B ′) is 0 to 15% by weight, preferably 0 to 10% by weight, more preferably 0 to 0% in the propylene-based resin composition for packaging materials (100% by weight). 5% by weight.

The ethylene-propylene copolymer (B ′) may be polymerized and added when the propylene polymer (A) and the propylene-ethylene copolymer (B) are polymerized in the same system.
Propylene polymer (I ')
Propylene-based polymer (I ′) added to the propylene-based resin composition for packaging materials of the present invention
Is a homopolymer of propylene, a copolymer of propylene and ethylene and an α-olefin having 4 or more carbon atoms, and a block copolymer of propylene, ethylene and an α-olefin having 4 or more carbon atoms. Specific examples of the α-olefin include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl- 1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene Propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-u Decene, 1-dodecene, and the like. Of these, α-olefins of 1-butene, 1-pentene, 1-hexene and 1-octene are preferable. Two or more ethylene and ethylene-copolymerized α-olefins having 4 or more carbon atoms may be used.

The melting point (Tm) of the propylene polymer (I ′) is usually 150 to 170 ° C., preferably 155 to 170 ° C. Further, the melt flow rate (M
FR: ASTM D1238, 230 ° C., load 2.16 kg) is usually 0.1 to 10 g.
/ 10 minutes, preferably 0.5 to 8 g / 10 minutes, more preferably 1.0 to 5 g / 10 minutes.

  The addition amount of the propylene polymer (I ′) is 0 to 50 wt%, preferably 0 to 25 wt%, more preferably 0 to 10 wt% in the propylene resin composition for packaging materials (100 wt%). %.

  The propylene-based resin composition for packaging materials of the present invention further includes an antioxidant, a nucleating agent, a lubricant, a flame retardant, an anti-blocking agent, a colorant, which are usually added to the olefin polymer, if necessary. Various additives such as inorganic or organic fillers and various synthetic resins may be added as long as the object of the present invention is not impaired.

Production Method of Propylene Resin Composition for Packaging Material The propylene resin composition for packaging material of the present invention can be obtained by various known production methods. For example, the propylene-based polymer (A) and the propylene-ethylene copolymer (B) obtained in advance are blended with the polymer or various additives as necessary in the amounts described above, for example, , Mixing using various known devices such as Henschel mixer, ribbon blender, Banbury mixer, etc., or after mixing, using various known kneaders such as single screw extruder or twin screw extruder, Brabender or roll And the method of melt-kneading at 170-300 degreeC, Preferably 190-250 degreeC etc. are mentioned.

The propylene-based resin composition for packaging materials of the present invention can also be produced by polymerizing propylene, ethylene, and the like by the following method.
When the propylene-based resin composition for packaging materials of the present invention, particularly, the composition C2 is produced by polymerization, the following two steps ([Step 1] and [Step 2]) are carried out in the presence of a metallocene catalyst as a catalyst. It is preferable to carry out continuously.
[Step 1] comprises homopolymerization or copolymerization of propylene and ethylene as required in the presence of a metallocene catalyst to produce the propylene polymer (A) or an n-decane soluble part (D _{sol at} 23 ° C. ) Is a step of producing a homopolymer or copolymer in an amount within the above range.
In [Step 2], propylene and ethylene are copolymerized in the presence of a metallocene catalyst, and the propylene-ethylene copolymer (B) or n-decane insoluble part (D _insol ) at 23 ° C. is 5.0 wt _%. % Is a step of producing a copolymer in an amount within the above range.

  Specifically, the propylene-based resin composition for a packaging material in the present invention uses a polymerization apparatus in which two or more reactors are connected in series, and the two steps ([Step 1] and [Step 2]) are performed. It is preferable to manufacture by carrying out continuously.

[Step 1] is a step of homopolymerizing propylene or copolymerizing propylene and a small amount of ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 1], by propylene homopolymerization or by copolymerizing propylene and a small amount of ethylene, the propylene-based (co) polymer produced in [Step 1] is contained in the propylene-based resin composition for packaging materials. The main component of the n-decane insoluble part (D _insol ) at 23 ° C. is used.

[Step 2] is a step of copolymerizing propylene and ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 2], the propylene-ethylene copolymer produced in [Step 2] is increased in the propylene-based resin composition for packaging material by increasing the amount of ethylene fed to propylene as compared with [Step 1]. The main component of the n-decane soluble part (D _sol ) at 23 ° C.

Here, the D _insol substantially corresponds to the propylene polymer (A) contained in the propylene resin composition for packaging materials. The D _sol substantially corresponds to the propylene-ethylene copolymer (B) contained in the propylene resin composition for packaging materials.

In the case of a propylene resin composition for packaging material, when D _insol substantially corresponding to the propylene polymer (A) has a large amount of 2,1-insertion bond and 1,3-insertion bond of propylene, In particular, the composition distribution of D _sol corresponding to the propylene-ethylene copolymer (B) becomes wide, and the rigidity and impact resistance may be lowered. 2,1-insertion and 1,3-insertion are propylene-positionally irregular units in a propylene-based resin composition for packaging materials, and partial structures containing these are represented by the following (i) and (ii) The

  Further, after completion of the polymerization in [Step 1] and [Step 2], a post-treatment step such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step is performed as necessary, so that A resin composition is obtained as a powder.

Metallocene Catalyst In the present invention, the propylene polymer (A), the propylene-ethylene copolymer (B) or the propylene resin composition is preferably produced in the presence of a metallocene catalyst.

The metallocene catalyst used in the present invention includes at least one compound selected from metallocene compounds and compounds capable of reacting with organometallic compounds, organoaluminum oxy compounds and metallocene compounds to form ion pairs, Furthermore, a metallocene catalyst which can be stereoregularly polymerized such as an isotactic or syndiotactic structure with a metallocene catalyst comprising a particulate carrier, if necessary, can be mentioned. Among the metallocene compounds, a crosslinkable metallocene compound that has already been published (WO01 / 27124) by an international application filed by the present applicant is preferably used.

In the above general formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are It is selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and each may be the same or different. Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Linear hydrocarbon groups such as nonyl and n-decanyl; isopropyl, tert-butyl, amyl, 3-
Methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, Branched hydrocarbon groups such as 1-methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group Cyclic unsaturated hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl, triphenylmethyl, and the like; cyclic unsaturated hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl, triphenylmethyl, and the like; and tolyl, naphthyl, biphenyl, phenanthryl, and anthracenyl A substituted saturated hydrocarbon group; methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, Group, and the like can be given heteroatom-containing hydrocarbon group such as a thienyl group. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. Further, the adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [I], R ¹ , R ² , R ³ and R ⁴ substituted on the cyclopentadienyl ring are preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups described above. More preferably, R ³ is a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula [I], R ⁵ to R ¹² substituted on the fluorene ring are preferably hydrocarbon groups having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups described above. The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring.

In the general formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element, more preferably carbon, silicon, or germanium, and further preferably a carbon atom. R ¹³ and R ¹⁴ substituted for Y are preferably hydrocarbon groups having 1 to 20 carbon atoms. These may be the same as or different from each other, or may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups described above. More preferably, R ¹⁴ is an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

In the general formula [I], M is preferably a Group 4 transition metal, more preferably Ti, Zr, Hf and the like. Q is selected from the same or different combinations from halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include those described above. Specific examples of anionic ligands include methoxy, tert-butoxy,
Examples include alkoxy groups such as phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy And ethers such as ethane. At least one Q is preferably a halogen or an alkyl group.

  Examples of such bridged metallocene compounds include isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl). ) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl- 5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert -Butyl fluoreni ) Zirconium dichloride are preferably used.

  Moreover, the metallocene compound represented by the following general formula [II] can also be preferably used.

In the general formula [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are selected from a hydrogen atom, a hydrocarbon atom group, and a silicon-containing group, and may be the same or different, and adjacent substituents from R ¹ to R ¹⁶ are bonded to each other to form a ring. Also good.
However, R ² is not an aryl group. The aryl group mentioned here refers to a substituent having a free valence on the conjugated sp ² carbon in an aromatic hydrocarbon group, such as a phenyl group, a tolyl group, a naphthyl group, and the like, such as a benzyl group, a phenethyl group, a phenyldimethyl group. Does not include silyl groups. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, linear hydrocarbon group such as n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl- Branched hydrocarbon groups such as 1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl; cyclopentyl, Cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, cyclic saturated hydrocarbon groups such as methylcyclohexyl, methyladamantyl; phenyl, tolyl, naphthyl, biphenyl, phenanthryl, anthra Cyclic unsaturated hydrocarbon groups such as nyl groups; saturated hydrocarbon groups substituted by cyclic unsaturated hydrocarbon groups such as benzyl groups, cumyl groups, 1,1-diphenylethyl groups, triphenylmethyl groups; methoxy groups, ethoxy groups And hetero atom-containing hydrocarbon groups such as phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group and thienyl group. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. Further, the adjacent substituents of R ⁹ to R ¹⁶ of the fluorenyl ring may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [II], R ¹ and R ³ are preferably hydrogen atoms. More preferably at least one selected from R ⁶ and R ⁷ are hydrogen atoms, more preferably R ⁶ and R ⁷ are both hydrogen atoms.

In the general formula [II], R ² substituted on the cyclopentadienyl ring is preferably not a aryl group but a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups described above. R ² is preferably a hydrocarbon group, preferably a methyl group, an ethyl group, an isopropyl group or a tert-butyl group, particularly preferably a tert-butyl group.

R ⁴ and R ⁵ are selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an aryl group, and preferably a hydrocarbon group having 1 to 20 carbon atoms. R ⁴ and R ⁵ are more preferably selected from a methyl group and a phenyl group, and R ⁴ and R ⁵ are particularly preferably the same.

In the general formula [II], R ⁹ , R ¹² , R ¹³ and R ¹⁶ on the fluorene ring are preferably hydrogen atoms.
In the general formula [II], M is a Group 4 transition metal, and specific examples thereof include Ti, Zr, and Hf. Q is selected from the group consisting of a halogen atom, a hydrocarbon atom group, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include those described above. Specific examples of anionic ligands include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, sulfonate groups such as mesylate and tosylate, dimethylamide, diisopropylamide, methylanilide, diphenylamide And amide groups such as Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy And ethers such as ethane. At least one Q is preferably a halogen atom or an alkyl group.

Examples of the metallocene compound represented by the general formula [II] according to the present invention include [3- (fluorenyl) (1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ′, 7'-di-tert-butylfluorenyl) (1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1 , 2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b , h] fluorenyl) (1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,1,3,5-tetramethyl-1,2,3,3a-tetrahydropenta Len)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,1,3,5-tetramethyl-1,2,3,3a-tetrahydropentalene)] Zirconium dichloride,

[3- (3 ′, 6′-di-tert-butylfluorenyl) (1,1,3,5-tetramethyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3,5-tetramethyl-1 , 2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,1-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ′, 7′-di-tert-butylfluorenyl) (1,1-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3 -(3 ', 6'-di-tert-butylfluorenyl) (1,1-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- ( 1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1-
Dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,1,3-triethyl-2-methyl 5-tert-butyl-1, 2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,1,3-triethyl-2-methyl 5-tert-butyl -1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1,1,3-triethyl-2-methyl-5- tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-triethyl-2 -Methyl 5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,3-dimethyl-5-tert-butyl-1,2,3,3a -Tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,3-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydro Pentane)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1,3-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene )] Zirconium dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,3-dimethyl-5-tert -Butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,1,3-trimethyl-5-ethyl-1,2,3,3a-tetrahydropentalene) ] Zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,1,3-trimethyl-5-ethyl-1,2,3,3a-tetrahydropentalene)] zirconium Dichloride, [3- (3 ′, 6′-di-tert-butylfluorenyl) (1,1,3-trimethyl-5-ethyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5 -Ethyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,1,3-trimethyl-5-trimethylsilyl-1,2,3,3a-teto Hydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,1,3-trimethyl-5-trimethylsilyl-1,2,3,3a-tetrahydropenta Len)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1,1,3-trimethyl-5-trimethylsilyl-1,2,3,3a-tetrahydropentalene) ]
Zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-trimethylsilyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene )] Zirconium dichloride,

[3- (2 ′, 7′-di-tert-butylfluorenyl) (3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- ( 3 ', 6'-di-tert-butylfluorenyl) (3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1', 1 ', 4', 4 ', 7', 7 ', 10', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (3-methyl-5-tert-butyl-1,2,3,3a -Tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1-phenyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- ( 2 ', 7'-di-tert-butylfluorenyl) (1-phenyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- ( 3 ', 6'-di-tert-butylfluorenyl) (1-phenyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] di Luconium dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1-phenyl-3-methyl-5 -tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1-p-tolyl-3-methyl-5-tert-butyl-1,2,3, 3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1-p-tolyl-3-methyl-5-tert-butyl-1,2, 3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1-p-tolyl-3-methyl-5-tert-butyl-1, 2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1-p-tolyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,3-diph Nyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,3-diphenyl- 5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1,3-diphenyl-5- tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyl Octahydrodibenzo [b, h] fluorenyl) (1,3-diphenyl-5-tert-butyl-1,
2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,3-
Diphenyl-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1, 3-diphenyl-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride,

  [3- (3 ', 6'-di-tert-butylfluorenyl) (1,3-diphenyl-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium Dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,3-diphenyl-1-methyl -5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,3-di (p-tolyl) -1-methyl-5-tert-butyl -1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,3-di (p-tolyl) -1- Methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1,3-di ( p-tolyl) -1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7 ', 10', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,3-di (p-tolyl) -1-methyl-5-tert-butyl-1,2,3,3a -Tetrahydropentalene)] zirconium dichlori [3- (fluorenyl) (3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butyl Fluorenyl) (3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (3-phenyl-5-tert-butyl -1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1-methyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) ] Zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1-methyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) ] Zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1-methyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) ] Zirconium dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1-methyl-3-phenyl-5 -tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (fluorenyl) (1,1-dimethyl-3-phenyl-5-tert-butyl-1,2,3, 3a-tetrahydropentalene)] zirconium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,1-dimethyl-3-phenyl-5-tert-butyl-1,2, 3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1,1-dimethyl-3-phenyl-5-tert-butyl-1, 2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1-dimethyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]
Zirconium dichloride, [3- (fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] hafnium dichloride, [3- (2 ', 7'- Di-tert-butylfluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] hafnium dichloride, [3- (3 ', 6'- Di-tert-butylfluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] hafnium dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5 -tert-butyl-1,2,3,3a-tetrahydropentalene)] hafnium dichloride, [3- (fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a- Tetrahydropentalene)] titanium dichloride, [3- (2 ', 7'-di-tert-butylfluorenyl) (1,1,
3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] titanium dichloride, [3- (3 ', 6'-di-tert-butylfluorenyl) (1,1, 3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] titanium dichloride,

[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5 -tert-butyl-1,2,3,3a-tetrahydropentalene)] titanium dichloride, particularly preferred compounds include [3- (fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1, 2,3,3a-tetrahydropentalene)] zirconium dichloride,

[3- (2 ′, 7′-di-tert-butylfluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (3 ′, 6′-di-tert-butylfluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5 -tert-Butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride. However, the metallocene compound [m] of the present invention is not limited to the above exemplified compounds, and includes all compounds that satisfy the requirements defined in the claims of the present application. The position numbers used for naming the above compounds are [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] Fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride, and [3- (2 ', 7'-di-tert-butylfurane) (Olenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride as an example, respectively [II ′] and [II ″] Shown in

In the metallocene catalyst according to the present invention, it reacts with the organometallic compound, organoaluminum oxy compound, and transition metal compound used together with the Group 4 transition metal compound represented by the general formulas [I] and [II]. Regarding at least one compound selected from compounds that form ion pairs, as well as the particulate carrier used as necessary, in the above-mentioned publication (WO01 / 27124) or JP-A-11-315109 by the present applicant. The disclosed compounds can be used without limitation.

Sheet or Film The sheet or film of the present invention is a sheet or film obtained from the propylene-based resin composition for packaging materials of the present invention.

  Such a sheet or film can be produced by using a propylene-based resin composition for packaging materials and various known molding methods, for example, a film molding machine equipped with a T-die or a circular die at the tip of an extruder.

  Although the thickness of the sheet | seat or film of this invention can be variously determined according to a use, it is 10 micrometers-2 mm normally, Preferably it exists in the range of 10-200 micrometers. The film of the present invention is excellent in impact resistance at low temperatures even as a relatively thin film.

The sheet or film of the present invention may be an unstretched film or a stretched film, but an unstretched film is preferred.
The sheet or film of the present invention can be used as a packaging material for a retort film or the like, even if it is a single layer, but it can be laminated by laminating with a stretched or unstretched polyamide film, a uniaxially or biaxially stretched polyester film, an aluminum foil, paper, or the like. It can be used as a film for layer retort. Moreover, it can be used as a surface protection material of an optical sheet or a metal by setting it as the protective film of a single layer and a multilayer.

EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example. The analysis method employed in the present invention is as follows.
[m1] MFR (melt flow rate)
MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).

[m2] Melting point (Tm)
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak in the third step was defined as the melting point (Tm).

(Measurement condition)
First step: The temperature is raised to 240 ° C. at 10 ° C./min and held for 10 min.
Second step: Decrease the temperature to 60 ° C at 10 ° C / min.

Third step: Increase the temperature to 240 ° C at 10 ° C / min.
[m3] Intrinsic viscosity [η]
Measurement was performed at 135 ° C. using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. Repeat this dilution operation two more times,
The value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (ηsp / C) (C → 0)
[m4] Mw / Mn measurement (weight average molecular weight (Mw), number average molecular weight (Mn))
Measurement was performed as follows using GPC-150C Plus manufactured by Waters. Separation columns are TSKgel GMH6-HT and TSK gel GMH6-HTL, and column sizes are 7.5 mm in inner diameter and 600 mm in length, respectively.
The column temperature was 140 ° C., o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase and 0.025 wt% BHT (Wako Pure Chemical Industries) was used as the antioxidant, and the column was moved at 1.0 ml / min. The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene is converted to PP using a general-purpose calibration method for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ using Tosoh Corporation, and for 1000 ≦ Mw ≦ 4 × 10 ⁶ using pressure chemical. did. The Mark-Houwink coefficients of PS and PP are the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)), respectively. Was used.
[m5] Amount of n-decane soluble part at 23 ° C (D _sol )
200 ml of n-decane was added to 5 g of a sample of the final product (that is, the propylene-based resin composition used in the present invention) and dissolved by heating at 145 ° C. for 30 minutes. The mixture was cooled to 23 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble portion at 23 ° C .: D _insol ) 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 (A) and acetone were separated by filtration, and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part at 23 ° C. was determined by the following equation.

Amount of soluble part of n-decane at 23 ° C. (wt%) = [precipitate (A) weight / sample weight] × 100
[m6] Content of structural units derived from ethylene To measure the concentration of structural units derived from ethylene in propylene-ethylene copolymer (B) and D _insol , D _sol , 4-trichlorobenzene / heavy benzene (2: 1) solution was dissolved in 0.6 ml, followed by carbon nuclear magnetic resonance analysis ( ¹³ C-NMR). Propylene, ethylene, and α-olefin were quantitatively determined from the dyad chain distribution. For example, propylene
In the case of an ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ were used, and the following formulas (Eq-1) and (Eq-2) were used. .

Propylene (mol%) = (PP + 1 / 2EP) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)… (Eq-1)
Ethylene (mol%) = (1 / 2EP + EE) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)… (Eq-2)
In this example, the _units of ethylene and α-olefin in D _insol are expressed in terms of% by weight.

[m7] 2,1-insertion bond and 1,3-insertion bond samples 20 to 30 mg were dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, followed by carbon nuclear magnetic resonance. Analysis ( ¹³ C-NMR) was performed. The monomer formed by 2,1-insertion forms a position irregular unit represented by the partial structure (i) in the polymer chain. The amount of 2,1-propylene monomer inserted relative to the total propylene insertion was calculated by the following formula.

In this formula, ΣICH ₃ represents the area of all methyl groups. Further, Iαδ and Iβγ indicate the area of the αβ peak (resonance around 37.1 ppm) and the area of the βγ peak (resonance around 27.3 ppm), respectively. These methylene peaks were named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781).

Similarly, the insertion amount of the 1,3-propylene monomer represented by the partial structure (ii) with respect to the total propylene insertion was calculated by the following formula.

[m8] Density The density of the ethylene-α-olefin copolymer was measured with a density gradient tube after heat-treating the measurement sample at 120 ° C. for 1 hour and linearly cooling to room temperature over 1 hour.

[m9] Film stiffness
The Young's modulus of the film was measured according to JIS K 6781 to evaluate the rigidity.
<Test conditions>
Temperature: 23 ℃
Tensile speed: 200mm / min
Chuck distance: 80mm
[m10] Impact resistance of film The film was sampled to 5 cm × 5 cm, and the impact resistance was evaluated by measuring the surface impact strength with an impact tester (a method of pushing a hammer from the bottom to the top) at a predetermined temperature.

<Test conditions>
Temperature: -10 ℃
Hammer: Tip 1 inch, load 3.0J
[m11] Haze of film (HAZE)
Measured according to ASTM D-1003.

[m12] Blocking resistance of the film The chill roll surfaces of the film of 10 cm in the MD direction × 10 cm in the TD direction are overlapped and held in a thermostatic bath at 50 ° C. under a load of 200 g / cm ² for 3 days. Then, after conditioning in a room at 23 ° C. and 50% humidity for 24 hours or more, the peel strength when peeled at a tensile speed of 200 mm / min was measured, and the value obtained by dividing the peel strength by the test piece width was the blocking coefficient. And blocking resistance was evaluated. Here, the smaller the blocking coefficient, the better the blocking resistance.

[m13] Heat Seal Strength of Film A film was sampled to a width of 5 mm, and sealed with a heat seal time of 1 second and a heat seal pressure of 0.2 MPa. Both ends of the sealed film were pulled at 300 mm / min, and the maximum strength at which the film peeled was measured. The upper part of the seal bar was set to a specified temperature of 200 ° C., and the lower temperature was set to 70 ° C.

[Production Example 1] Production of propylene-based resin composition (C2-1) for packaging materials
(1) Production of a solid catalyst carrier 300 g of SiO ₂ was sampled in a 1 L branch flask, and 800 mL of toluene was added.
After slurrying, the solution was transferred to a 5 L 4-neck flask, and 260 mL of toluene was added. 2830 mL of a toluene solution (10 wt% solution) of methylaluminoxane (hereinafter referred to as MAO) was added and stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour and reacted for 4 hours. After completion of the reaction, the temperature was lowered to room temperature. After cooling, the supernatant toluene solution was removed, toluene was added again, and substitution was performed until the substitution rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, add a 5-L four-necked flask to [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h ] Fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride was weighed in 2.0 g. The flask was taken out and MAO / Si prepared with 0.46 liters of toluene and (1)
1.4 liters of O ₂ / toluene slurry was added under nitrogen and stirred for 30 minutes to carry. The resulting [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]
Zirconium dichloride / MAO / SiO ₂ / toluene slurry is 99 in n-heptane.
% Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (2) above, 218 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C. and 1212 g of ethylene was inserted. And allowed to react with stirring for 180 minutes. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 30 kg / hour, hydrogen is 2 NL / hour, the catalyst slurry produced in (3) is 3.5 g / hour as a solid catalyst component, and 2.3 ml of triethylaluminum. / Time was continuously supplied, and the polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 L, and further polymerization was performed. Propylene was supplied at 15 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, gasified, gas-solid separated, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization. went. Propylene, ethylene, and hydrogen are continuously supplied so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.52 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). did. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.

The obtained propylene-based resin composition for packaging material was vacuum-dried at 80 ° C.
[Production Example 2] Production of propylene-based resin composition for packaging material (C2-2) Propylene-based resin composition for packaging material is produced in the same manner as in Production Example 1 except that the polymerization method is changed as follows. did.

(1) Main polymerization In a tubular polymerization vessel having an internal capacity of 58 L, propylene is 30 kg / hour, hydrogen is 1 NL / hour, the catalyst slurry produced in Production Example 1 (3) is 6.2 g / hour, triethylaluminum 2 .3 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, gasified, gas-solid separated, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization. went. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerizer would be ethylene / (ethylene + propylene) = 0.10 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.

The obtained propylene-based resin composition for packaging material was vacuum-dried at 80 ° C.
[Production Example 3] Production of propylene resin composition for packaging material (C2-3) Production of propylene resin composition for packaging material in the same manner as in Production Example 1 except that the polymerization method was changed as follows. did.

(1) Propylene 30 kg / hour, hydrogen 1 NL / hour, catalyst slurry produced in Production Example 1 (3) as a solid catalyst component 6.2 g / hour, triethylaluminum 2 .3 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied at 15 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, gasified, gas-solid separated, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization. went. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerizer would be ethylene / (ethylene + propylene) = 0.10 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.9 MPa / G.

The obtained propylene-based resin composition for packaging material was vacuum-dried at 80 ° C.
[Production Example 4] Production of propylene-based resin composition for packaging material (C2-4) Propylene-based resin composition for packaging material is produced in the same manner as in Production Example 1 except that the polymerization method is changed as follows. did.

(1) Main polymerization In a tubular polymerization vessel having an internal capacity of 58 L, propylene is 30 kg / hour, hydrogen is 1 NL / hour, the catalyst slurry produced in Production Example 1 (3) is 6.2 g / hour, triethylaluminum 2 .3 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, gasified, gas-solid separated, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization. went. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization temperature 70 ° C, pressure 1.0 MPa / G
The polymerization was carried out at

The obtained propylene-based resin composition for packaging material was vacuum-dried at 80 ° C.
[Production Example 5] Production of propylene-based resin composition for packaging material (C2-5) Using the solid catalyst carrier produced in Production Example 1 (1), a propylene-based resin composition for packaging material was produced by the following method. .

(1) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, weigh 2.0 g of diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-t-butylfluorenyl) zirconium dichloride into a 5 L four-necked flask. It was. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in (1) were added under nitrogen and stirred for 30 minutes to carry. The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% in n-heptane. Substituting and the final slurry volume is 4.5
Liters. This operation was performed at room temperature.

(2) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (1) above, 218 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C. to 606 g of ethylene. Inserted and allowed to react with stirring for 180 minutes. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(3) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, 30 kg / hour of propylene, 1 NL / hour of hydrogen, 10.0 g / hour of the catalyst slurry produced in the above (2) as a solid catalyst component, 2.3 ml of triethylaluminum / Time was continuously supplied, and the polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 L, and further polymerization was performed. Propylene was supplied at 15 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, gasified, gas-solid separated, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization. went. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerizer would be ethylene / (ethylene + propylene) = 0.10 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.

The obtained propylene-based resin for packaging material was vacuum-dried at 80 ° C.
[Production Example 6] Production of propylene-based resin composition for packaging material (C2-6) A propylene-based resin composition for packaging material was produced by the following method using the solid catalyst carrier produced in Production Example 1 (1). .

(1) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 2.0 g of dimethylsilylene bis- (2-methyl-4-phenylindenyl) zirconium dichloride was weighed into a 5 L four-necked flask. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in (1) were added under nitrogen and stirred for 30 minutes to carry. The obtained dimethylsilylene bis- (2-methyl-4-phenylindenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% substituted with n-heptane, and the final slurry volume was 4.5 liters. It was. This operation was performed at room temperature.

(2) Production of prepolymerization catalyst 202 g of the solid catalyst component prepared in (1) above, 109 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C., and 606 g of ethylene was inserted. And allowed to react with stirring for 180 minutes. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 2 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(3) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 30 kg / hour, hydrogen is 2 NL / hour, the catalyst slurry produced in (2) is 1.2 g / hour as a solid catalyst component, and 2.3 ml of triethylaluminum. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied at 15 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.14 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, gasified, gas-solid separated, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization. went. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerizer was ethylene / (ethylene + propylene) = 0.45 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.7 MPa / G.

The obtained propylene-based resin composition for packaging material was vacuum-dried at 80 ° C.
[Production Example 7] Production of propylene polymer (A-1) A propylene polymer was produced by the following method using the solid catalyst carrier produced in Production Example 1 (1).

(1) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 2.0 g of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride is added to a 5 L four-necked flask. Weighed. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in (1) were added under nitrogen and stirred for 30 minutes to carry. The resulting dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was obtained with n-heptane. 99% substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

(2) Production of prepolymerization catalyst 202 g of the solid catalyst component prepared in (1) above, 109 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C., and 606 g of ethylene was inserted. And allowed to react with stirring for 180 minutes. After polymerization is complete,
The solid component was allowed to settle and the supernatant was removed and washed twice with heptane. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 2 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(3) Main polymerization In a tubular polymerization vessel with an internal volume of 58 L, propylene is 30 kg / hour, hydrogen is 3 NL / hour, the catalyst slurry produced in (2) is 8.0 g / hour, and triethylaluminum 5.5 ml. / Time was continuously supplied, and the polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and further polymerization was performed. Propylene was supplied to 160 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.07 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 16 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.07 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied at 12 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.07 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out polymerization. To the polymerization vessel, propylene was supplied at 17 kg / hour and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.07 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.8 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based polymer. The resulting propylene polymer was vacuum dried at 80 ° C.
[Production Example 8] Production of propylene polymer (A-2) A propylene polymer was produced in the same manner as in Production Example 5 except that the polymerization method was changed as follows.

(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 57 kg / hour, hydrogen is 4 NL / hour, catalyst slurry prepared by pre-polymerization is 7.1 g / hour, and triethylaluminum is 4.0 mL / hour. Was continuously fed and polymerized in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 2.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and further polymerization was performed. Propylene was supplied to the polymerization vessel at 50 kg / hour, ethylene was supplied at 1.7 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.16 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to 11 kg / hour, ethylene was supplied to 1.2 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.16 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.4 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based polymer. The resulting propylene polymer was vacuum dried at 80 ° C.
[Production Example 9] Production of propylene-ethylene copolymer (B-1) A propylene-based polymer was produced in the same manner as in Production Example 5 except that the polymerization method was changed as follows.

(1) Main polymerization 9 kg of liquid propylene was charged into a 30 L SUS autoclave sufficiently purged with nitrogen and brought to 10 ° C., and 0.5 MPa was charged with ethylene as a partial pressure. The mixture was heated to 45 ° C. with sufficient stirring, and a mixed solution of 0.6 g / 300 ml of heptane and 0.5 ml of triethylaluminum as a solid catalyst component was pressure-inserted into the autoclave with nitrogen from the catalyst insertion pot. After carrying out the polymerization at 60 ° C. for 20 minutes, methanol was added to stop the polymerization. After the polymerization was completed, propylene was purged, and nitrogen substitution was sufficiently performed to fractionate the polymer. Vacuum dried at 80 ° C.

[Production Example 10] Production of propylene-ethylene copolymer (B-2)
(1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of the solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was kept at the same temperature while stirring for 2 hours. Retained. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The prepared solid titanium catalyst component was stored as a hexane slurry, and a part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Production of pre-polymerization catalyst 56 g of transition metal catalyst component, 9.8 mL of triethylaluminum, and 80 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 200 L, and 560 g of propylene was inserted while maintaining the internal temperature at 5 ° C., followed by stirring for 60 minutes. It was made to react. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted with heptane so that the transition metal catalyst component concentration was 1.0 g / L. This prepolymerization catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization 9 kg of SUS autoclave with sufficient nitrogen substitution was charged with 9 kg of liquid propylene and heated to 45 ° C. with sufficient stirring. Ethylene was used as a partial pressure, and 0.15 MPa and hydrogen of 20 NL were charged. From a catalyst insertion pot, a mixed solution of 0.2 g / heptane 200 ml, triethylaluminum 2.0 ml and dicyclopentyldimethoxysilane 0.4 ml as a solid catalyst component was pressure-inserted into the autoclave with nitrogen. Polymerization was carried out at 50 ° C. for 15 minutes, and methanol was added to terminate the polymerization. After the polymerization was completed, propylene was purged, and nitrogen substitution was sufficiently performed to fractionate the polymer. Vacuum dried at 80 ° C. The obtained propylene-ethylene copolymer (B-2) had an ethylene content of 20 mol% and an intrinsic viscosity [η] of 2.1 dl / g.

[Example 1]
For 100 parts by weight of the propylene-based resin composition for packaging material (C2-1) produced in Production Example 1, 0.1 part by weight of thermal stabilizer IRGANOX 1010 (manufactured by Chiba Specialty Chemicals Co., Ltd.), thermal stabilizer IRGAFOS168 ( 0.1 parts by weight of Ciba Specialty Chemicals Co., Ltd.), 0.1 parts by weight of calcium stearate, 0.5 parts by weight of anti-blocking agent Silo Hovic 505 (manufactured by Fuji Silysia Chemical Co., Ltd.) are mixed with a tumbler and then mixed with a twin screw extruder. A propylene-based resin composition for a packaging material in a pellet form was prepared by melt-kneading, and a cast film was formed with a T-die extruder [product number GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd.]. Table 2 shows the physical properties of the film.

<Melting and kneading conditions>
Same-direction biaxial kneader: Part number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 240 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm
<Film forming>
25mmΦT die extruder: Part No. GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd. Extrusion temperature: 230 ℃
Chill roll temperature: 30 ℃
Drawing speed: about 4.5m / min Film thickness: 70μm
[Example 2]
In Example 1, 100 parts by weight of propylene-based resin composition (C2-1) for packaging material was produced in Production Example 2.
A cast film was formed in the same manner except that the content was changed to 100 parts by weight of the propylene-based resin composition for packaging material (C2-2) produced in 1. Table 2 shows the physical properties of the obtained film.

[Example 3]
95 parts by weight of the propylene-based resin composition for packaging materials (C2-3) produced in Production Example 3 and ethylene-octene copolymer (D-1) (engage 8003 (registered trademark): manufactured by DuPont Dow Elastomer Co., Ltd., Density = 0.885 (g / cm ³ )) 5 parts by weight and 100 parts by weight Thermal stabilizer IRGANOX1010 (Ciba Specialty Chemicals Co., Ltd.) 0.1 part by weight Thermal stabilizer IRGAFOS168 (Ciba Specialty)・ Chemicals Co., Ltd.) 0.1 parts by weight, calcium stearate 0.1 parts by weight, anti-blocking agent Silo Hovic 505 (Fuji Silysia Chemical Co., Ltd.) 0.5 parts by weight are mixed in a tumbler and then melt-kneaded in a twin screw extruder. Then, a propylene-based resin composition for a packaging material in a pellet form was prepared, and a cast film was formed using a T-die extruder [product number GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd.]. Table 2 shows the physical properties of the film.

<Melting and kneading conditions>
Same-direction biaxial kneader: Part number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 240 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm
<Film forming>
25mmΦT die extruder: Part No. GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd. Extrusion temperature: 230 ℃
Chill roll temperature: 30 ℃
Drawing speed: about 4.5m / min Film thickness: 70μm
[Example 4]
In Example 3, 5 parts by weight of ethylene-octene copolymer (D-1) (engagement 8003 (registered trademark): manufactured by DuPont Dow Elastomer Co., Ltd., density = 0.885 (g / cm ³ )) was added to ethylene-octene copolymer. A cast film was formed in the same manner except that 5 parts by weight of polymer (D-2) (engage 8480 (registered trademark): manufactured by DuPont Dow Elastomer Co., Ltd., density = 0.902 (g / cm ³ )) was used. Table 2 shows the physical properties of the obtained film.

[Example 5]
In Example 3, 5 parts by weight of ethylene-octene copolymer (D-1) (engagement 8003 (registered trademark): manufactured by DuPont Dow Elastomer Co., Ltd., density = 0.885 (g / cm ³ )) was added to ethylene-octene copolymer. A cast film was formed in the same manner except that 5 parts by weight of polymer (D-3) (engage 8100 (registered trademark): manufactured by DuPont Dow Elastomer Co., Ltd., density = 0.870 (g / cm ³ )) was used. Table 2 shows the physical properties of the obtained film.

[Example 6]
In Example 1, 100 parts by weight of propylene-based resin composition (C2-1) for packaging material was produced in Production Example 5
A cast film was formed in the same manner except that 100 parts by weight of the propylene-based resin composition for packaging material (C2-5) produced in (1) was used. Table 2 shows the physical properties of the obtained film.

[Example 7]
80 parts by weight of the propylene polymer (A-1) produced in Production Example 7 and 20 parts by weight of the propylene-ethylene copolymer (B-1) produced in Production Example 9 are combined to 100 parts by weight. Thermal stabilizer IRGANOX1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight, thermal stabilizer IRGAFOS168 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight, calcium stearate 0.1 parts by weight, anti-blocking agent Silo Hovic After mixing 0.5 parts by weight of 505 (manufactured by Fuji Silysia Chemical Co., Ltd.) with a tumbler, melt-kneading with a twin screw extruder to prepare a propylene-based resin composition for a packaging material in a pellet form, A cast film was formed using GT-25A, manufactured by Plastic Engineering Laboratory. Table 2 shows the physical properties of the film.

<Melting and kneading conditions>
Two-axis kneader in the same direction: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 240 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm
<Film forming>
25mmΦT die extruder: Part No. GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd. Extrusion temperature: 230 ℃
Chill roll temperature: 30 ℃
Drawing speed: about 4.5m / min Film thickness: 70μm
[Example 8]
In Example 7, 80 parts by weight of the propylene-based polymer (A-1) was replaced with 80 parts by weight of the propylene homopolymer (A-3) (F102W: manufactured by Prime Polymer Co., Ltd.) produced with a Ziegler-Natta catalyst system. A cast film was formed in the same manner except that. Table 2 shows the physical properties of the obtained film.

[Comparative Example 1]
A cast film was prepared in the same manner as in Example 7, except that 20 parts by weight of the propylene-ethylene copolymer (B-1) was replaced with 20 parts by weight of the propylene-based polymer (A-2) produced in Production Example 8. Was formed. Table 2 shows the physical properties of the obtained film.

(Comparative Example 2)
In Example 1, 100 parts by weight of propylene-based resin composition (C2-1) for packaging material was used in Production Example 4
A cast film was formed in the same manner except that 100 parts by weight of the propylene-based resin composition for packaging material (C2-4) produced in (1) was used. Table 2 shows the physical properties of the obtained film.

[Comparative Example 3]
In Example 1, 100 parts by weight of propylene-based resin composition for packaging material (C2-1) was added to Production Example 6
A cast film was formed in the same manner except that 100 parts by weight of the propylene-based resin composition for packaging material (C2-6) produced in (1) was used. Table 2 shows the physical properties of the obtained film.

[Comparative Example 4]
100 parts by weight of 80 parts by weight of the propylene polymer (A-3) (F102W: manufactured by Prime Polymer Co., Ltd.) and 20 parts by weight of the propylene-ethylene copolymer (B-2) produced in Production Example 10 Heat stabilizer IRGANOX1010 (Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight, heat stabilizer IRGAFOS168 (Ciba Specialty Chemicals Co., Ltd.) 0.1
Part by weight, 0.1 parts by weight of calcium stearate, 0.5 parts by weight of anti-blocking agent Sirohovic 505 (Fuji Silysia Chemical Co., Ltd.) are mixed in a tumbler, and then melt-kneaded in a twin-screw extruder for pelletized packaging materials A propylene-based resin composition was prepared, and a cast film was formed using a T-die extruder [product number GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd.]. Table 2 shows the physical properties of the film.

<Melting and kneading conditions>
Two-axis kneading machine in the same direction: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 240 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm
<Film forming>
25mmΦT die extruder: Part No. GT-25A, manufactured by Plastic Engineering Laboratory Co., Ltd. Extrusion temperature: 230 ℃
Chill roll temperature: 30 ℃
Drawing speed: about 4.5m / min Film thickness: 70μm

The film and sheet obtained by molding the propylene resin composition satisfying specific properties of the present invention are excellent in high transparency, rigidity, low temperature impact resistance, and blocking resistance. The film and medical container packaging film and these sheets can be suitably used.

Claims (10)

Propylene-based polymer (A) satisfying the following requirements (a1) to (a2): 60 to 90% by weight and propylene-ethylene copolymer (B) satisfying the following requirements (b1) to (b4): 40 to 10% by weight (Wherein (A) + (B) = 100% by weight)
Propylene polymer (A);
(A1) Melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) is 0.1 to 10 (g / 10 min).
(A2) Melting point (Tm) measured with a differential scanning calorimeter (DSC) is 145 ° C to 170 ° C.
Propylene-ethylene copolymer (B);
(B1) Content of the structural unit derived from ethylene is 15 mol% to 25 mol%.
(B2) Decalin solvent, intrinsic viscosity [η] at 135 ° C. is 1.8 dl / g to 3.5 dl / g.
(B3) Molecular weight distribution (Mw / Mn) is 3.5 or less.
(B4) The n-decane soluble part at 23 ° C. is 95% by weight or more.   The propylene-based resin composition for packaging materials according to claim 1, wherein the propylene-based polymer (A) has a molecular weight distribution (Mw / Mn) of 3.5 or less.   The propylene-ethylene copolymer (B) is polymerized in the presence of a metallocene catalyst, and the propylene-based resin composition for packaging materials according to claim 1 or 2. N-decane insoluble part (D _insol ) at 23 ° C. satisfying the following requirements (a1 ′) to (a2 ′) satisfying the following requirements (b1 ′) to (b3 ′) at 23 ° C. n-decane soluble part ( _Dsol ) consists of 40 to 10 weight%, and melt flow rate (MFR; ASTM D1238, 230 degreeC, load 2.16kg) is 0.1-20 (g /
10 min) in the range of propylene-based resin composition for packaging materials;
n-decane insoluble part (D _insol );
(A1 ′) The content of structural units derived from ethylene is 2% by weight or less.
(A2 ′) The melting point (Tm) measured with a differential scanning calorimeter (DSC) is 145 ° C. to 170 ° C.
n-decane soluble part (D _sol );
(B1 ′) The content of structural units derived from ethylene is 15 mol% to 25 mol%.
(B2 ′) Decalin solvent, intrinsic viscosity [η] at 135 ° C. is 1.8 dl / g to 3.5 dl / g.
(B3 ′) Molecular weight distribution (Mw / Mn) is 3.5 or less. In the presence of a metallocene catalyst, the propylene-based resin composition is
[Step 1] Propylene and, if necessary, polymerizing ethylene to produce a polymer having an n-decane soluble part (D _sol ) at 23 ° C. of 0.5% by weight or less,
[Step 2] Propylene and ethylene are copolymerized to obtain a copolymer having a n-decane insoluble part (D _insol ) at 23 ° C. of 5.0% by weight or less continuously. The propylene-based resin composition for packaging materials according to claim 4, wherein Further, ethylene-α-olefin copolymer (D) having a density of 0.850 to 0.910 g / cm ³
The propylene-type resin composition for packaging materials in any one of Claims 1-5 characterized by the above-mentioned.   Furthermore, ethylene-propylene copolymer (B ') whose content of the structural unit derived from ethylene is 25-85 mol% is contained, The propylene-type resin for packaging materials in any one of Claims 1-5 characterized by the above-mentioned. Composition.   A retort film or sheet obtained by molding the propylene-based resin composition for packaging materials according to claim 1.   The film or sheet for protection obtained by shape | molding the propylene-type resin composition for packaging materials in any one of Claims 1-7.   A medical container packaging film or sheet obtained by molding the propylene-based resin composition for packaging materials according to any one of claims 1 to 7.