JP2011057852A - Polypropylene-based resin composition and film thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based resin composition which hardly causes die build-up or fish eye even when producing a film for a long time and can obtain the film excellent in transparency. <P>SOLUTION: The polypropylene-based resin composition comprises 70 to 99 wt.% of a polypropylene-based resin (A) having a molecular weight distribution (Aw/An) measured by GPC of 5 or less and 1 to 30 wt.% of a polypropylene-based resin (B), wherein the polypropylene-based resin (B) is provided by a polymerization method including a process of producing 38 to 80 wt.% of crystalline propylene polymer component (i) having an intrinsic viscosity of 3.5 to 10 dl/g and a process of producing 62 to 20 wt.% of crystalline propylene polymer component (ii) having an intrinsic viscosity of 0.5 to 1.5 dl/g, and a ratio (MFR(A)/MFR(B)) of MFR(A) of the polypropylene-based resin (A) to MFR(B) of the polypropylene-based resin (B) is 0.5 to 12. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polypropylene resin composition and a polypropylene film comprising the same.

  Polypropylene-based films have been used mainly for food packaging applications because they are not only excellent in transparency, rigidity, film strength, and heat seal performance, but also excellent in hygiene when in contact with food.

  Currently, as a raw material for a polypropylene film that satisfies the above requirements, for example, a polypropylene type produced by combining a vapor phase process with a simple production process and a high performance catalyst typified by a Ti-Mg composite Ziegler Natta catalyst. Resin. Such a resin is superior in anti-blocking properties and food hygiene because it has fewer low molecular weight components and less sticky components than the polypropylene-based resin produced with the titanium trichloride type Ziegler Natta catalyst that has been used for a long time. Can be obtained. However, when the polypropylene resin obtained in this way is formed into a film for a long time using a large film processing machine, a processing defect phenomenon called “Meanyi” is likely to occur, and an additive for improving processability in particular. In applications that cannot be added, film productivity is reduced and becomes a problem.

  “Mayani” is a phenomenon in which additives and deteriorated PP adhere to the exit portion of the die through which the film is extruded, and when the amount generated is increased, the film is damaged or mixed into the film and causes fish eyes. The mechanism of the occurrence of this stubble is not clear at present, but it has been confirmed that it can be improved by broadening the molecular weight distribution. As a method for widening the molecular weight distribution, for example, a multi-stage polymerization method in which polymerization tanks are connected in series and continuously polymerized has been reported (for example, Patent Documents 1 and 2).

  However, since the polypropylene resin obtained by the above-mentioned multistage polymerization has a small ratio of the high molecular weight polypropylene component to the low molecular weight polypropylene component, the high molecular weight polypropylene component should be uniformly dispersed in the low molecular weight polypropylene component. However, there is a problem that fish eyes are likely to occur during film formation.

Patent Documents 3 to 5 describe methods for obtaining a polypropylene resin having a large ratio of a high molecular weight polypropylene component to a low molecular weight polypropylene component by multistage polymerization.
However, a film made of a polypropylene resin containing a large amount of these high molecular weight polypropylene components improves the fish eye, but the transparency of the film is extremely deteriorated.

JP-A-11-228629 JP2002-80656 JP-A-6-192497 JP 2002-348423 JP2001-329010A

  In view of such circumstances, an object of the present invention is to provide a polypropylene-based resin composition capable of obtaining a film having less transparency and excellent transparency even when a film is produced for a long time, and a polypropylene system comprising the same. To provide a film.

  As a result of intensive studies, the present inventor has found that the present invention can solve the above problems, and has completed the present invention.

That is, the present invention is a polypropylene containing 70 to 99% by weight of a polypropylene resin (A) having a molecular weight distribution (Aw / An) measured by GPC of 5 or less and 1 to 30% by weight of the polypropylene resin (B). A resin composition (the total of the weight of the polypropylene resin (A) and the weight of the polypropylene resin is 100% by weight),
The polypropylene resin (B) includes a step of producing 38 to 80% by weight of a crystalline propylene polymer component (i) having an intrinsic viscosity of 3.5 to 10 dl / g, and an intrinsic viscosity of 0.5 to 1.5 dl / g. And a step of producing 62 to 20% by weight of a crystalline propylene polymer component (ii) of (the weight of the crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii) The total weight is 100% by weight),
It is related with the said composition whose ratio (MFR (A) / MFR (B)) of MFR (A) of polypropylene resin (A) with respect to MFR (B) of polypropylene resin (B) is 0.5-12.

Furthermore, the present invention relates to polypropylene containing 70 to 99% by weight of polypropylene resin (A) having a molecular weight distribution (Aw / An) measured by GPC of 5 or less, and 1 to 30% by weight of polypropylene resin (C). A resin composition (the total of the weight of the polypropylene resin (A) and the weight of the polypropylene resin (C) is 100% by weight),
The polypropylene resin (C) includes 50 to 99.9% by weight of the polypropylene resin (B) and 0.1 to 50% by weight of the polypropylene resin (iii) having an intrinsic viscosity of 0.5 to 2 dl / g. Including (the total of the weight of the polypropylene resin (B) and the weight of the polypropylene resin (iii) is 100% by weight),
The polypropylene resin (B) includes a step of producing 38 to 80% by weight of a crystalline propylene polymer component (i) having an intrinsic viscosity of 3.5 to 10 dl / g, and an intrinsic viscosity of 0.5 to 1.5 dl / g. And a step of producing 62 to 20% by weight of a crystalline propylene polymer component (ii) of (the weight of the crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii) The total weight is 100% by weight),
When the weight of the polypropylene resin (C) is 100% by weight, the weight of the crystalline propylene polymer component (i) is 37-60% by weight,
It is related with the said composition whose ratio (MFR (A) / MFR (C)) of MFR (A) of polypropylene resin (A) with respect to MFR (C) of polypropylene resin (C) is 0.5-12.

  According to the present invention, even when a film is produced for a long time, it is difficult to generate a sag or fish eye, and a film having excellent transparency can be obtained.

The present invention will be described in detail below.

<Polypropylene resin (A)>
The polypropylene resin (A) of the present invention is a polymer obtained by polymerizing a monomer mainly composed of propylene, a propylene-ethylene random copolymer, a propylene-ethylene-α-olefin terpolymer, and mainly propylene. A polymer component obtained by polymerizing a monomer comprising, and a copolymer component obtained by polymerizing a monomer comprising ethylene and / or an α-olefin having 4 to 12 carbon atoms and propylene. Examples thereof include polypropylene-based copolymers (sometimes referred to as propylene-ethylene block copolymers) obtained by the above multistage production. Preferred are a propylene homopolymer, a propylene-ethylene random copolymer, and a propylene-ethylene-α-olefin terpolymer. These may be used alone or in combination of two or more.

  Examples of the α-olefin include α-olefins having 4 to 12 carbon atoms, such as 1-butene, 2-methyl-1-propene, 1-pentene, 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-undecene, 1-dodecene and the like. 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene and 1-hexene are more preferable from the viewpoints of copolymerization characteristics and economy.

  The content of ethylene in the copolymer is usually 0.1 to 10% by weight, and the content of α-olefin is usually 0.1 to 30% by weight.

The melt flow rate (MFR (A)) measured at 230 ° C. of the polypropylene resin (A) is preferably 0.1 to 20 g / 10 min, more preferably 1 from the viewpoint of fluidity or film formation. -10 g / 10 min.

The polypropylene resin (A) has a molecular weight distribution (Aw / An) measured by GPC of 5 or less, and when the molecular weight distribution exceeds 5, the anisotropy and transparency of the film may deteriorate. . The range of the preferred molecular weight distribution is 4 or less, more preferably 3 or less.

The molecular weight distribution referred to in the present invention is evaluated by the ratio (Aw / An) of the weight average molecular weight (Aw) to the number average molecular weight (An).

The propylene-based resin (A) includes, for example, a Ti-Mg-based catalyst composed of a solid catalyst component in which a Ti compound is combined with a magnesium compound, an organoaluminum compound and, if necessary, an electron-donating compound, etc. Obtained by using a catalyst system in which the third component is combined, or a metallocene catalyst, such as JP-A-61-218606, JP-A-61-287904, JP-A-7-216017, etc. Can be obtained with the catalyst system described in 1).

Examples of the polymerization method of the polypropylene resin (A) of the present invention include, for example, a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method without a solvent, a gas phase polymerization method, or a continuous polymerization thereof. The liquid phase-gas phase polymerization method to be performed and the like are mentioned. From the viewpoint of productivity, the gas phase polymerization method, the liquid phase-gas phase polymerization method and the like are preferable.

<Polypropylene resin (B)>
The polypropylene resin (B) includes a step of producing a crystalline propylene polymer component (i) having an intrinsic viscosity of 3.5 to 10 dl / g and a crystalline propylene polymer having an intrinsic viscosity of 0.5 to 1.5 dl / g. It is obtained by a polymerization method including a step of producing a coalescing component (ii). The proportion of the crystalline propylene component (i) is 38 to 80% by weight, the proportion of the crystalline propylene polymer component (ii) is 20 to 62% by weight, and preferably the proportion of the crystalline propylene component (i). Is 40 to 60% by weight, and the proportion of the crystalline propylene polymer component (ii) is 40 to 60% by weight (the weight of the crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii) And 100% by weight).

  As a specific method for producing the polypropylene resin (B), for example, after the crystalline propylene polymer component (i) is polymerized in the first stage, the crystalline propylene polymer component (i) is subsequently polymerized in the second stage. A batch polymerization method in which the crystalline propylene polymer component (ii) is polymerized in the same polymerization tank as in the polymerization, or two or more polymerization tanks are arranged in series, and the crystalline propylene polymer component is used as the first stage. After polymerization of (i), the product is transferred to the next polymerization tank, and a continuous polymerization method in which the crystalline propylene polymer component (ii) is polymerized as the second stage in the polymerization tank can be mentioned. From the viewpoint of this, a continuous polymerization method is preferred. In the case of the continuous polymerization method, the polymerization tanks in the first stage and the second stage may be one tank or two or more tanks.

The intrinsic viscosity of the crystalline propylene polymer component (i) is 3.5 to 10 dl / g, preferably 3.5 to 6.0 dl / g. When the intrinsic viscosity exceeds 10 dl / g, the kneadability with the crystalline propylene polymer component (ii) is deteriorated to generate fish eyes, or the MFR of the polypropylene resin (B) obtained by kneading is lowered. The kneadability with the polypropylene resin (A) deteriorates and fish eyes are generated.
On the other hand, when the intrinsic viscosity is less than 3.5 dl / g, a sufficient improvement effect of Meani cannot be obtained.

The intrinsic viscosity of the crystalline propylene polymer component (ii) is 0.5 to 1.5 dl / g, preferably 0.7 to 1.2 dl / g.
The intrinsic viscosity of the crystalline propylene polymer component (ii) is the polypropylene resin (B) comprising the crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii), assuming that the intrinsic viscosity can be added. In the case of the above, the intrinsic viscosity [η] B of the finally obtained polypropylene resin (B), the intrinsic viscosity [η] i of the crystalline propylene polymer component (i), and the crystalline propylene polymer component (i) And the intrinsic viscosity [η] ii (dl / g) of the crystalline propylene polymer component (ii) from the content ratio (% by weight) in (B) of each of the crystalline propylene polymer component (ii) according to the following formula 1. Ask.

[Η] ii = ([η] B × 100− [η] i × Wi) ÷ Wii [Equation 1]
[Η] B: Intrinsic viscosity (dl / g) of polypropylene resin (B)
[Η] i: Intrinsic viscosity (dl / g) of crystalline propylene polymer component (i)
Wi: Content of crystalline propylene polymer component (i) (% by weight)
Wii: Content of crystalline propylene polymer component (ii) (% by weight)

  From the viewpoint of improving fish eyes, the polypropylene resin (B) is a crystalline propylene polymer using a kneading apparatus such as a single-screw extruder, a co-directional twin-screw extruder, a different-direction twin-screw extruder, or a Banbury mixer. The component (i) and the crystalline propylene polymer component (ii) are preferably kneaded and then mixed with the polypropylene resin (A).

  The MFR (B) of the polypropylene resin (B) is preferably 0.1 to 20 g / min, more preferably 0.5 to 10 g / 10 min, most preferably from the viewpoint of dispersibility with the polypropylene resin (A). 1 to 5 g / min.

  The ratio of MFR (A) to MFR (B) (MFR (A) / MFR (B)) is 0.5 to 12 from the viewpoint of dispersibility of the polypropylene resin (A) and the polypropylene resin (B). , Preferably 1-7.

  The crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii) are crystalline propylene polymer components each having an isotactic polypropylene crystal structure, and are propylene homopolymer or propylene and crystallinity. A copolymer of ethylene and / or an α-olefin comonomer having 4 to 12 carbon atoms in such an amount that does not lose the amount is preferable. Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. For example, in the case of ethylene, the content of repeating units derived from ethylene in the copolymer is usually 10% by weight or less, and the number of carbon atoms such as 1-butene is 4 or less. In the case of -12 α-olefins, the content of repeating units derived from α-olefins in the copolymer is usually 30% by weight or less.

As the crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii), particularly preferred are propylene homopolymer and propylene having a content of repeating units derived from ethylene of 10% by weight or less, respectively. A random copolymer of ethylene and ethylene, a random copolymer of propylene and 1-butene having a repeating unit content derived from 1-butene of 30% by weight, or a repeating unit content derived from ethylene It is a ternary random copolymer of propylene, ethylene and 1-butene having a content of repeating units derived from 1-butene of 30% by weight or less.
The crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii) may be the same or different.

  The polypropylene resin (B) includes, for example, a Ti—Mg catalyst comprising a solid catalyst component obtained by complexing a Ti compound with a magnesium compound, an organoaluminum compound and, if necessary, an electron donating compound, etc. Obtained by using a catalyst system in which the third component is combined, or a metallocene catalyst, such as JP-A-61-218606, JP-A-61-287904, JP-A-7-216017, etc. Can be obtained with the catalyst system described in 1).

  Examples of the polymerization method of the polypropylene resin (B) include a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method without a solvent, a gas phase polymerization method, or a liquid phase in which they are continuously performed. -Although vapor phase polymerization method etc. are mentioned, From a viewpoint of productivity, Preferably a gas phase polymerization method, a liquid phase-gas phase polymerization method, etc. are mentioned.

<Polypropylene resin (iii)>
The polypropylene resin (iii) is a polymer obtained by polymerizing a monomer mainly composed of propylene, a propylene-ethylene random copolymer, a propylene-ethylene-α-olefin terpolymer, and a monomer mainly composed of propylene. And a polymer component obtained by polymerizing ethylene and / or a monomer composed of ethylene and / or an α-olefin having 4 to 12 carbon atoms and propylene, in at least two or more stages. And polypropylene-based copolymers (sometimes referred to as propylene-ethylene block copolymers) obtained by the production of Preferred are a propylene homopolymer, a propylene-ethylene random copolymer, and a propylene-ethylene-α-olefin terpolymer. These may be used alone or in combination of two or more.

  Examples of the α-olefin include α-olefins having 4 to 12 carbon atoms, such as 1-butene, 2-methyl-1-propene, 1-pentene, 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-undecene, 1-dodecene and the like. 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene and 1-hexene are more preferable from the viewpoints of copolymerization characteristics and economy.

  The content of ethylene in the copolymer is usually 0.1 to 10% by weight, and the content of α-olefin is usually 0.1 to 30% by weight.

  The intrinsic viscosity of the polypropylene resin (iii) is preferably 0.5 to 2 dl / g, more preferably 0.8 to 0.5% from the viewpoint of further improving the dispersibility of the polypropylene resin (A) and the polypropylene resin (B). 1.8 dl / g.

  The polypropylene resin (iii) is, for example, a Ti-Mg catalyst comprising a solid catalyst component obtained by complexing a Ti compound with a magnesium compound, an organoaluminum compound and, if necessary, an electron donating compound, etc. It is mentioned that it can be obtained by using a catalyst system in which the third component is combined or a metallocene catalyst. For example, JP-A-61-218606, JP-A-61-287904, JP-A-7- It can be obtained by the catalyst system described in Japanese Patent No. 216017.

  Examples of the polymerization method of the polypropylene resin (iii) include a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method without a solvent, a gas phase polymerization method, or a liquid phase in which they are continuously performed. -Although vapor phase polymerization method etc. are mentioned, From a viewpoint of productivity, Preferably a gas phase polymerization method, a liquid phase-gas phase polymerization method, etc. are mentioned.

<Polypropylene resin (C)>
The polypropylene resin (C) contains 50 to 99.9% by weight of the polypropylene resin (B) and 0.1 to 50% by weight of the polypropylene resin (iii). Preferably, the polypropylene resin (B) 60 to 90% by weight and 10 to 40% by weight of the polypropylene resin (iii) (the total of the weight of the polypropylene resin (A) and the weight of the polypropylene resin (C) is 100% by weight). Polypropylene resin (C) is preferable because of its excellent dispersibility with respect to polypropylene resin (A).
At this time, the ratio of the crystalline polypropylene component (i) (the weight of the polypropylene resin (C) is 100% by weight) is 37 to 60% by weight, preferably 40 to 55% by weight.

  From the viewpoint of improving the fish eye, the polypropylene resin (C) is kneaded by using a kneading apparatus such as a single screw extruder, a same direction twin screw extruder, a different direction twin screw extruder, a Banbury mixer, and the like. It is preferable to mix with resin (A).

  The MFR (C) of the polypropylene resin (C) is preferably from 0.1 to 20 g / min, more preferably from 0.5 to 10 g / 10 min, most preferably from the viewpoint of dispersibility with the polypropylene resin (A). 1 to 5 g / min.

  The ratio of MFR (A) to MFR (C) (MFR (A) / MFR (C)) is 0.5 to 12 from the viewpoint of dispersibility of the polypropylene resin (A) and the polypropylene resin (C). , Preferably 1-7.

<Additives>
The polypropylene resin composition of the present invention comprises 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane. Phenolic stabilizers represented by (IRGANOX 1010) and n-octadecyl-3- (4′-hydroxy-3,5′-di-t-butylphenyl) propionate (IRGANOX 1076), bis (2,4-di -T-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite and other phosphite stabilizers, lubricants represented by higher fatty acid amides and higher fatty acid esters, Glycerin esters and sorbitan esters of fatty acids having 8 to 22 carbon atoms, polyethylene glycol An antistatic agent such as a ruester, and an antiblocking agent represented by silica, calcium carbonate, talc and the like can be contained.
The polypropylene resin composition of the present invention can also contain a polyethylene resin represented by an ethylene-α-olefin copolymer, low density polyethylene, high density polyethylene, and the like.

  Processability improvers, stabilizers, lubricants, anti-blocking agents, etc. to be blended according to various purposes may be subjected to film processing after melt-kneading with the polypropylene resin composition of the present invention in advance, or individually. You may dry-blend or make into one or more master batches, and may use for film processing after dry blending.

<Polypropylene film>
The polypropylene film of the present invention may be a single layer film made of the polypropylene resin composition of the present invention, or a laminated film including at least one film made of the polypropylene resin composition of the present invention. Good. In the case of a laminated film, the film made of the polypropylene resin composition is preferably formed on the outermost surface of the film.

  The preferred thickness of the polypropylene film of the present invention is 10 to 250 μm, more preferably 20 to 150 μm, and most preferably 20 to 100 μm.

  Examples of the method for producing the polypropylene film of the present invention include a method for forming a film under known molding conditions using a known inflation film production apparatus, T-die film production apparatus, or the like. Among these, a production method using a T-die film production apparatus is preferable.

In the case of using a T-die film manufacturing apparatus, examples of the molding process conditions include the following examples.
Temperature of molten resin extruded from die lip 180-300 ° C
Cutting speed of molten resin at the die lip 10 to 1500 sec ⁻¹
Chill roll rotation speed 10-500m / min
Chill roll temperature 10-80 ° C

  Examples of the method for producing a multilayer film on which the polypropylene film of the present invention is laminated include a commonly used coextrusion method, extrusion lamination method, thermal lamination method, and dry lamination method.

  The polypropylene film of the present invention can be produced by stretching a film or sheet obtained by molding in advance. Examples of the stretching method include a method of stretching uniaxially or biaxially by a roll stretching method, a tenter stretching method, a tubular stretching method, or the like.

  Although the use which uses the polypropylene film of this invention is not specifically limited, For example, it can be used for food packaging uses, such as bread and vegetables, clothing packaging uses, such as a shirt, and industrial parts packaging use.

The film is made of a cellophane, paper, woven fabric, paperboard, aluminum foil, polyamide resin such as nylon 6 or nylon 66, polyester such as polyethylene terephthalate or polybutylene terephthalate by a known technique such as a lamination method such as dry lamination or sand lamination. It can also be used as a film laminated on a substrate such as resin or stretched polypropylene.
Further, the film can be used as a metal-deposited polypropylene film obtained by depositing metal vapor on the film surface.

  Examples of the method for producing a metal-deposited polypropylene film include a method in which the polypropylene-based film of the present invention is placed under a high vacuum, and vaporized metal vapor is introduced and deposited on the film surface. Examples of the metal to be deposited include aluminum, titanium, chromium, nickel, copper, germanium, tin, and selenium, with aluminum being preferred.

Hereinafter, the present invention will be described with reference to examples and specific examples.
The measured value of each item of an Example and a comparative example was measured with the following method.

(1) Intrinsic viscosity of polymer (unit: dl / g)
The measurement was performed in 135 ° C. tetralin using an Ubbelohde viscometer. In addition, the intrinsic viscosity of the crystalline propylene polymer portion (b) in Reference Example 1 below is determined from the crystalline propylene polymer portion (a) and the intrinsic viscosity of the entire polymer, using the calculation formula described in the specification. It was.

(2) Melt flow rate (MFR)
It measured at 230 degreeC according to the method of the conditions 14 (Condition Number 14) of JISK7210. (Unit: g / 10 minutes)

(3) Molecular weight distribution (GPC)
G. P. C. (Gel permeation chromatography) was measured under the following conditions. The molecular weight distribution was evaluated by the ratio (Aw / An) of the weight average molecular weight (Aw) and the number average molecular weight (An).
Model: 150CV type (Millipore Waters);
Column: Shodex M / S 80;
Measurement temperature: 145 ° C;
Solvent: orthodichlorobenzene;
Sample concentration: 5 mg / 8 mL;
A calibration curve was prepared using standard polystyrene.

(4) Transparency (HAZE, unit:%)
It measured according to JIS K7105.

(5) Fish Eye Evaluation After film formation using a T-die film molding machine, one film was cut out and the number of all fish eyes seen at 16 cm square (256 cm 2) was visually measured.

(6) Evaluation of Meani Using a 90-mmφ extruder and a T-die film processing machine equipped with two 65 mmφ extruders, film formation was carried out for 2 hours continuously, and the state of adherence to the die lip portion was evaluated. The film forming conditions and the evaluation criteria are as follows.
Molding conditions Filter: Uses a sintered filter with a filtration accuracy of 60 μm.
Extruder set temperature: 280 ° C
Die set temperature: 260 ° C
Die lip gap 0.8mm
Total extrusion rate: 220 kg / hr
Film forming speed: 50 m / min Chill roll temperature: 40 ° C.
Film thickness: 70μm
Two hours after the start of processing of the meani evaluation criteria film, the appearance of the meani attached to the die lip was photographed and evaluated.
5 points ... Situation where no sealant adheres at all 4 points ... The mean value of the mean length measured from the photograph is less than 0.05 mm 3 points ... The mean value of the mean length measured from the photograph is 0.05 to 0 .1mm
2 points ... The mean value of the length measured from the photograph is 0.1 to 0.2 mm.
1 point: The average length of the measured length of the photograph is 0.2 mm or more.

The polymers used in the examples and comparative examples were as follows.
[Phosphorous esters (1)]
Compound name: 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-tbutylphenyl) propoxy] dibenzo [d, f] [1,3 2] Dioxaphosphepine Product name: Sumilizer GP (manufactured by Sumitomo Chemical)

[Phenolic antioxidant (1)]
Product Name: Irganox 1010 (Ciba Specialty Chemicals)

[HDPE]
High density polyethylene with MFR measured at 230 ° C. of 13 g / 10 min and density of 0.96 g / cm ³

<Polypropylene resin (A)>
[PP-A (1)]
A copolymer of propylene and ethylene was polymerized in the gas phase using a Ti-Mg catalyst based Ziegler-Natta type catalyst. When the obtained resin was melt-extruded and pelletized, the molecular weight distribution Aw / An of the pellet was 4.2, and the MFR was 1.3 g / 10 min.

[PP-A (2)]
A copolymer of propylene and ethylene was polymerized in the gas phase using a Ti-Mg catalyst based Ziegler-Natta type catalyst. When the obtained resin was melt-extruded by a granulator and pelletized, the molecular weight distribution Aw / An of the pellet was 4.2, and the melt flow rate measured at 230 ° C. was 2.5 g / 10 min. .

[PP-A (3)]
A copolymer of propylene, ethylene and butene-1 was polymerized in the gas phase using a Ti-Mg catalyst based Ziegler-Natta type catalyst. When the obtained resin was melt-extruded by a granulator and pelletized, the molecular weight distribution Aw / An of the pellet was 4.4, and the melt flow rate measured at 230 ° C. was 6.9 g / 10 min. .

[PP-A (4)]
A propylene homopolymer was polymerized in the gas phase using a Ziegler-Natta type catalyst based on a Ti-Mg catalyst. The intrinsic viscosity of the obtained resin was 3.0 dl / g. The molecular weight distribution Aw / An was 3.2.

[PP-A (5)]
A copolymer of propylene and ethylene was polymerized in the gas phase using a Ti-Mg catalyst based Ziegler-Natta type catalyst. MFR which measured the obtained resin at 230 degreeC was 7 g / 10min. The molecular weight distribution Aw / An was 3.8.

<Polypropylene resin (B)>
[PP-B (1)]
(Synthesis of solid catalyst components)
After a 200 LSUS reaction vessel equipped with a stirrer was replaced with nitrogen, 80 L of hexane, 6.55 mol of tetrabutoxytitanium, 2.8 mol of diisobutyl phthalate, and 98.9 mol of tetraethoxysilane were added to obtain a uniform solution. Next, 51 L of a diisobutyl ether solution of butyl magnesium chloride having a concentration of 2.1 mol / L was gradually added dropwise over 5 hours while keeping the temperature in the reaction vessel at 5 ° C. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, and then solid-liquid separation was performed at room temperature. Next, toluene was added so that the slurry concentration became 0.2 kg / L, 47.6 mol of diisobutyl phthalate was added, and the reaction was performed at 95 ° C. for 30 minutes. After the reaction, it was separated into solid and liquid and washed twice with toluene. Next, 3.13 mol of diisobutyl phthalate, 8.9 mol of butyl ether and 274 mol of titanium tetrachloride were added, and the reaction was carried out at 105 ° C. for 3 hours. After the completion of the reaction, solid-liquid separation was performed at the same temperature, followed by washing twice with 90 L of toluene at the same temperature. Next, after adjusting the slurry concentration to 0.4 kg / L, 8.9 mol of butyl ether and 137 mol of titanium tetrachloride were added, and the reaction was carried out at 105 ° C. for 1 hour. After the completion of the reaction, solid-liquid separation was performed at the same temperature, followed by washing with 90 L of toluene three times at the same temperature, and further washing with 70 L of hexane three times, followed by drying under reduced pressure to obtain 11.4 kg of a solid catalyst component. The solid catalyst component contains 1.8% by weight of titanium base paper, 20.1% by weight of magnesium atom, 8.4% by weight of phthalate ester, 0.3% by weight of ethoxy group, 0.2% by weight of butoxy group, Had no good particle properties.

(Preactivation of solid catalyst component)
Made of SUS with an internal volume of 3 L, fully dehydrated and degassed 1.5 L of n-hexane, 30.0 mmol of triethylaluminum, 3.00 mmol of cyclohexylethyldimethoxysilane, and 13.1 g of the above solid catalyst component. Then, 19.7 g of propylene was continuously supplied over 45 minutes while keeping the temperature in the tank at 3 to 8 ° C., and preactivation was performed.
(Polymerization of crystalline propylene polymer component (ia))
While supplying liquid propylene at 40 kg / h so as to maintain a polymerization temperature of 55 ° C. and a polymerization pressure of 2.28 MPa in a 40 L internal polymerization tank made of SUS, 40.8 mmol / h of triethylaluminum, cyclohexylethyldimethoxysilane 6.12 mmol / h, ethylene 0.2 kg / h, hydrogen 5.0 NL / h, and preactivated solid catalyst component 0.436 g / h are continuously fed to perform ethylene / propylene random copolymerization, A polymer of 0.81 kg / h was obtained. The amount of polymer produced was 1858 g per gram of catalyst, and as a result of sampling and analysis of a part thereof, the intrinsic viscosity was 4.15 dl / g. The obtained polymer was continuously transferred to the second tank without being deactivated.
(Polymerization of crystalline propylene polymer component (ib))
In a fluidized bed reactor with an internal volume of 1 m ^{3 with} a stirrer, a polymerization temperature of 80 ° C., a polymerization pressure of 1.8 MPa, propylene in the gas phase, ethylene, a hydrogen concentration in hydrogen of 0.016 vol%, and ethylene in propylene and ethylene A polymer of 13.4 kg / h is obtained by continuously continuing propylene polymerization with the catalyst-containing polymer transferred from the first tank while supplying propylene and ethylene so as to maintain the concentration of 2.81 vol%. was gotten. The intrinsic viscosity [η] _i of this polymer (crystalline propylene polymer component (i)) was 4.10 dl / g.
(Polymerization of crystalline propylene polymer component (ii))
In a fluidized bed reactor with an internal volume of 1 m ^{3 with} a stirrer, a polymerization temperature of 80 ° C., a polymerization pressure of 1.4 MPa, a hydrogen concentration of propylene, ethylene and hydrogen in the gas phase of 15.4 vol%, and ethylene in propylene and ethylene While supplying propylene, ethylene and hydrogen so as to maintain the concentration of 2.49 vol%, by continuing the propylene polymerization with the catalyst-containing polymer transferred from the second tank, 19.5 kg / h A polymer was obtained. The intrinsic viscosity of this polymer (polypropylene resin (B)) was 3.08 dl / g.
From the above results, the amount of polymer produced during polymerization of the crystalline propylene polymer component (ib) was 28876 g per gram of catalyst, and the amount of polymer produced during polymerization of the crystalline propylene polymer component (ii) was 1 g of catalyst. The polymerization weight ratio of the first tank, the second tank, and the third tank is 4.1: 64.6: 31.3, and the intrinsic viscosity of the crystalline propylene polymer component (ii) is [Η] _ii was determined to be 0.84 dl / g.
(Melt kneading of polypropylene resin (B))
After mixing 100 parts by weight of the above polypropylene resin (B), 0.1 part by weight of phosphites (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, Nippon Steel Works Using the same direction twin screw extruder; TEX30, pelletization was performed by melt extrusion at a cylinder temperature of 200 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr. The melt flow rate of the obtained pellets measured at 230 ° C. was 0.7 g / 10 minutes.

[PP-B (2)]
Using a Ziegler-Natta type catalyst of a Ti-Mg catalyst system, the copolymer part of propylene and ethylene (crystalline propylene polymer component (i)) is polymerized in liquefied propylene in the first step, and then the second step The polymer portion of propylene and ethylene (crystalline propylene polymer component (ii)) was polymerized in the gas phase. In the obtained resin (polypropylene resin (B)), the content of the crystalline propylene polymer component (i) is 65% by weight, and the content of the crystalline propylene polymer component (ii) is 35% by weight. Yes, the intrinsic viscosity [η] _i of the crystalline propylene polymer component (i) is 8.5 dl / g, and the intrinsic viscosity [η] _{ii of} the crystalline propylene polymer component (ii) is 0.9 dl / g. there were.

(Melt kneading of polypropylene resin (B))
After mixing 100 parts by weight of the above polypropylene resin, 0.1 part by weight of phosphites (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, Nippon Steel Directional twin screw extruder: Using TEX30, pelletization was performed by melt extrusion at a cylinder temperature of 230 ° C., a screw rotation speed of 200 rpm, and an extrusion rate of 12 kg / hr. The melt flow rate of the obtained pellets measured at 230 ° C. was 0.2 g / 10 minutes.

[PP-B (3)]
(Synthesis of solid catalyst)
A Ti-Mg catalyst based Ziegler-Natta catalyst was synthesized in the same manner as PP-B (1).
(Preactivation of solid catalyst component)
Made of SUS with an internal volume of 3 L, fully dehydrated and degassed in an autoclave with a stirrer, 1.5 L of n-hexane, 30.0 mmol of triethylaluminum, 3.00 mmol of t-butyl-n-propyldimethoxysilane, the above solid catalyst 24.0 g of components were added, and 48 g of propylene was continuously supplied over 45 minutes while maintaining the temperature in the tank at 5 to 15 ° C., and preactivation was performed.
(Polymerization of crystalline propylene polymer component (i))
In a polymerization tank made of SUS with an internal volume of 200 L, while supplying liquid propylene at 45 kg / h so as to maintain a polymerization temperature of 55 ° C. and a polymerization pressure of 2.1 MPa, 62.0 mmol / h of triethylaluminum, t-butyl- N-propyldimethoxysilane (6.16 mmol / h) and a preactivated solid catalyst component (1.064 g / h) were continuously fed to carry out propylene polymerization in the substantial absence of hydrogen, and 3.3 kg / h. The following polymer was obtained. The amount of polymer produced at this time was 1 g of catalyst and 3102 g per hour. As a result of sampling and analysis of a part thereof, the intrinsic viscosity [η] _i was 7.5 dl / g. The obtained polymer was continuously transferred to the second tank without being deactivated.
(Polymerization of crystalline propylene polymer component (ii))
In a fluidized bed reactor with an internal volume of 1 m ^{3 with} a stirrer, propylene and hydrogen are supplied so as to maintain a polymerization temperature of 80 ° C., a polymerization pressure of 1.8 MPa, and a hydrogen concentration of 3.77 vol% in propylene and hydrogen in the gas phase However, the propylene polymerization with the catalyst-containing polymer transferred from the first tank was continuously continued to obtain a polymer of 20.8 kg / h. The intrinsic viscosity of this polymer (polypropylene resin (B)) was 2.19 dl / g.
From the above results, the amount of polymer produced during the polymerization of the crystalline propylene polymer component (ii) is 1549 g per catalyst and 19549 g per hour, and the polymerization weight ratio between the first tank and the second tank is 15.9: The intrinsic viscosity [η] _ii of the crystalline propylene polymer component (ii) was 1.19 dl / g. Further, Mw / Mn of this polymer was 14.6.
(Melt kneading of polypropylene resin (B))
After mixing 100 parts by weight of the above polypropylene resin, 0.1 part by weight of phosphites (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, Nippon Steel Directional twin screw extruder: Using TEX30, pelletization was performed by melt extrusion at a cylinder temperature of 200 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr. The obtained pellet had a molecular weight distribution Aw / An of 9.9 and a melt flow rate measured at 230 ° C. of 6.3 g / 10 min.

[PP-B (4)]
(Synthesis of solid catalyst)
A Ti-Mg catalyst based Ziegler-Natta catalyst was synthesized in the same manner as PP-B (1).
(Preactivation of solid catalyst component)
Made of SUS with an internal volume of 3 L, fully dehydrated and degassed 1.5 L of n-hexane, 30.0 mmol of triethylaluminum, 3.00 mmol of cyclohexylethyldimethoxysilane, and 21.9 g of the above solid catalyst component. Then, 21.9 g of propylene was continuously supplied over 45 minutes while maintaining the temperature in the tank at 3 to 10 ° C., and preactivation was performed.
(Polymerization of crystalline propylene polymer component (i))
In a polymerization tank made of SUS with an internal volume of 40 L, while supplying liquid propylene at 40 kg / h so as to maintain a polymerization temperature of 60 ° C. and a polymerization pressure of 2.50 MPa, 41.1 mmol / h of triethylaluminum, cyclohexylethyldimethoxysilane 10.2 mmol / h, ethylene 0.06 kg / h, butene 2.4 kg / h, hydrogen 1.0 NL / h, and preactivated solid catalyst component 0.64 g / h were continuously fed. Propylene / butene random copolymerization was performed to obtain a polymer of 1.65 kg / h. The amount of polymer produced at this time was 2579 g per gram of catalyst, and as a result of sampling and analysis of a part thereof, the intrinsic viscosity [η] _i was 3.85 dl / g. The obtained polymer was continuously transferred to the second tank without being deactivated.
(Polymerization of crystalline propylene polymer component (ii))
In a fluidized bed reactor with an internal volume of 1 m ^{3 with} a stirrer, a polymerization temperature of 80 ° C., a polymerization pressure of 1.8 MPa, a gas phase of propylene, ethylene, butene, a hydrogen concentration in hydrogen of 2.11 vol%, propylene, ethylene, butene Containing catalyst transferred from the first tank while supplying propylene, ethylene, butene and hydrogen so as to maintain an ethylene concentration of 1.32 vol% in propylene, ethylene and butene in a concentration of 5.62 vol% By continuing the polymerization of propylene with the polymer continuously, a polymer of 21.96 kg / h was obtained. The intrinsic viscosity of this polymer (polypropylene resin (B)) was 1.74 dl / g.
From the above results, the amount of polymer produced during the polymerization of the crystalline propylene polymer component (ii) is 31733 g per 1 g of the catalyst, and the polymerization weight ratio of the first tank and the second tank is 7.5: 92.5. The intrinsic viscosity [η] _ii of the crystalline propylene polymer component (ii) was determined to be 1.57 dl / g.
(Melt kneading of polypropylene resin (B))
After mixing 0.125 parts by weight of the phenolic antioxidant (1) with the above-mentioned polypropylene resin using a Henschel mixer, the same direction twin screw extruder manufactured by Nippon Steel Works; TEX30, cylinder temperature 200 ° C., screw rotation Melt extrusion was performed at several 170 rpm and an extrusion rate of 15 kg / hr to form pellets. The melt flow rate of the obtained pellets measured at 230 ° C. was 6.3 g / 10 minutes.

[PP-B (5)]
After mixing 60 parts by weight of PP-A (4), 40% by weight of polypropylene resin (iii) (PP-iii (1)) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, Tanabe Melt extrusion was carried out using a single-axis 65 mmφ extruder manufactured by Plastics Machinery, and pelletized.

[PP-B (6)]
Using a Ziegler-Natta type catalyst of a Ti-Mg catalyst system, the copolymer part of propylene and ethylene (crystalline propylene polymer component (i)) is polymerized in liquefied propylene in the first step, and then the second step The polymer portion of propylene and ethylene (crystalline propylene polymer component (ii)) was polymerized in the gas phase. In the obtained resin (polypropylene resin (B)), the content of the crystalline propylene polymer component (i) is 10% by weight, and the content of the crystalline propylene polymer component (ii) is 90% by weight. Yes, the intrinsic viscosity [η] _A of the crystalline propylene polymer component (i) is 8.0 dl / g, and the intrinsic viscosity [η] _B of the crystalline propylene polymer component (ii) is 1.2 dl / g. there were.
After mixing 100 parts by weight of the above polypropylene resin, 0.1 part by weight of phosphites (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, Nippon Steel Directional twin screw extruder: Using TEX30, pelletization was performed by melt extrusion at a cylinder temperature of 200 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr.

<Polypropylene resin (iii)>
[PP-iii (1)]
A propylene homopolymer was polymerized in the gas phase using a Ziegler-Natta type catalyst based on a Ti-Mg catalyst. The intrinsic viscosity of the obtained resin was 0.9 dl / g.

[PP-iii (2)]
A propylene homopolymer was polymerized in the gas phase using a Ziegler-Natta type catalyst based on a Ti-Mg catalyst. The intrinsic viscosity of the obtained resin was 1.7 dl / g.

<Polypropylene resin (C)>
[PP-C (1)]
Phosphite ester with respect to a total of 100 parts by weight of the polypropylene resin powder 73% by weight obtained with PP-B (1) and 27% by weight of the polypropylene resin (iii) (PP-iii (1)). After mixing 0.1 part by weight of class (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, the same-direction twin screw extruder manufactured by Nippon Steel Works; Melt extrusion was performed at 0 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr to form pellets. The obtained pellet had a molecular weight distribution Aw / An of 9.9, and a melt flow rate measured at 230 ° C. of 1.1 g / 10 min.

[PP-C (2)]
Phosphite ester with respect to 50 weight% of the polypropylene resin powder obtained with PP-B (1), 50 weight% of the polypropylene resin (iii) (PP-iii (1)) and a total of 100 weight parts thereof. (1) 0.1 part by weight and phenolic antioxidant (1) 0.2 part by weight were mixed with a Henschel mixer, and then a Nippon Steel Works Co-Directional Twin Screw Extruder; TEX30 was used and the cylinder temperature was 200 ° C. The mixture was pelletized by melt extrusion at a screw rotation speed of 170 rpm and an extrusion rate of 15 kg / hr. The melt flow rate of the obtained pellets measured at 230 ° C. was 3.8 g / 10 minutes.

[PP-C (3)]
(Synthesis of solid catalyst)
A Ti-Mg catalyst based Ziegler-Natta catalyst was synthesized in the same manner as PP-B (1).
(Preactivation of solid catalyst component)
Made of SUS with an internal volume of 3 L, fully dehydrated and degassed 1.5 L of n-hexane, 30.0 mmol of triethylaluminum, 3.00 mmol of cyclohexylethyldimethoxysilane, and 13.1 g of the above solid catalyst component. Then, 19.7 g of propylene was continuously supplied over 45 minutes while keeping the temperature in the tank at 3 to 8 ° C., and preactivation was performed.
(Polymerization of crystalline propylene polymer component (ia))
In a polymerization tank made of SUS with an internal volume of 40 L, while supplying liquid propylene at 40 kg / h so as to maintain a polymerization temperature of 55 ° C. and a polymerization pressure of 2.32 MPa, 40.8 mmol / h of triethylaluminum, cyclohexylethyldimethoxysilane 6.08 mmol / h, ethylene 0.2 kg / h, hydrogen 5.0 NL / h, and preactivated solid catalyst component 0.343 g / h were continuously fed to conduct ethylene / propylene random copolymerization. 0.64 kg / h polymer was obtained. The amount of the polymer produced at this time was 1866 g per 1 g of the catalyst, and as a result of sampling and analyzing a part thereof, the intrinsic viscosity was 3.26 dl / g. The obtained polymer was continuously transferred to the second tank without being deactivated.
(Polymerization of crystalline propylene polymer component (ib))
In a fluidized bed reactor with an internal volume of 1 m ^{3 with} a stirrer, a polymerization temperature of 80 ° C., a polymerization pressure of 1.8 MPa, propylene in the gas phase, ethylene, a hydrogen concentration in hydrogen of 0.027 vol%, and ethylene in propylene and ethylene While propylene ethylene and hydrogen were supplied so as to maintain the concentration of 2.88 vol%, propylene polymerization with the catalyst-containing polymer transferred from the first tank was continuously continued, whereby a weight of 12.05 kg / h was obtained. Coalescence was obtained. The intrinsic viscosity [η] _i of this polymer (crystalline propylene polymer component (i)) was 3.72 dl / g.
(Polymerization of crystalline propylene polymer component (ii))
In a fluidized bed reactor with an internal volume of 1 m ³ , a polymerization temperature of 80 ° C., a polymerization pressure of 1.4 MPa, propylene in the gas phase, ethylene, a hydrogen concentration of 14.8 vol% in hydrogen, and ethylene in propylene and ethylene By continuously propylene polymerization with the catalyst-containing polymer transferred from the second tank while supplying propylene, ethylene and hydrogen so as to maintain the concentration of 2.55 vol%, 15.1 kg / h A polymer was obtained. The intrinsic viscosity of this polymer (polypropylene resin) was 3.14 dl / g.
From the above results, the amount of polymer produced during polymerization of the crystalline propylene polymer component (ib) was 33265 g per gram of catalyst, and the amount of polymer produced during polymerization of the crystalline propylene polymer component (ii) was 1 g of catalyst. And the polymerization weight ratio of the first tank, the second tank, and the third tank is 4.2. 75.6: 20.2, and the intrinsic viscosity [η] _ii of the crystalline propylene polymer component (ii) was determined to be 0.85 dl / g.

(Melt kneading of polypropylene resin (C))
With respect to the obtained polypropylene resin powder 63% by weight, polypropylene resin (iii) (PP-iii (1)) 37% by weight, and a total of 100 parts by weight thereof, phosphites (1) 0.1 Part by weight and 0.2 part by weight of phenolic antioxidant (1) were mixed with a Henschel mixer, and then the same direction twin screw extruder manufactured by Nippon Steel Works; TEX30, cylinder temperature 200 ° C., screw rotation speed 170 rpm, extrusion It was pelletized by melt extrusion at an amount of 15 kg / hr. The obtained pellet had a molecular weight distribution Aw / An of 5.9 and a melt flow rate measured at 230 ° C. of 2.5 g / 10 min.

[PP-C (4)]
Phosphite ester based on 77% by weight of polypropylene resin powder obtained from PP-B (2), 23% by weight of polypropylene resin (iii) (PP-iii (1)), and 100 parts by weight in total. After mixing 0.1 part by weight of class (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, the same-direction twin screw extruder manufactured by Nippon Steel Works; Melt extrusion was performed at 0 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr to form pellets. The melt flow rate of the obtained pellets measured at 230 ° C. was 0.6 g / 10 minutes.

[PP-C (5)]
Phosphite ester with respect to the polypropylene resin powder 54% by weight obtained with PP-B (2), polypropylene resin (iii) (PP-iii (1)) 46% by weight, and a total of 100 parts by weight thereof. After mixing 0.1 part by weight of class (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, the same-direction twin screw extruder manufactured by Nippon Steel Works; Melt extrusion was performed at 0 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr to form pellets. The melt flow rate of the obtained pellets measured at 230 ° C. was 2.9 g / 10 minutes.

[PP-C (6)]
Phosphite ester with respect to 31 parts by weight of polypropylene resin powder obtained with PP-B (2), 69% by weight of polypropylene resin (iii) (PP-iii (1)), and 100 parts by weight in total. After mixing 0.1 part by weight of class (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, the same-direction twin screw extruder manufactured by Nippon Steel Works; Melt extrusion was performed at 0 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr to form pellets. The melt flow rate of the obtained pellets measured at 230 ° C. was 7.1 g / 10 minutes.

[PP-C (7)]
Phosphite ester with respect to 100% by weight of polypropylene resin powder 60% by weight obtained with PP-B (2) and polypropylene resin (iii) (PP-iii (2)) 40% by weight. After mixing 0.1 part by weight of class (1) and 0.2 part by weight of phenolic antioxidant (1) with a Henschel mixer, the same-direction twin screw extruder manufactured by Nippon Steel Works; Melt extrusion was performed at 0 ° C., a screw rotation speed of 170 rpm, and an extrusion rate of 15 kg / hr to form pellets. The melt flow rate of the obtained pellets measured at 230 ° C. was 0.8 g / 10 minutes.

[ABA master batch (1)]
PP-A (3) 30% by weight, PP-A (5) 70% by weight, and 2.3 parts by weight of the total of 100 parts by weight of these were manufactured by Fuji Silysia Chemical Co., Ltd. (trade name Cylicia 420). It knead | mixed and pelletized using the shaft granulator.

[ABA masterbatch (2)]
100 parts by weight of PP-A (5) and 10 parts by weight of Fuji Silysia Chemical Co., Ltd. (trade name Cylicia 550) were kneaded using a twin-screw granulator and pelletized.

[Example 1]
A composition in which PP-A (1) 89% by weight, PP-B (1) 10% by weight, and ABA masterbatch (2) 1% by weight are pellet-blended are melt-kneaded in a 50 mmφ extruder at 250 ° C. The mixture was introduced into a T die (die width 600 mm) heated to 250 ° C. and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Example 2]
A composition in which PP-A (1) 89% by weight, PP-B (2) 10% by weight, and ABA masterbatch (2) 1% by weight are pellet-blended are melt-kneaded in a 50 mmφ extruder at 250 ° C. The mixture was introduced into a T die (die width 600 mm) heated to 250 ° C. and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Example 3]
A composition in which PP-A (1) 89% by weight, PP-C (1) 10% by weight and ABA masterbatch (2) 1% by weight are pellet-blended are melt-kneaded at 250 ° C. in a 50 mmφ extruder. The mixture was introduced into a T die (die width 600 mm) heated to 250 ° C. and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Example 4]
A composition in which PP-A (1) 89% by weight, PP-C (7) 10% by weight, and ABA masterbatch (2) 1% by weight are pellet-blended are melt-kneaded in a 50 mmφ extruder at 250 ° C. The mixture was introduced into a T die (die width 600 mm) heated to 250 ° C. and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Example 5]
A composition obtained by pellet-blending PP-A (2) 81.7%, PP-C (1) 10%, ABA masterbatch (1) 6.8%, HDPE (1) 1.5% by weight. The mixture was melt-kneaded at a temperature of 250 ° C. with a 50 mmφ extruder, introduced into a T die (die width 600 mm) heated to 250 ° C., and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Example 6]
A composition obtained by pellet-blending PP-A (2) 81.7%, PP-C (3) 10%, ABA masterbatch (1) 6.8%, HDPE (1) 1.5% by weight. The mixture was melt-kneaded at a temperature of 250 ° C. with a 50 mmφ extruder, introduced into a T die (die width 600 mm) heated to 250 ° C., and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Example 7]
A composition obtained by pellet-blending PP-A (2) 81.7%, PP-C (4) 10%, ABA masterbatch (1) 6.8%, HDPE (1) 1.5% by weight. The mixture was melt-kneaded at a temperature of 250 ° C. with a 50 mmφ extruder, introduced into a T die (die width 600 mm) heated to 250 ° C., and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 1]
A composition obtained by pellet-blending 99 wt% of PP-B (2) and 1 wt% of ABA masterbatch (2) was melt-kneaded in a 50 mmφ extruder at 250 ° C. and heated to 250 ° C. The mixture was introduced into a die width (600 mm) and subjected to melt extrusion. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 2]
A composition obtained by pellet-blending 99 wt% of PP-B (3) and 1 wt% of ABA masterbatch (2) was melt-kneaded in a 50 mmφ extruder at 250 ° C. and heated to 250 ° C. The mixture was introduced into a die width (600 mm) and subjected to melt extrusion. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 3]
A composition obtained by pellet-blending 99% by weight of PP-B (4) and 1% by weight of ABA masterbatch (2) was melt-kneaded in a 50 mmφ extruder at 250 ° C. and heated to 250 ° C. The mixture was introduced into a die width (600 mm) and subjected to melt extrusion. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 4]
A composition in which PP-A (1) 89% by weight, PP-B (3) 10% by weight, and ABA masterbatch (2) 1% by weight are pellet-blended are melt-kneaded in a 50 mmφ extruder at 250 ° C. The mixture was introduced into a T die (die width 600 mm) heated to 250 ° C. and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 5]
A composition obtained by pellet-blending PP-A (2) 81.7%, PP-B (2) 10%, ABA masterbatch (1) 6.8%, HDPE (1) 1.5% by weight. The mixture was melt-kneaded at a temperature of 250 ° C. with a 50 mmφ extruder, introduced into a T die (die width 600 mm) heated to 250 ° C., and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 6]
A composition obtained by pellet-blending PP-A (2) 81.7%, PP-C (2) 10%, ABA masterbatch (1) 6.8%, HDPE (1) 1.5% by weight. The mixture was melt-kneaded at a temperature of 250 ° C. with a 50 mmφ extruder, introduced into a T die (die width 600 mm) heated to 250 ° C., and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 7]
A composition obtained by pellet-blending PP-A (2) 81.7%, PP-C (5) 10%, ABA masterbatch (1) 6.8%, HDPE (1) 1.5% by weight. The mixture was melt-kneaded at a temperature of 250 ° C. with a 50 mmφ extruder, introduced into a T die (die width 600 mm) heated to 250 ° C., and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Comparative Example 8]
A composition obtained by pellet-blending PP-A (2) 81.7%, PP-C (6) 10%, ABA masterbatch (1) 6.8%, HDPE (1) 1.5% by weight. The mixture was melt-kneaded at a temperature of 250 ° C. with a 50 mmφ extruder, introduced into a T die (die width 600 mm) heated to 250 ° C., and melt extruded. The extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 18 m / min to obtain a single-layer unstretched film having a thickness of 30 μm.

[Example 8]
PP-A (3) 81.7% by weight, PP-C (1) 10% by weight, ABA masterbatch (1) 6.8% by weight, HDPE 1.5% by weight of the pellet blended composition of two 65 mmφ In an extruder and a 90 mmφ extruder, the feed block was melt-kneaded under the condition that the cylinder temperature was set to 280 ° C., filtered through a sintered filter (NF13D manufactured by Nippon Seisen) with a filtration accuracy of 60 μm, and then heated to 260 ° C. It was introduced into a mold T die (die width 1250 mm, lip opening 0.8 mm) and melt extrusion was performed. The melt-extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 40 ° C. and rotated at 50 m / min to obtain a single-layer unstretched film having a thickness of 70 μm.

[Example 9]
PP-A (3) 81.7 wt%, PP-C (3) 10 wt%, ABA masterbatch (1) 6.8 wt%, HDPE 1.5 wt% were pellet-blended. In a 65 mmφ extruder and a 90 mmφ extruder, melt-kneaded under conditions where the cylinder temperature is set to 280 ° C., filtered through a sintered filter (NF13D manufactured by Nippon Seisen) with a filtration accuracy of 60 μm, and then heated to 260 ° C. It was introduced into a block type T die (die width 1250 mm, lip opening 0.8 mm) and melt extrusion was performed. The melt-extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 40 ° C. and rotated at 50 m / min to obtain a single-layer unstretched film having a thickness of 70 μm.

[Example 10]
PP-A (3) 81.7 wt%, PP-C (4) 10 wt%, ABA masterbatch (1) 6.8 wt%, HDPE 1.5 wt% were pellet-blended. In a 65 mmφ extruder and a 90 mmφ extruder, melt-kneaded under conditions where the cylinder temperature is set to 280 ° C., filtered through a sintered filter (NF13D manufactured by Nippon Seisen) with a filtration accuracy of 60 μm, and then heated to 260 ° C. It was introduced into a block type T die (die width 1250 mm, lip opening 0.8 mm) and melt extrusion was performed. The melt-extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 40 ° C. and rotated at 50 m / min to obtain a single-layer unstretched film having a thickness of 70 μm.

[Comparative Example 9]
PP-A (3) 91.7% by weight, ABA masterbatch (1) 6.8% by weight, HDPE 1.5% by weight of the pellet blended composition in two 65 mmφ extruder and 90 mmφ extruder, The mixture was melt-kneaded under the condition where the cylinder temperature was set at 280 ° C., filtered through a sintered filter (NF13D manufactured by Nippon Seisen) with a filtration accuracy of 60 μm, and then heated to 260 ° C. (die width 1250 mm, die width 1250 mm, (Lip opening 0.8 mm) and melt extrusion was performed. The melt-extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 40 ° C. and rotated at 50 m / min to obtain a single-layer unstretched film having a thickness of 70 μm.

[Comparative Example 10]
PP-A (3) 81.7 wt%, PP-B (5) 10 wt%, ABA masterbatch (1) 6.8 wt%, HDPE 1.5 wt% were pellet-blended. In a 65 mmφ extruder and a 90 mmφ extruder, melt-kneaded under conditions where the cylinder temperature is set to 280 ° C., filtered through a sintered filter (NF13D manufactured by Nippon Seisen) with a filtration accuracy of 60 μm, and then heated to 260 ° C. It was introduced into a block type T die (die width 1250 mm, lip opening 0.8 mm) and melt extrusion was performed. The melt-extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 40 ° C. and rotated at 50 m / min to obtain a single-layer unstretched film having a thickness of 70 μm.

[Comparative Example 11]
PP-A (3) 81.7 wt%, PP-B (6) 10 wt%, ABA masterbatch (1) 6.8 wt%, HDPE 1.5 wt% were pellet-blended. In a 65 mmφ extruder and a 90 mmφ extruder, melt-kneaded under conditions where the cylinder temperature is set to 280 ° C., filtered through a sintered filter (NF13D manufactured by Nippon Seisen) with a filtration accuracy of 60 μm, and then heated to 260 ° C. It was introduced into a block type T die (die width 1250 mm, lip opening 0.8 mm) and melt extrusion was performed. The melt-extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 40 ° C. and rotated at 50 m / min to obtain a single-layer unstretched film having a thickness of 70 μm.

Claims (8)

A polypropylene resin composition comprising 70 to 99% by weight of a polypropylene resin (A) having a molecular weight distribution (Aw / An) measured by GPC of 5 or less and 1 to 30% by weight of a polypropylene resin (B). (The total of the weight of the polypropylene resin (A) and the weight of the polypropylene resin is 100% by weight),
The polypropylene resin (B) includes a step of producing 38 to 80% by weight of a crystalline propylene polymer component (i) having an intrinsic viscosity of 3.5 to 10 dl / g, and an intrinsic viscosity of 0.5 to 1.5 dl / g. And a step of producing 62 to 20% by weight of a crystalline propylene polymer component (ii) of (the weight of the crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii) The total weight is 100% by weight),
The said polypropylene resin composition whose ratio (MFR (A) / MFR (B)) of MFR (A) of polypropylene resin (A) with respect to MFR (B) of polypropylene resin (B) is 0.5-12 .   The polypropylene resin composition according to claim 1, wherein the polypropylene resin (B) is obtained by melt-kneading, and the MFR (B) of the polypropylene resin (B) is 0.1 to 20 g / 10 min.   The polypropylene resin composition according to claim 1 or 2, wherein the polypropylene resin (A) has an MFR (A) of 1 to 20 g / 10 min. A polypropylene resin composition comprising 70 to 99% by weight of a polypropylene resin (A) having a molecular weight distribution (Aw / An) measured by GPC of 5 or less and 1 to 30% by weight of a polypropylene resin (C). (The total of the weight of the polypropylene resin (A) and the weight of the polypropylene resin (C) is 100% by weight),
The polypropylene resin (C) includes 50 to 99.9% by weight of the polypropylene resin (B) and 0.1 to 50% by weight of the polypropylene resin (iii) having an intrinsic viscosity of 0.5 to 2 dl / g. Including (the total of the weight of the polypropylene resin (B) and the weight of the polypropylene resin (iii) is 100% by weight),
The polypropylene resin (B) includes a step of producing 38 to 80% by weight of a crystalline propylene polymer component (i) having an intrinsic viscosity of 3.5 to 10 dl / g, and an intrinsic viscosity of 0.5 to 1.5 dl / g. And a step of producing 62 to 20% by weight of a crystalline propylene polymer component (ii) of (the weight of the crystalline propylene polymer component (i) and the crystalline propylene polymer component (ii) The total weight is 100% by weight),
When the weight of the polypropylene resin (C) is 100% by weight, the weight of the crystalline propylene polymer component (i) is 37-60% by weight,
The said polypropylene resin composition whose ratio (MFR (A) / MFR (C)) of MFR (A) of polypropylene resin (A) with respect to MFR (C) of polypropylene resin (C) is 0.5-12 .   The polypropylene resin composition according to claim 4, wherein the polypropylene resin (C) is obtained by melt-kneading, and the MFR (C) of the polypropylene resin (C) is 0.1 to 20 g / 10 min.   The polypropylene resin composition according to claim 4 or 5, wherein the MFR (A) of the polypropylene resin (A) is 1 to 20 g / 10 min.   The polypropylene resin composition according to any one of claims 1 to 6, wherein the intrinsic viscosity of the crystalline propylene polymer component (i) is 3.5 to 6 dl / g.   A polypropylene film comprising the polypropylene resin composition according to claim 1.