JP2018076396A - Polypropylene composition and mat-like film obtained by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene composition providing a film which has good appearance and high mat tone.SOLUTION: A polypropylene composition contains 85-55 pts.wt. of a propylene (co)polymer containing 0-3.5 wt.% of an ethylene-derived unit as component (1) and 15-45 wt.% of a propylene-ethylene copolymer containing 15-45 wt.% of an ethylene-derived unit as component (2), and satisfies the following requirements: 1) Mw/Mn of a xylene insoluble matter of the composition measured by GPC of 7 or more; 2) intrinsic viscosity of the xylene insoluble matter of the composition of 2-4.5 dl/g; 3) a melt flow rate (230°C and load of 21.18 N) of the composition of 2-20 g/10 min; and 4) a melt tension index of the composition of 1.5 or more.SELECTED DRAWING: None

Description

  The present invention relates to a polypropylene composition and a matte film formed by molding the same.

  Polypropylene is used as a food film because it has excellent physical properties and excellent hygiene. In recent years, matte film with a matte finish has been actively used to enhance the aesthetics and design of packaged foods. For example, Patent Document 1 proposes a matte film made of a polypropylene composition that can achieve a sufficient matte feeling without impairing mechanical properties and the like.

JP 2011-194588 A

  A matte film can be obtained by adjusting the composition and physical properties of the components in the polypropylene composition to form irregularities on the surface, but the inventors tried to increase the matte tone by using so-called fish eyes in the film. It has been found that there is a problem that a foreign matter called is generated and an appearance defect occurs. In view of such circumstances, an object of the present invention is to provide a polypropylene composition that provides a film having a good appearance and a high matte tone.

The inventors have found that the above problem can be solved by setting the intrinsic viscosity of the xylene-insoluble component of the polypropylene composition within a specific range and the ethylene content in the second component within the specific range. That is, the said subject is solved by the following this invention.
[1] 85 to 55 parts by weight of propylene (co) polymer containing 0 to 3.5% by weight of ethylene-derived units as component (1), and 15 to 45% by weight of ethylene as component (2) A polypropylene composition comprising 15 to 45 parts by weight of a propylene-ethylene copolymer comprising units,
The following requirements:
1) Mw / Mn measured by GPC of xylene-insoluble matter of the composition is 7 or more 2) The intrinsic viscosity of xylene-soluble matter of the composition is 2 to 4.5 dl / g 3) The composition The melt flow rate (230 ° C., load 21.18 N) is 2 to 20 g / 10 min. 4) The polypropylene composition satisfies the melt tension index of the composition is 1.5 or more.
[2] The polypropylene composition according to [1], wherein the ethylene-derived unit of the propylene-ethylene copolymer in the component (2) is 25 to 35% by weight.
[3] The polypropylene composition according to [1] or [2], wherein Mw / Mn of the xylene insoluble matter is 9 or more.
[4] The polypropylene composition according to any one of [1] to [3], wherein an intrinsic viscosity of the xylene-soluble component is 2.4 to 3.8 dl / g.
[5] The polypropylene composition according to any one of [1] to [4], wherein the melt flow rate is 4 to 10 g / 10 minutes.
[6] The polypropylene composition according to any one of [1] to [5], comprising 82 to 70 parts by weight of the component (1) and 18 to 30 parts by weight of the component (2).
[7] (A) a solid catalyst containing, as an essential component, an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound;
(B) Organoaluminum compound; and (C) The polypropylene composition according to any one of [1] to [6], obtained by polymerizing propylene and ethylene using a catalyst containing an external electron donor compound. .
[8] A film formed by molding the polypropylene composition according to any one of [1] to [7].
[9] A multilayer film including the film according to [8].

  A polypropylene composition that provides a film having a good appearance and a high matte tone can be provided.

  Hereinafter, the present invention will be described in detail. In the present invention, “X to Y” includes X and Y which are the end values.

1. Polypropylene composition The polypropylene composition of the present invention comprises:
Component (1): 85 to 55 parts by weight of propylene (co) polymer containing 0 to 3.5% by weight of ethylene-derived units Component (2): Propylene-ethylene copolymer containing 15 to 45% by weight of ethylene-derived units 15 to 45 parts by weight The polypropylene composition of the present invention satisfies all the following requirements 1) to 4).
1) Mw / Mn measured by GPC of xylene-insoluble matter of the composition is 7 or more 2) The intrinsic viscosity of xylene-soluble matter of the composition is 2 to 4.5 dl / g 3) The composition The melt flow rate (230 ° C., load 21.18 N) is 2 to 20 g / 10 min. 4) The melt tension index of the composition is 1.5 or more.

(1) Component (1): Propylene (co) polymer A propylene (co) polymer is a propylene homopolymer or a copolymer of ethylene and propylene of more than 0% by weight and not more than 3.5% by weight. . In view of the balance between the matte tone and rigidity when formed into a film, the component (1) is preferably a propylene homopolymer. On the other hand, when flexibility or the like is required, the component (1) is preferably a copolymer. The copolymer of propylene containing 1.0% by weight of ethylene-derived units is a copolymer having a weight ratio of ethylene-derived units to propylene-derived units of 1.0: 99.0. The same applies to other copolymers. The upper limit of the content of the ethylene-derived unit is 3.5% by weight or less, but preferably 3% by weight or less. When the amount exceeds the upper limit value, haze is lowered, a sufficient matte tone cannot be obtained, and rigidity is lowered. Although the lower limit when an ethylene-derived unit is present is not limited, it is preferably 0.5% by weight or more, and more preferably 1.0% by weight or more.

(2) Component (2): Propylene-ethylene copolymer The propylene-ethylene copolymer used in the present invention contains 15 to 45% by weight of ethylene-derived units. When the content of the ethylene-derived unit is less than the lower limit, the haze is lowered and a sufficient matte tone cannot be obtained, and the impact strength is also lowered. On the other hand, when the content of the ethylene-derived unit exceeds the upper limit, appearance defects such as an increase in fish eyes occur. From this viewpoint, the upper limit of the content of ethylene-derived units is preferably 35% by weight or less, and the lower limit of the content is preferably 25% by weight or more.

(3) Composition ratio The weight ratio of components (1) and (2) is (1) :( 2) = 85-55: 15-45. If the amount of component (2) exceeds this upper limit, production becomes difficult. When the amount of the component (2) is less than the lower limit, haze is lowered and sufficient matte tone cannot be obtained, and impact strength is also lowered. From this viewpoint, the ratio is preferably 82 to 70:18 to 30.

(4) Other components Further, the masterbatch composition includes an antioxidant, a chlorine absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorbent, an internal lubricant, an external lubricant, an antiblocking agent, an antistatic agent, and an antifogging agent. In the field, such as agents, crystal nucleating agents, flame retardants, dispersants, copper damage inhibitors, neutralizers, plasticizers, anti-bubble agents, crosslinking agents, peroxides, oil-extended and other organic and inorganic pigments You may add the usual additive used normally. The addition amount of each additive may be a known amount.

(5) Characteristics 1) Mw / Mn of xylene insoluble matter
Mw and Mw / Mn of xylene insoluble matter (XI) are obtained by obtaining a component insoluble in xylene at 25 ° C. and measuring the component by a GPC (gel permeation chromatography) method. Mw / Mn measured by GPC of XI of the polypropylene composition of the present invention is as wide as 7 or more. When Mw / Mn is less than 7, the load at the time of extrusion is increased, and the thickness accuracy of the film is lowered. Therefore, since the polypropylene composition of the present invention has a wide molecular weight distribution, it gives a film having excellent moldability and thickness accuracy. From this viewpoint, Mw / Mn is preferably 9 or more. However, when Mw / Mn is excessively high, the dispersibility of the high molecular weight component and the low molecular weight component is deteriorated, which makes it difficult to produce a product having homogeneous characteristics. Therefore, the upper limit of Mw / Mn is preferably 20 or less.

2) XSIV
The intrinsic viscosity (XSIV) of the xylene-soluble component (XS) of the composition is also an indicator of the molecular weight of the component having no crystallinity in the composition. XSIV is obtained by obtaining a component soluble in xylene at 25 ° C. and measuring the intrinsic viscosity of the component by a conventional method. In the present invention, XSIV is 2 to 4.5 dl / g. If XSIV exceeds the upper limit, the fish eye increases, and if it is less than the lower limit, haze decreases and a sufficient matte tone cannot be obtained. Therefore, when the XSIV is in this range, the appearance of the film can be improved. From this viewpoint, the intrinsic viscosity is preferably 2.4 to 3.8 dl / g.

3) Melt flow rate The melt flow rate (hereinafter also referred to as “MFR”) at 230 ° C. and a load of 21.18 N of the polypropylene composition of the present invention is 2 to 20 g / 10 min. When the melt flow rate exceeds the upper limit, fish eyes increase and impact strength decreases. When the melt flow rate is less than the lower limit, the load during extrusion molding increases. From this viewpoint, the melt flow rate is preferably 4 to 10 g / 10 min. More preferably, it is more than 5 g / 10 minutes and less than 10 g / 10 minutes.

4) Melt tension index The polypropylene composition of the present invention has a melt tension index of 1.5 or more. The melt tension index is an index of tension generated when a molten resin is pulled. Generally, tensile stress is generated when molten resin flows into the die. It is known that when the tensile stress exceeds a critical value, a brittle fracture called melt fracture occurs, an unstable flow occurs at the die exit, and minute irregularities are formed on the surface of the molded body. A general melt fracture becomes striped and causes a defective appearance as a molded product. However, in film forming, the melt fracture is very small, so it is presumed that the appearance will be a high-quality matte tone. Therefore, when the melt tension index is 1.5 or more, the tensile stress increases and a good matte tone can be obtained in film forming. From this viewpoint, the melt tension index is preferably 1.6 or more. However, if the above XSIV is set high in order to increase the melt tension index, there is a problem that fish eyes increase or the viscosity of the composition increases and the load during extrusion molding increases. From such a viewpoint, the upper limit of the melt tension index is preferably 3.0 or less.

The melt tension index can be measured by the following procedure using a capillary rheometer (for example, Capirograf 1C manufactured by Toyo Seiki Seisakusho Co., Ltd.).
i) The polypropylene composition is extruded from an orifice at 200 ° C. at an extrusion speed of 15 mm / min.
ii) The extrudate is taken up at a take-up speed of 6.5 m / min, and the tension at that time is measured as melt tension MT (g weight).
iii) Obtain the melt tension index using the following equation.
Melt tension index = log (MT) + 0.85 × log (MFR) −0.82
In the present invention, an orifice having a flat top surface with L = 8.0 mm and D = 2.095 mm is attached to the measuring machine, and the composition is measured at a measurement temperature of 200 ° C., extrusion speed of 15 mm / min, take-up speed of 6.5 m / min. It is preferable to measure the tension when the object is taken up as the melt tension MT (unit: g weight).

5) Haze 65% or more of the haze of the film obtained from the polypropylene composition of this invention is preferable. Haze is measured according to JIS K7136.

6) Fish Eye The film eye obtained from the polypropylene composition of the present invention has a medium (maximum diameter of 0.2 to 0.5 mm), preferably 2 pieces / 0.1 m ² or less. Those having a small size (maximum diameter of 0.1 mm or more and less than 0.2 mm) are preferably 10 / 0.1 m ² or less. Fish eye can be measured using a fish eye counter.

7) Tensile modulus The film obtained from the polypropylene composition of the present invention preferably has a tensile modulus of 500 MPa or more. The tensile elastic modulus is measured according to JIS K7127.

8) Impact strength The impact strength of the film obtained from the polypropylene composition of the present invention is preferably 5.0 kJ / m or more at 0 ° C. Impact strength is measured according to ASTM D3420.

9) Mechanism of operation The polypropylene composition of the present invention is free from foreign matters such as fish eyes and provides an excellent matte film. In general, when the copolymer component (2) having a different density is introduced by expanding the molecular weight distribution (Mw / Mn) of XI of the composition, the matte tone of the film can be improved, but the fish eye is increased to cause poor appearance. However, in the present invention, by reducing the ethylene amount and XSIV of the component (2) within a specific range, fish eye reduction and high matte tone can be achieved. Although this reason is not limited, it is guessed as follows.

  If the tensile stress generated when the molten resin flows into the die exceeds the critical value, a brittle fracture called melt fracture occurs, causing unstable flow at the die exit, and minute irregularities on the surface of the molded product Is known to form. The unevenness due to the general melt fracture becomes striped and becomes a cause of poor appearance of the molded product. However, since the melt fracture is minute in film molding, it may be possible to have a high-quality matte appearance. When the above melt tension index is 1.5 or more, it is considered that the tensile stress becomes large at a strain rate in a general molding process, and a good matte tone can be obtained in film molding. In the polypropylene composition of the present invention, the dispersibility of the copolymer component (2) is improved, and as a result of having a melt tension index of 1.5 or more, it is possible to produce a high matte film with less fish eyes. Seem.

(6) Production Method The polypropylene composition of the present invention may be produced by any method, but the raw material monomer of component (1) and the raw material monomer of component (2) are (A) magnesium, titanium, halogen, and internal components. It is preferable to obtain by a method including a step of polymerizing using a solid catalyst containing a succinate compound as an electron donor, (B) an organoaluminum compound, and (C) a catalyst containing an external electron donor compound.

1) Solid catalyst (component A)
Component (A) can be prepared by a known method, for example, by bringing a magnesium compound, a titanium compound and an electron donor compound into contact with each other.

As a titanium compound used for preparation of a component (A), the tetravalent titanium compound represented by general formula: Ti (OR) _{gX4 -g} is suitable. In the formula, R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4. As titanium compounds, TiCl ₄ and more specifically, TiBr _4, titanium tetrahalides such as _{TiI 4; Ti (OCH 3)} Cl 3, Ti (OC 2 H 5) Cl 3, Ti (O n -C 4 H _{9) Cl 3, Ti (OC} 2 H 5) Br 3, Ti (OisoC 4 H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl ₂ , Di (halogenated alkoxytitanium) such as Ti (O _n —C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ ; Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl _{, Ti (O n -C 4 H} 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H 5) _{4, Ti (O n -C 4} H 9) 4 and the like tetraalkoxytitanium such. Among these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalides, and more particularly preferred is titanium tetrachloride.

  Magnesium compounds used for the preparation of component (A) include magnesium compounds having a magnesium-carbon bond or magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, Examples include decylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, butylmagnesium hydride and the like. These magnesium compounds can also be used, for example, in the form of a complex compound with organic aluminum or the like, and may be liquid or solid. Further preferred magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, and the like. Alkoxymagnesium halides; aryloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; phenoxy Allyloxy Magnesium like Magnesium, Dimethylphenoxy Magnesium ; Magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

  The electron donor compound used for the preparation of component (A) is generally referred to as “internal electron donor”. In the present invention, it is preferable to use an internal electron donor that gives a broad molecular weight distribution. In general, it is known that the molecular weight distribution can be increased by performing polymerization in multiple stages, but it is difficult to increase the molecular weight distribution when the molecular weight of XI is low. However, by using a specific internal electron donor, the molecular weight distribution can be increased even when the molecular weight of XI is low. A composition polymerized using the catalyst is a composition having the same molecular weight distribution obtained by pelletizing or powder blending a polymer polymerized using another catalyst, and a composition having the same molecular weight distribution by multistage polymerization. It shows different characteristics from the object. This is because the composition produced using the catalyst is united in a state where the high molecular weight component and the low molecular weight component are close to the molecular level, but the latter resin composition does not mix in the state close to the molecular level. This is thought to be due to the apparent molecular weight distribution. However, it is not realistic to express this in words in the claims. Hereinafter, preferred internal electron donors will be described.

  A preferred internal electron donor in the present invention is a succinate compound. In the present invention, the succinate compound means a diester of succinic acid or a substituted succinic acid. Hereinafter, the succinate compound will be described in detail. The succinate compound preferably used in the present invention is represented by the following formula (I).

In which the radicals R ₁ and R ₂ are identical or different from one another and optionally contain heteroatoms, C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkyl An aryl group; the groups R _{3 to} R ₆ are the same or different from each other and are hydrogen, or optionally a heteroatom, C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, The groups R _{3 to} R ₆ which are arylalkyl or alkylaryl groups and are bonded to the same carbon atom or different carbon atoms may be bonded together to form a ring.

R ₁ and R ₂ are preferably C ₁ -C ₈ alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Particularly preferred are compounds wherein R ₁ and R ₂ are selected from primary alkyls, especially branched primary alkyls. Examples of suitable R ₁ and R ₂ groups are C ₁ -C ₈ alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.

One preferred group of compounds represented by formula (I) are branched alkyl, cycloalkyl, aryl, arylalkyl, wherein R _{3 to} R ₅ are hydrogen and R ₆ has 3 to 10 carbon atoms. And an alkylaryl group. Preferred specific examples of such mono-substituted succinate compounds include diethyl-sec-butyl succinate, diethyl hexyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl perihydrosuccinate, diethyl Trimethylsilyl succinate, diethyl methoxy succinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexyl Methyl succinate, diethyl-t-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopenty Succinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenyl succinate, 1-ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyl hexyl succinate, diisobutylcyclopropyl succinate , Diisobutyl norbornyl succinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilyl succinate, diisobutyl methoxy succinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutyl cyclohexyls Succinate, diisobutylbenzyl succinate, diisobutylcyclohexylmethyl succinate, diisobutyl-t-butyl succinate Diisobutyl isobutyl succinate, diisobutyl isopropyl succinate, diisobutyl neopentyl succinate, diisobutyl isopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenyl succinate, dineopentyl-sec- Butyl succinate, dineopentyl texyl succinate, dineopentyl cyclopropyl succinate, dineopentyl norbornyl succinate, dineopentyl perhydrosuccinate, dineopentyl trimethylsilyl succinate, dineo Pentylmethoxy succinate, dineopentyl-p-methoxyphenyl succinate, dineopentyl-p-chlorophenyl succinate, dineopentylphenyl succinate, dinene Opentyl cyclohexyl succinate, dineopentyl benzyl succinate, dineopentyl cyclohexyl methyl succinate, dineopentyl-t-butyl succinate, dineopentyl isobutyl succinate, dineopentyl isopropyl succinate, di Neopentyl neopentyl succinate, dineopentyl isopentyl succinate, dineopentyl (1-trifluoromethylethyl) succinate, dineopentyl fluorenyl succinate.

Another preferred group of compounds within the scope of formula (I) are C ₁ -C ₂₀ linear, wherein at least two groups from R _{3 to} R ₆ are different from hydrogen and optionally contain heteroatoms. Or a branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl group. Particularly preferred are compounds in which two groups different from hydrogen are bonded to the same carbon atom. Specifically, R ₃ and R ₄ are different from hydrogen, and R ₅ and R ₆ are hydrogen atoms. Preferred specific examples of such disubstituted succinates are diethyl-2,2-dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diethyl-2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutyl succinate, diethyl-2-cyclopentyl-2-n-butyl succinate, diethyl-2, 2-diisobutyl succinate, diethyl-2-cyclohexyl-2-ethyl succinate , Diethyl-2-isopropyl-2-methylsuccinate, diethyl-2-tetradecyl-2-ethylsuccinate, diethyl-2-isobutyl-2-ethylsuccinate, diethyl-2- (1-trifluoro Methylethyl) -2-methylsuccinate, diethyl-2-isopentyl-2- Sobutyl succinate, diethyl-2-phenyl-2-n-butyl succinate, diisobutyl-2,2-dimethyl succinate, diisobutyl-2-ethyl-2-methyl succinate, diisobutyl-2-benzyl- 2-isopropyl succinate, diisobutyl-2-cyclohexylmethyl-2-isobutyl succinate, diisobutyl-2-cyclopentyl-2-n-butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2 -Cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methyl succinate, diisobutyl-2-tetradecyl-2-ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl -2- (1-trifluoro Tilethyl) -2-methylsuccinate, diisobutyl-2-isopentyl-2-isobutylsuccinate, diisobutyl-2-phenyl-2-n-butylsuccinate, dineopentyl-2,2-dimethylsuccinate, dineopentyl 2-ethyl-2-methyl succinate, dineopentyl-2-benzyl-2-isopropyl succinate, dineopentyl-2-cyclohexylmethyl-2-isobutyl succinate, dineopentyl-2-cyclopentyl-2-n-butyl Succinate, dineopentyl-2,2-diisobutyl succinate, dineopentyl-2-cyclohexyl-2-ethyl succinate, dineopentyl-2-isopropyl-2-methyl succinate, dineopentyl-2-tetradecyl-2-ethyl succinate , Dineopentyl-2-isobutyl-2-ethyl succinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methyl succinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl 2-Phenyl-2-n-butyl succinate.

Furthermore, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are particularly preferred. Specifically, it is a compound in which R ₃ and R ₅ are groups different from hydrogen. In this case, R ₄ and R ₆ may be a hydrogen atom or a group different from hydrogen, but it is preferable that either one is a hydrogen atom (trisubstituted succinate). Preferred examples of such compounds are diethyl-2,3-bis (trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2- (3,3,3- Trifluoropropyl) -3-methylsuccinate, diethyl-2,3-bis (2-ethylbutyl) succinate, diethyl-2,3-diethyl-2-isopropylsuccinate, diethyl-2,3-diisopropyl-2 -Methyl succinate, diethyl-2,3-dicyclohexyl-2-methyldiethyl-2,3-dibenzyl succinate, diethyl-2,3-diisopropyl succinate, diethyl-2,3-bis (cyclohexylmethyl) ) Succinate, diethyl-2,3-di-t-butylsuccinate, diethyl-2,3-diisobuty Succinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diisopentyl succinate, diethyl-2,3- (1-trifluoromethylethyl) succinate, diethyl-2,3- Tetradecyl succinate, diethyl-2,3-fluorenyl succinate, diethyl-2-isopropyl-3-isobutyl succinate, diethyl-2-tert-butyl-3-isopropyl succinate, diethyl-2- Isopropyl-3-cyclohexyl succinate, diethyl-2-isopentyl-3-cyclohexyl succinate, diethyl-2-tetradecyl-3-cyclohexylmethyl succinate, diethyl-2-cyclohexyl-3-cyclopentyl succinate, diisobutyl -2,3-diethyl-2-iso Lopyl succinate, diisobutyl-2,3-diisopropyl-2-methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methyl succinate, diisobutyl-2,3-dibenzyl succinate, diisobutyl-2 , 3-diisopropyl succinate, diisobutyl-2,3-bis (cyclohexylmethyl) succinate, diisobutyl-2,3-di-t-butyl succinate, diisobutyl-2,3-diisobutyl succinate, diisobutyl-2 , 3-Dineopentyl succinate, diisobutyl-2,3-diisopentyl succinate, diisobutyl-2,3- (1-trifluoromethylethyl) succinate, diisobutyl-2,3-tetradecyl succinate Diisobutyl-2,3-fluorenylsuccinate Diisobutyl-2-isopropyl-3-isobutyl succinate, diisobutyl-2-tert-butyl-3-isopropyl succinate, diisobutyl-2-isopropyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3- Cyclohexyl succinate, diisobutyl-2-tetradecyl-3-cyclohexylmethyl succinate, diisobutyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,3-bis (trimethylsilyl) succinate, dineopentyl-2,2- sec-butyl-3-methyl succinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methyl succinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, cine Pentyl-2,3-diethyl-2-isopropyl succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3 -Dibenzyl succinate, dineopentyl-2,3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2, 3-diisobutyl succinate, dineopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl -2,3-tetradeci Succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl-3-isopropyl succinate, dineopentyl-2-isopropyl-3- They are cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, and dineopentyl-2-cyclohexyl-3-cyclopentyl succinate.

Among the compounds of the formula (I), compounds in which some of the groups R _{3 to} R ₆ are bonded together to form a ring can also be preferably used. As such compounds, compounds listed in JP-T-2002-542347, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- ( Ethoxyacetyl) -2,5-monodimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2 monomethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned. In addition, for example, cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate and diisobutyl cyclohexane-1,2-dicarboxylate as disclosed in WO2009 / 069483 are also suitable. Can be used. As another example of the cyclic succinate compound, a compound disclosed in International Publication No. 2009/057747 is also preferable.

Of the compounds of formula (I), when the groups R _{3 to} R ₆ contain heteroatoms, the heteroatoms may be group 15 atoms including nitrogen and phosphorus atoms or group 16 atoms including oxygen and sulfur atoms. preferable. Examples of the compound in which the groups R _{3 to} R ₆ include a Group 15 atom include compounds disclosed in JP-A-2005-306910. On the other hand, examples of the compound in which the groups R _{3 to} R ₆ include a Group 16 atom include compounds disclosed in JP-A No. 2004-131537.

  In addition, an internal electron donor that gives a molecular weight distribution equivalent to that of the succinate compound may be used. Examples of such internal electron donors include diphenyl dicarboxylic acid esters described in JP2013-28704A, cyclohexene dicarboxylic acid esters described in JP2014-201602A, and JP2013-28705A. And didiol dibenzoate described in Japanese Patent No. 4959920, and 1,2-phenylene dibenzoate described in WO 2010/078494.

2) Organoaluminum compound (component B)
The following are mentioned as an organoaluminum compound of a component (B).
Trialkylaluminum such as triethylaluminum, tributylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;

Partially halogenated alkylaluminums such as alkylaluminum dihalogenides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide and the like;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.

3) Electron donor compound (component C)
The electron donor compound of component (C) is generally referred to as an “external electron donor”. Such an electron donor compound is preferably an organosilicon compound. The following is mentioned as a preferable organosilicon compound.
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxy Silane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyl Riethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyl Triethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chloro Triethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxy Lan, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, Dimethyltetraethoxydisiloxane.

  Among them, ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl (perhydroisoquinoline 2- Yl) dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropenyloxy) phenylsilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltrie Xysilane, phenyltrimethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyli-propyldimethoxysilane, cyclopentyl t-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, Cyclohexyl i-butyldimethoxysilane, cyclopentyl i-butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, Phenyltriethoxylane, bis p-tolyldimethoxy Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, methyl (3,3,3-trifluoropropyl) dimethoxy Silane and ethyl silicate are preferred.

4) Polymerization Polymerization is performed by bringing the raw material monomer into contact with the catalyst prepared as described above. At this time, it is preferable to first perform prepolymerization using the catalyst. Preliminary polymerization is a step of forming a polymer chain as a foothold for subsequent polymerization of raw material monomers on a solid catalyst component. The prepolymerization can be performed by a known method. The prepolymerization is usually performed at 40 ° C or lower, preferably 30 ° C or lower, more preferably 20 ° C or lower.
Next, the prepolymerized catalyst is introduced into the polymerization reaction system to perform main polymerization of the raw material monomers. In the main polymerization, the raw material monomer of component (1) and the raw material monomer of component (2) are preferably polymerized using two or more reactors. The polymerization may be carried out in the liquid phase (liquid monomer), in the gas phase or in the liquid-gas phase. The polymerization temperature is preferably from room temperature to 150 ° C, more preferably from 40 ° C to 100 ° C. The polymerization pressure is preferably in the range of 33 to 45 bar when carried out in the liquid phase and in the range of 5 to 30 bar when carried out in the gas phase. Conventional molecular weight regulators known in the art such as chain transfer agents (eg, hydrogen or ZnEt ₂ ) may be used.

  Further, a polymerization vessel having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerization vessel, for example, a monomer in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by gas phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region including a riser, and a monomer is supplied and polymerized in a downcomer connected to the riser. The polymer product is recovered while circulating. This method comprises means for completely or partially preventing the gas mixture present in the riser from entering the downcomer. Also, a gas and / or liquid mixture having a different composition from the gas mixture present in the riser is introduced into the downcomer. As the above polymerization method, for example, a method described in JP-T-2002-520426 can be applied.

2. Film A film obtained from the polypropylene composition of the present invention (also referred to as “the film of the present invention”) has an excellent matte tone, excellent mechanical properties, and few foreign substances, and is therefore useful as a food film. is there. Although the thickness of a film is not limited, It is preferable that they are 5 micrometers-100 micrometers. The film of the present invention and other films can be laminated to form a multilayer film. Examples of other films include films such as LDPE and EVA having relatively low mechanical strength, polyethylene terephthalate films having relatively good tearability, and the like. In the multilayer film, the film of the present invention is preferably the innermost layer. In addition, for the purpose of recycling, when a recycled material generated by end face cutting during film formation is used as an intermediate layer, it is possible to form a multilayer film (two types and three layers) while being a single material. It can also be combined with other films described above.

[Example 1]
A solid catalyst component was prepared according to the preparation method described in Examples of JP2011-500907A. Specifically:
In a 500 mL 4-neck round bottom flask purged with nitrogen, 250 mL of TiCl ₄ was introduced at 0 ° C. While stirring, 10.0 g of fine spherical MgCl ₂ .1.8C ₂ H ₅ OH (produced according to the method described in Example 2 of US Pat. No. 4,399,054, but operated at 3000 rpm instead of 10000 rpm) ) And 9.1 mmol of diethyl-2,3- (diisopropyl) succinate was added. The temperature was raised to 100 ° C. and held for 120 minutes. Next, stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was siphoned off. The following procedure was then repeated twice: 250 mL of fresh TiCl ₄ was added and the mixture was allowed to react at 120 ° C. for 60 minutes and the supernatant was siphoned off. The solid was washed 6 times with anhydrous hexane (6 × 100 mL) at 60 ° C.
The solid catalyst, triethylaluminum (TEAL) and dicyclopentyldimethoxysilane (DCPMS) are mixed in an amount such that the weight ratio of TEAL to the solid catalyst is 18 and the weight ratio of TEAL / DCPMS is 10 at room temperature. Touched for a minute. The resulting catalyst system was prepolymerized by holding it in liquid propylene in suspension for 5 minutes at 20 ° C.
The obtained prepolymer is introduced into a first-stage liquid phase polymerization reactor to obtain a propylene homopolymer, and then the obtained polymer is introduced into a second-stage gas phase polymerization reactor. A polymer (propylene / ethylene copolymer) was polymerized. During the polymerization, temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier. The polymerization temperature and the ratio of the reactants are as follows: polymerization temperature and hydrogen concentration in the first reactor are 70 ° C. and 0.35 mol%, respectively, polymerization temperature, hydrogen concentration, C2 / ( C2 + C3) were 80 ° C., 1.13 mol% and 0.22 mol ratio, respectively. Moreover, the residence time distribution of the 1st stage and the 2nd stage was adjusted so that the quantity of a copolymer component might be 24 weight part in 100 weight part of polymers. To 100 parts by weight of the obtained polypropylene polymer, 0.2 parts by weight of BASF B225 as an antioxidant, 0.05 parts by weight of calcium stearate manufactured by Tamnan Chemical Co., Ltd. as a neutralizer, After stirring and mixing with a Henschel mixer for 1 minute, it was extruded at a cylinder temperature of 230 ° C with an NVC φ50mm single screw extruder manufactured by Nakatani Machinery Co., Ltd., and the strand was cooled in water, then cut with a pelletizer, and a pellet-shaped polypropylene resin composition I got a thing.

  The polypropylene composition thus produced was subjected to the conditions of a cylinder setting temperature of 230 ° C., a die setting temperature of 250 ° C., and a screw rotation speed of 50 rpm using a 25 mmφ3 type three-layer downward T-die molding machine manufactured by Thermoplastics Industries Co., Ltd. To form a film. The obtained film was evaluated by the method described later.

[Example 2]
A polypropylene resin composition for this example was produced as follows, and a film was produced and evaluated in the same manner as in Example 1.
Using the same prepolymer as in Example 1, a propylene homopolymer was produced by multistage polymerization using two liquid phase polymerization reactors. The hydrogen concentration in the first polymerization reactor was 0.13 mol%, the hydrogen concentration in the second polymerization reactor was 1.43 mol%, the polymerization pressure was adjusted at a polymerization temperature of 70 ° C., and the respective ratios The residence time distribution was adjusted so as to be 50:50. The obtained propylene homopolymer was introduced into a gas phase polymerization reactor, and a copolymer (propylene / ethylene copolymer) was polymerized in the same manner as in Example 1.
When broadening the molecular weight distribution by multi-stage polymerization as described above, there is generally concern about poor dispersion of the high molecular weight component and the low molecular weight component, but when a succinate catalyst is used, the molecular weight distribution of each component becomes wide. The high molecular weight component and the low molecular weight component overlap each other, and the dispersion failure does not cause a problem.

[Example 3]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that the hydrogen concentration and ethylene concentration in the first-stage reactor were changed to 0.48 mol% and 0.56 mol%, respectively. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 4]
Other than adjusting the residence time distribution of the first and second stages so that the hydrogen concentration in the first stage reactor is 0.37 mol% and the amount of the copolymer component is 29 parts by weight in 100 parts by weight of the polymer. Produced a polypropylene resin composition for this example in the same manner as in Example 1. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 5]
The polypropylene resin composition for this example was the same as in Example 4 except that the residence time distributions in the first and second stages were adjusted so that the amount of the copolymer component was 19 parts by weight in 100 parts by weight of the polymer. The thing was manufactured. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 6]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that C2 / (C2 + C3) in the second stage reactor was changed to 0.28 molar ratio. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 7]
The polypropylene resin composition for this example was the same as in Example 1 except that the hydrogen concentration in the first-stage reactor was 0.25 mol% and the hydrogen concentration in the second-stage reactor was 1.61 mol%. The thing was manufactured. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 8]
The polypropylene resin composition for this example was the same as in Example 1, except that the hydrogen concentration in the first-stage reactor was 0.47 mol% and the hydrogen concentration in the second-stage reactor was 0.83 mol%. The thing was manufactured. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 9]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that the hydrogen concentration in the first-stage reactor was 0.27 mol%. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 10]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that the hydrogen concentration in the first-stage reactor was changed to 0.56 mol%. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Example 11]
Using the polypropylene resin composition of Example 1, a multilayer film of two types and three layers having a recycled material in the process as an intermediate layer was obtained. The manufacturing conditions were the same as in Example 1 except that multilayer extrusion was performed.

[Comparative Example 1]
A polypropylene resin composition for this example was produced as follows, and a film was produced and evaluated in the same manner as in Example 1.
A solid catalyst in which Ti and diisobutyl phthalate as an internal donor were supported on MgCl ₂ was prepared by the method described in Example 5 of European Patent No. 728769. Next, using the above solid catalyst, triethylaluminum (TEAL) as the organoaluminum compound and dicyclopentyldimethoxysilane (DCPMS) as the external electron donor compound, the weight ratio of TEAL to the solid catalyst is 20, and the weight ratio of TEAL / DCPMS. Was contacted at 12 ° C. for 24 minutes. The resulting catalyst system was preliminarily polymerized by keeping it in suspension in liquid propylene at 20 ° C. for 5 minutes. The obtained prepolymer is introduced into a first polymerization reactor of a polymerization apparatus equipped with a two-stage polymerization reactor in series to produce a propylene homopolymer, and ethylene-propylene is produced in the second polymerization reactor. A copolymer was produced. During the polymerization, temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier.
The polymerization temperature and the ratio of the reactants are as follows: the polymerization temperature and hydrogen concentration in the first-stage reactor are 70 ° C. and 0.49 mol%, respectively, and the polymerization temperature, hydrogen concentration, C2 / ( C2 + C3) were 80 ° C., 1.13 mol%, and 0.21 mol ratio, respectively. Moreover, the residence time distribution of the 1st stage and the 2nd stage was adjusted so that the quantity of a copolymer component might be 24 weight part in 100 weight part of polymers.

[Comparative Example 2]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that the hydrogen concentration and ethylene concentration in the first-stage reactor were changed to 0.64 mol% and 0.95 mol%, respectively. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Comparative Example 3]
The polypropylene resin composition for this example was the same as in Example 1 except that the residence time distributions of the first and second stages were adjusted so that the amount of the copolymer component was 14 parts by weight per 100 parts by weight of the polymer. The thing was manufactured. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Comparative Example 4]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that C2 / (C2 + C3) in the second-stage reactor was changed to 0.05 molar ratio. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Comparative Example 5]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that C2 / (C2 + C3) in the second-stage reactor was changed to 0.41 molar ratio. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Comparative Example 6]
The polypropylene resin composition for this example was the same as in Example 1 except that the hydrogen concentration in the first-stage reactor was 0.20 mol% and the hydrogen concentration in the second-stage reactor was 2.96 mol%. The thing was manufactured. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Comparative Example 7]
The polypropylene resin composition for this example was the same as in Example 1, except that the hydrogen concentration in the first-stage reactor was 0.82 mol% and the hydrogen concentration in the second-stage reactor was 0.51 mol%. The thing was manufactured. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Comparative Example 8]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that the hydrogen concentration in the first-stage reactor was changed to 0.11 mol%. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.

[Comparative Example 9]
A polypropylene resin composition for this example was produced in the same manner as in Example 1 except that the hydrogen concentration in the first-stage reactor was 1.26 mol%. In the same manner as in Example 1, a film was produced from the polypropylene resin composition and evaluated.
The results are shown in Table 1.

Each physical property was evaluated as follows.
[MFR]
According to JIS K 7210, the measurement was performed under the conditions of 230 ° C. and a load of 21.18 N.
[Ethylene concentration in copolymer]
A sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene was measured by ¹³ C-NMR method using JNM LA-400 ( ¹³ C resonance frequency 100 MHz) manufactured by JEOL Ltd. .

[Collecting xylene solubles]
Place 2.5 g of polymer in a flask containing 250 mL of o-xylene (solvent) and stir for 30 minutes at 135 ° C. while purging with nitrogen at 135 ° C. using a hot plate and reflux apparatus to completely dissolve the composition. Then, cooling was performed at 25 ° C. for 1 hour. The resulting solution was filtered using filter paper. 100 mL of the filtrate after filtration was collected, transferred to an aluminum cup or the like, evaporated and dried at 140 ° C. while purging with nitrogen, and allowed to stand at room temperature for 30 minutes to obtain a xylene-soluble component (XS). The container was then maintained in an oven at 80 ° C. under vacuum until a constant weight was obtained, and then the weight of polymer dissolved in xylene at room temperature was determined. The weight percent of the polymer dissolved in xylene with respect to the total polymer was calculated and used as the amount of xylene solubles at 25 ° C.
[XSIV]
Using the xylene-soluble matter as a sample, the intrinsic viscosity was measured in 135 ° C. tetrahydronaphthalene using an Ubbelohde viscometer (SS-780-H1, manufactured by Shibayama Scientific Instruments).

[Collecting xylene-insoluble matter]
As described above, when the xylene-soluble component is filtered, acetone is added to the residue (mixture of xylene-insoluble component and solvent) remaining on the filter paper and filtered, and then the unfiltered component is vacuumed at 80 ° C. In a drying oven, it was evaporated to dryness to obtain xylene-insoluble matter (XI).
[Mw and Mw / Mn of xylene insoluble matter]
Using the xylene-insoluble matter as a sample, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured as follows.
PL GPC220 manufactured by Polymer Laboratories is used as an apparatus, 1,2,4-trichlorobenzene containing an antioxidant is used as a mobile phase, and UT-G (1), UT-807 (Showa Denko KK) is used as a column. 1) and UT-806M (2) connected in series were used, and a differential refractometer was used as a detector. Moreover, the same solvent as the mobile phase was used as a solvent for the sample solution of xylene-insoluble matter, and a measurement sample was prepared by dissolving at a sample concentration of 1 mg / mL for 2 hours while shaking at a temperature of 150 ° C. 500 μL of the sample solution thus obtained was injected into the column and measured at a flow rate of 1.0 mL / min, a temperature of 145 ° C., and a data acquisition interval of 1 second. For column calibration, a polystyrene standard sample (shodex STANDARD, manufactured by Showa Denko KK) having a molecular weight of 580 to 7.45 million was used and approximated by a cubic equation. The Mark-Houkins coefficients are K = 1.21 × 10 ⁻⁴ and α = 0.707 for the polystyrene standard sample, and K = 1.37 × 10 ⁻⁴ and α = 0. 75 was used.

[Extruder load]
In film forming, the pressure after 5 minutes from the start of forming was measured.
[Thickness accuracy]
A film thickness of 30 μm was molded under the following conditions.
Extruder: Thermoplastics Industries Co., Ltd. 25mmφ3 type 3 layer downward T-die molding machine Setting temperature: Cylinder 230 ° C, Die 250 ° C
Take-up machine chill roll temperature: 30 ° C
Take-up machine take-off speed: 10m / min
Screw rotation speed: 30rpm
With air knife Standard deviation was determined from the thickness of a central portion of the film molded under the above conditions, measured at 10 points at equal intervals in the TD direction. The standard deviation was divided by the average thickness and expressed as a percentage.
This measurement was carried out at two locations with an interval of 1 m or more in the MD direction, and the standard deviation was obtained and divided by the average thickness and expressed as a percentage.
The percentage values obtained at these three locations were averaged to obtain thickness accuracy.

[Melt tension index]
Capillograp 1C manufactured by Toyo Seiki Seisakusho Co., Ltd. is equipped with an orifice with a flat top surface of L = 8.0 mm and D = 2.095 mm, polypropylene at a measurement temperature of 200 ° C., extrusion speed of 15 mm / min, take-up speed of 6.5 m / min. The tension at the time when the composition was taken was measured to obtain the melt tension (MT). The melt tension index was measured using the following formula.
Melt tension index = log (MT) + 0.85 × log (MFR) −0.82

[Haze]
Based on JIS K7136, it measured by n = 3 using the haze measuring apparatus (HM-150 type | mold by Murakami Color Research Laboratory Co., Ltd.).
[Fish eye]
Nagase Sangyo Co., Ltd. Fisheye counter SCANTEC7000 was used for measurement. The categories are as follows.
Fisheye small: maximum diameter 0.1 mm or more and less than 0.2 mm Fisheye medium: maximum diameter 0.2-0.5 mm

[Tensile modulus]
Based on JIS K7127, the tensile elastic modulus of the film MD direction was measured using TS Co., Ltd. manual tensile testing machine Autocom AC-C series. The conditions are as follows.
Test speed: 5mm / min
Distance between grips: 100mm
Specimen type 2 (width 10mm)
Number of tests: n = 5 (average value is tensile modulus)

[Impact strength]
Based on ASTM D3420 conformity, evaluation was performed using a film impact tester with a thermostatic chamber manufactured by Toyo Seiki Seisakusho. The conditions are as follows.
Maximum capacity: 3.0J
Pendulum tip shape: 1 inch (R; 12.7 mm, diameter; 25.4 mm) hemisphere Atmosphere in the tank: 0 ° C. (± 0.4 ° C.)
Number of tests: n = 16 (average value is impact strength)

Claims (9)

85 to 55 parts by weight of a propylene (co) polymer containing 0 to 3.5% by weight of ethylene-derived units as component (1), and 15 to 45% by weight of ethylene-derived units as component (2) A polypropylene composition comprising 15 to 45 parts by weight of a propylene-ethylene copolymer,
The following requirements:
1) Mw / Mn measured by GPC of xylene-insoluble matter of the composition is 7 or more 2) The intrinsic viscosity of xylene-soluble matter of the composition is 2 to 4.5 dl / g 3) The composition The melt flow rate (230 ° C., load 21.18 N) is 2 to 20 g / 10 min. 4) The polypropylene composition satisfies the melt tension index of the composition is 1.5 or more.   The polypropylene composition according to claim 1, wherein the ethylene-derived unit of the propylene-ethylene copolymer in the component (2) is 25 to 35% by weight.   The polypropylene composition according to claim 1 or 2, wherein Mw / Mn of the xylene-insoluble matter is 9 or more.   The polypropylene composition according to any one of claims 1 to 3, wherein the intrinsic viscosity of the xylene-soluble component is 2.4 to 3.8 dl / g.   The polypropylene composition according to any one of claims 1 to 4, wherein the melt flow rate is 4 to 10 g / 10 min.   The polypropylene composition according to any one of claims 1 to 5, comprising 82 to 70 parts by weight of the component (1) and 18 to 30 parts by weight of the component (2). (A) a solid catalyst containing, as an essential component, an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound;
(B) Organoaluminum compound; and (C) The polypropylene composition according to any one of claims 1 to 6, obtained by polymerizing propylene and ethylene using a catalyst containing an external electron donor compound.   The film formed by shape | molding the polypropylene composition in any one of Claims 1-7.   A multilayer film comprising the film according to claim 8.