JP6860326B2 - Polypropylene composition and matte film formed by molding the polypropylene composition - Google Patents

Description

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

Polypropylene is used as a food film because it has excellent physical properties and is also excellent in hygiene. Recently, in order to enhance the aesthetics and design of packaged foods, the use of matte-like films with matte finish has become popular. For example, Patent Document 1 proposes a matte-like film made of a polypropylene composition capable of achieving a sufficient matte feeling without impairing mechanical properties and the like.

Japanese Unexamined Patent Publication No. 2011-194588

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 improve the matte tone by forming so-called fish eyes in the film. It was found that there is a problem that a foreign substance called is generated and a poor appearance occurs. In view of such circumstances, it is an object of the present invention to provide a polypropylene composition that gives a film having a good appearance and a high matte tone.

The inventors have found that the above-mentioned problems can be solved by setting the ultimate viscosity of the xylene insoluble component of the polypropylene composition within a specific range and setting the ethylene content in the second component within a specific range. That is, the above-mentioned problem is solved by the following invention.
[1] As component (1), 85 to 55 parts by weight of a propylene (co) polymer containing 0 to 3.5% by weight of ethylene-derived units, and as component (2), 15 to 45% by weight of ethylene-derived A polypropylene composition containing 15 to 45 parts by weight of a propylene-ethylene copolymer containing a unit.
The following requirements:
1) Mw / Mn of the xylene-insoluble component of the composition measured by GPC is 7 or more. 2) The ultimate viscosity of the xylene-soluble component 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 minutes. 4) A polypropylene composition satisfying that 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 the xylene insoluble Mw / Mn is 9 or more.
[4] The polypropylene composition according to any one of [1] to [3], wherein the xylene-soluble component has an ultimate viscosity of 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], which comprises 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 an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component;
The polypropylene composition according to any one of [1] to [6], obtained by polymerizing propylene and ethylene using a catalyst containing (B) an organoaluminum compound and (C) an external electron donor compound. ..
[8] A film obtained by molding the polypropylene composition according to any one of the above [1] to [7].
[9] A multilayer film containing the film according to the above [8].

It is possible to provide a polypropylene composition which gives a film having a good appearance and a high matte tone.

Hereinafter, the present invention will be described in detail. In the present invention, "X to Y" includes the fractional values X and Y.

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

(1) Component (1): Propylene (co) polymer The propylene (co) polymer is a propylene homopolymer or a copolymer of ethylene and propylene in an amount of more than 0% by weight and not more than 3.5% by weight. .. From the viewpoint of the balance between the matte tone and the rigidity of the film, a propylene homopolymer is preferable as the component (1). On the other hand, when flexibility and the like are required, a copolymer is preferable as the component (1). The propylene copolymer containing 1.0% by weight of ethylene-derived units is a copolymer in which the weight ratio of ethylene-derived units to propylene-derived units is 1.0: 99.0. The same applies to other copolymers. The upper limit of the content of ethylene-derived units is 3.5% by weight or less, but 3% by weight or less is preferable. When the amount exceeds the upper limit value, the haze is lowered, a sufficient matte tone cannot be obtained, and the rigidity is lowered. The lower limit in the presence of ethylene-derived units is not limited, but 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. If the content of the ethylene-derived unit is less than the lower limit, the haze is lowered, a sufficient matte tone cannot be obtained, and the impact strength is also lowered. On the other hand, if the content of ethylene-derived units 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 the components (1) and (2) is (1) :( 2) = 85-55: 15-45. If the amount of the component (2) exceeds this upper limit, production becomes difficult. If the amount of the component (2) is less than the lower limit, the haze is lowered, a sufficient matte tone cannot be obtained, and the impact strength is also lowered. From this point of view, the ratio is preferably 82-70: 18-30.

(4) Other components In addition, the masterbatch composition includes antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, and antifogging agents. In the field of agents, crystal nucleating agents, flame retardants, dispersants, copper damage inhibitors, neutralizing agents, plasticizers, bubble inhibitors, cross-linking agents, peroxides, oil spreads and other organic and inorganic pigments. Commonly used additives may be added. The amount of each additive added may be a known amount.

(5) Characteristics 1) Mw / Mn of xylene insoluble matter
Mw and Mw / Mn of xylene insoluble matter (XI) can be obtained by obtaining a component insoluble in xylene at 25 ° C. and measuring the component by a GPC (gel permeation chromatography) method. The Mw / Mn of the polypropylene composition of the present invention measured by GPC of XI is as wide as 7 or more. When Mw / Mn is less than 7, the load during extrusion molding becomes large, and the thickness / thinness accuracy of the film decreases. Therefore, since the polypropylene composition of the present invention has a wide molecular weight distribution, it provides a film having excellent moldability and thickness / thinness accuracy. From this viewpoint, Mw / Mn is preferably 9 or more. However, if Mw / Mn is excessively high, the dispersibility between the high molecular weight component and the low molecular weight component deteriorates, which causes a problem that it becomes difficult to manufacture a product having homogeneous characteristics. Therefore, the upper limit of Mw / Mn is preferably 20 or less.

2) XSIV
The ultimate viscosity (XSIV) of the xylene-soluble component (XS) of the composition is also an index of the molecular weight of the non-crystalline component in the composition. XSIV is obtained by obtaining a component soluble in xylene at 25 ° C. and measuring the ultimate viscosity of the component by a conventional method. In the present invention, XSIV is 2 to 4.5 dl / g. If the XSIV exceeds the upper limit, the fish eye increases, and if it is less than the lower limit, the haze decreases and a sufficient matte tone cannot be obtained. Therefore, when XSIV is in this range, the appearance of the film can be improved. From this point of view, the ultimate viscosity is preferably 2.4 to 3.8 dl / g.

3) Melt flow rate The melt flow rate (hereinafter, also referred to as “MFR”) of the polypropylene composition of the present invention at 230 ° C. and a load of 21.18 N is 2 to 20 g / 10 minutes. When the melt flow rate exceeds the upper limit, the fish eye increases and the impact strength decreases. If the melt flow rate is less than the lower limit, the load during extrusion molding increases. From this point of view, the melt flow rate is preferably 4 to 10 g / 10 minutes. 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 the molten resin flows into the die. It is known that when the elongation stress exceeds the critical value, brittle fracture called melt fracture occurs, unstable flow occurs at the die outlet, and minute irregularities are formed on the surface of the molded product. A general melt fracture becomes striped and causes a poor appearance as a molded product. However, in film molding, since the melt fracture is minute, it is presumed that the appearance will be a high-class matte tone. Therefore, when the melt tension index is 1.5 or more, the tensile stress becomes large and a good matte tone can be obtained in film molding. From this viewpoint, the melt tension index is preferably 1.6 or more. However, if the XSIV is set high in order to increase the melt tension index, there arises a problem that the fish eye increases or the viscosity of the composition increases and the load during extrusion molding increases. From this point of view, 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, CAPIROGRAPH 1C manufactured by Toyo Seiki Seisakusho Co., Ltd.).
i) The polypropylene composition is extruded from the orifice at 200 ° C. at an extrusion rate of 15 mm / min.
ii) The extruded product is picked up at a pick-up speed of 6.5 m / min, and the tension at that time is measured as the melt tension MT (g weight).
iii) Obtain the melt tension index using the following equation.
Melt tension index = log (MT) +0.85 x log (MFR) -0.82
In the present invention, the measuring machine is equipped with an orifice having a flat upper surface of L = 8.0 mm and D = 2.095 mm, and is composed at a measurement temperature of 200 ° C., an extrusion speed of 15 mm / min, and a take-up speed of 6.5 m / min. It is preferable to measure the tension at the time of picking up the object as the melt tension MT (unit: g weight).

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

6) Fish eyes The fish eyes of the film obtained from the polypropylene composition of the present invention ^{are preferably medium (maximum diameter 0.2 to 0.5 mm) of 2 pieces / 0.1 m 2} or less. Smaller ones (maximum diameter of 0.1 mm or more and less than 0.2 mm) ^{are preferably 10 pieces / 0.1 m 2} or less. Fish eyes can be measured using a fish eye counter.

7) Tension elastic modulus The tensile elastic modulus of the film obtained from the polypropylene composition of the present invention is preferably 500 MPa or more. The tensile 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 action The polypropylene composition of the present invention provides an excellent matte-like film with few foreign substances such as fish eyes. Generally, when the molecular weight distribution (Mw / Mn) of XI of the composition is widened and the copolymer component (2) having a different density is introduced, the matte tone of the film can be improved, but the fish eyes increase and the appearance is deteriorated. However, in the present invention, reduction of fish eyes and high matte tone can be achieved by setting the amount of ethylene of the component (2) and XSIV within a specific range. The reason for this is not limited, but it can be inferred as follows.

When the elongation stress generated when the molten resin flows into the die exceeds the critical value, brittle fracture called melt fracture occurs, unstable flow occurs at the die outlet, and minute irregularities are generated on the surface of the molded product. Is known to be formed. The unevenness caused by a general melt fracture becomes striped and causes a poor appearance of the molded product. However, since the melt fracture is minute in film molding, it is considered that the appearance has a high-class matte appearance. When the above-mentioned melt tension index is 1.5 or more, it is considered that the tensile stress becomes large at the strain rate in the general molding process, and a good matte tone can be obtained in the film forming. In the polypropylene composition of the present invention, the dispersibility of the copolymer component (2) is improved, and as a result of the melt tension index of 1.5 or more, it is possible to produce a high matte film with few 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 the component (1) and the raw material monomer of the component (2) are mixed with (A) magnesium, titanium, halogen, and the inside. 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)
The component (A) can be prepared by a known method, for example, by bringing the magnesium compound, the titanium compound and the electron donor compound into mutual contact.

As the titanium compound used for the preparation of the component (A), a tetravalent titanium compound represented by _{the general formula: Ti (OR) g} X _{4-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 ) _{Trihalogenated alkoxytitanium such as Cl 3} , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl _{2, Ti (O n -C 4} H 9) 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated alkoxy titanium such as _{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) monohalide trialkoxy titanium such as _{3 Br; Ti (OCH 3)} 4, Ti (OC 2 H 5) 4, Ti ( such as O _n -C ₄ tetraalkoxy titanium such as H _{9) 4} and the like. Among these, a halogen-containing titanium compound, particularly titanium tetrahalogenate, is preferable, and a more particularly preferable one is titanium tetrachloride.

Examples of the magnesium compound used for the preparation of the component (A) include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, and dihexylmagnesium. Examples thereof include decyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxymagnesium, ethyl butyl magnesium, and butyl magnesium hydride. These magnesium compounds can be used in the form of a complex compound with, for example, organoaluminum, and may be in a liquid state or a solid state. More suitable magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; magnesium methoxychloride, magnesium ethoxychloride, magnesium isopropoxychloride, magnesium butoxychloride, magnesium octoxychloride. Alkoxymagnesium halide; Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; Alyloxymagnesium such as magnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate can be mentioned.

The electron donor compound used for the preparation of the component (A) is generally referred to as an "internal electron donor". In the present invention, it is preferable to use an internal electron donor that gives a wide molecular weight distribution. Generally, it is known that the molecular weight distribution can be increased by carrying out polymerization in multiple steps, 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, it is possible to increase the molecular weight distribution even when the molecular weight of XI is low. The composition polymerized using the catalyst is a composition having the same molecular weight distribution obtained by pelleting or powder blending a polymer polymerized using another catalyst, and a composition having the same molecular weight distribution by further polymerizing in multiple stages. It shows different characteristics from the thing. This is because the composition produced by using the catalyst is integrated with the high molecular weight component and the low molecular weight component in a state close to the molecular level, but the latter resin composition is not mixed in a state close to the molecular level. It is considered that this is because they seem to show the same molecular weight distribution. However, it is not realistic to express this in words in the claims. Hereinafter, preferred internal electron donors will be described.

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

In the formula, the groups R ₁ and R ₂ are linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkyl of _{C 1 to} C ₂₀ , which are the same or different from each other and sometimes contain a heteroatom. Aryl groups; groups R _{3 to} R ₆ are linear or branched alkyl, alkenyl, cycloalkyl, aryl, of _{C 1 to} C ₂₀ , which are identical or different from each other and contain hydrogen or, in some cases, heteroatoms. _{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. Compounds in which R ₁ and R ₂ are selected from primary alkyls, particularly branched primary alkyls, are particularly preferred. 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 of the preferred groups of compounds represented by formula (I) is branched alkyl, cycloalkyl, aryl, arylalkyl _{, where 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 a monosubstituted succinate compound are diethyl-sec-butyl succinate, diethyl texyl succinate, diethyl cyclopropyl succinate, diethyl norbonyl succinate, diethyl perihydro succinate, 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 isopentyl succinate, diethyl (1-trifluoromethyl ethyl) succinate , Diethylfluorenyl succinate, 1-ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyltexyl succinate, diisobutylcyclopropyl succinate, diisobutylnorbonyl succinate, diisobutylperihydro Succinate, diisobutyltrimethylsilyl succinate, diisobutylmethoxysuccinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutylcyclohexylsuccinate, diisobutylbenzyl succinate, diisobutylcyclohexylmethyl Succinate, diisobutyl-t-butyl succinate, diisobutylisobutyl succinate, diisobutylisopropyl succinate, diisobutylneopentyl succinate, diisobutylisopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, Diisobutylfluorenyl succinate, dineopentyl-sec-butyl succinate, dineopentyltexyl succinate, geneopentylcyclopropyl succinate, dineopentyl norbonyl succinate, dineopentyl perihydrosuccinate , Dineopentyltrimethylsilyl succinate, dineopentylmethoxysuccinate, geneopentyl-p-methoxyphenyl succinate, geneopentyl-p-chlorophenyl succinate, geneopentylphenyl succinate, genine Opentyl Cyclohexyl succinate, Dineopentyl benzyl succinate, Dineopentyl cyclohexylmethyl 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 range of formula (I) is a _{linear C 1 to} C ₂₀ in which _{at least two groups from R 3 to} R ₆ differ from hydrogen and in some cases contain heteroatoms. Alternatively, it is selected from branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups. A compound in which two groups different from hydrogen are bonded to the same carbon atom is particularly preferable. Specifically, it is a compound in which _{R 3} and R ₄ are different groups 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-isobutylsuccinate, diethyl-2-cyclopentyl-2-n-butylsuccinate, diethyl-2,2-diisobutylsuccinate, diethyl-2-cyclohexyl-2-ethylsuccinate Nate, 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-isobutylsuccinate, diethyl-2-phenyl-2-n-butylsuccinate, diisobutyl-2,2-dimethylsuccinate, Diisobutyl-2-ethyl-2-methylsuccinate, diisobutyl-2-benzyl-2-isopropylsuccinate, diisobutyl-2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl-2-cyclopentyl-2-n- Butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2-cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methylsuccinate, diisobutyl-2-tetradecyl-2- Ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl-2- (1-trifluoromethylethyl) -2-methyl succinate, diisobutyl-2-isopentyl-2-isobutyl succinate , Diisobutyl-2-phenyl-2-n-butyl succinate, dineopentyl-2,2-dimethylsuccinate, dineopentyl-2-ethyl-2-methylsuccinate, dineopentyl-2-benzyl-2-isopropyls Xinate, 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 succine , Dineopentyl-2-isobutyl-2-ethyl succinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methylsuccinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl It is -2-phenyl-2-n-butyl succinate.

Further, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are also particularly preferable. Specifically, it is _{a compound in which R 3} and R ₅ are different groups from hydrogen. In this case, R ₄ and R ₆ may be hydrogen atoms or groups different from hydrogen, but it is preferable that one of them is a hydrogen atom (trisubstituted succinate). Preferred specific 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-dibenzylsuccinate, diethyl-2,3-diisopropylsuccinate, diethyl-2,3-bis (cyclohexylmethyl) ) Succinate, diethyl-2,3-di-t-butyl succinate, diethyl-2,3-diisobutyl succinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diiso Pentyl 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-isopropylsuccinate, diisobutyl-2,3-diisopropyl-2 -Methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methylsuccinate, diisobutyl-2,3-dibenzylsuccinate, diisobutyl-2,3-diisopropylsuccinate, 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-fluorenyl succinate , Diisobutyl-2-isopropyl-3-isobutyl succinate, diisobutyl-2-tert-butyl-3-isopropyl succinate, diisobutyl-2-isopropyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3-3 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-methylsuccinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methylsuccinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, dineopentyl- 2,3-Diethyl-2-isopropyl succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3-di Benzyl succinate, dineopentyl-2,3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2,3- Diisobutyl succinate, geneopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl-2 , 3-Tetradecyl succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl-3-isopropyl succinate, dineopentyl -2-Isopropyl-3-cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, dineopentyl-2-cyclohexyl-3-cyclopentyl succinate Nate.

Among the compounds of formula (I), a compound some are bonded to form a ring together of the radicals R ₃ to R ₆ may be also preferably used. As such compounds, the compounds listed in Special Table 2002-542347, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1-( Ethoxyacetyl) -2,5-1 dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -21methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned. In addition, cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid and diisobutyl cyclohexane-1,2-dicarboxylic acid as disclosed in International Publication No. 2009/069483 are also preferable. Can be used. As an example of other cyclic succinate compounds, the compounds disclosed in WO 2009/057747 are also preferred.

Among the compounds of formula (I), if the group R ₃ to R ₆ is a hetero atom, it heteroatom is 16 atoms containing Group 15 atom or an oxygen and sulfur atom containing nitrogen and phosphorus atoms preferable. Examples of the compound in which the groups R _{3 to} R ₆ contain a Group 15 atom include compounds disclosed in JP-A-2005-306910. On the other hand, groups _R 3 to R ₆ are Examples of the compound containing a Group 16 atom include compounds disclosed in JP-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 an internal electron donor include the diphenyldicarboxylic acid ester described in JP2013-288704, the cyclohexenedicarboxylic acid ester described in JP2014-2016002, and JP2013-28705. Dicycloalkyldicarboxylic acid ester, diol dibenzoate described in Japanese Patent No. 4959920, 1,2-phenylenedibenzoate described in International Publication No. 2010/078494.

2) Organoaluminium compound (component B)
Examples of the organoaluminum compound of the component (B) include the following.
Trialkylaluminum such as triethylaluminum and tributylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide;

Partially halogenated alkylaluminum such as alkylaluminum dihalogenide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Partially hydrogenated alkylaluminum such as alkylaluminum dihydrides such as ethylaluminum dihydrides and propylaluminum dihydrides;
Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid.

3) Electron donor compound (component C)
The electron donor compound of component (C) is generally referred to as an "external electron donor". As such an electron donor compound, an organosilicon compound is preferable. Preferred organosilicon compounds include:
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyldiethoxysilane, biso-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane Silane, Cyclohexylmethyldimethoxysilane, Cyclohexylmethyldiethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Methyltrimethoxysilane, n-propyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n-butyltriethoxysilane, iso- Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornantrimethoxysilane , 2-Norbornanthriethoxysilane, 2-norbornanmethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyl Tetraethoxydisiloxane.

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 (perhydroisoquinolin 2-) Il) dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropeniroxy) phenylsilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltri Butoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyl i-propyldimethoxysilane, cyclopentyl t-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyl i-butyldimethoxysilane, cyclopentyl i -Butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxylan, bisp-tolyl Dimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, diphenyldiethoxysilane, methyl (3,3,3-trifluoropropyl) Dimethoxysilane, ethyl silicate and the like are preferable.

4) Polymerization The raw material monomer is brought into contact with the catalyst prepared as described above to polymerize. At this time, it is preferable to first perform prepolymerization using the catalyst. The prepolymerization is a step of forming a polymer chain as a foothold for the subsequent main polymerization of the raw material monomer in the solid catalyst component. Prepolymerization can be carried out by a known method. Prepolymerization is usually carried out at 40 ° C. or lower, preferably 30 ° C. or lower, and more preferably 20 ° C. or lower.
Next, the prepolymerized catalyst is introduced into the polymerization reaction system to carry out the main polymerization of the raw material monomer. In this polymerization, it is preferable to polymerize the raw material monomer of the component (1) and the raw material monomer of the component (2) using two or more reactors. The polymerization may be carried out in a liquid phase (liquid monomer), in a gas phase or in a liquid-gas phase. The polymerization temperature is preferably normal temperature to 150 ° C., more preferably 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 modifiers known in the art, such as chain transfer agents (eg, hydrogen or ZnEt _{2), may be used.}

Further, a polymerizer having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerizer, for example, one in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by vapor phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region consisting of an ascending tube, and a monomer is supplied and polymerized by a descending tube connected to the ascending tube. The polymer product is recovered while circulating. This method comprises means to prevent the gas mixture present in the ascending tube from entering the descending tube in whole or in part. Also, a gas and / or liquid mixture having a composition different from that of the gas mixture present in the ascending tube is introduced into the descending tube. As the above polymerization method, for example, the method described in JP-A-2002-520426 can be applied.

2. Film The film obtained from the polypropylene composition of the present invention (also referred to as the "film of the present invention") is useful as a food film because it has excellent matte tone, excellent mechanical properties, and few foreign substances. is there. The thickness of the film is not limited, but is preferably 5 μm to 100 μm. Further, the film of the present invention and another film can be laminated to form a multilayer film. Examples of other films include films such as LDPE and EVA having relatively low mechanical strength, and polyethylene terephthalate films having relatively good tearability. In the multilayer film, the film of the present invention is preferably the innermost layer. Further, for the purpose of recycling, when a recycled material generated by cutting the end face during film molding is used as an intermediate layer, it is possible to use a single material as a multilayer film (2 types and 3 layers), and further. It can also be combined with the other films mentioned above.

[Example 1]
A solid catalyst component was prepared according to the preparation method described in Examples of JP-A-2011-500907. Specifically:
_{250 mL of TiCl 4} was introduced at 0 ° C. into a 500 mL four-necked round bottom flask purged with nitrogen. While stirring, according to the method described in Example 2 10.0g of the fine spherical _{MgCl 2 · 1.8C 2 H 5 OH} ( US Patent 4,399,054, however operating at 3000rpm instead of 10000rpm production And 9.1 mmol of diethyl-2,3- (diisopropyl) succinate were added. The temperature was raised to 100 ° C. and held for 120 minutes. The stirring was then stopped, the solid product was allowed to settle and the supernatant was sucked out. The following operation was then repeated twice: 250 mL of fresh TiCl ₄ was added, the mixture was reacted at 120 ° C. for 60 minutes and the supernatant was sucked out. The solid was washed 6 times with anhydrous hexane (6 x 100 mL) at 60 ° C.
The solid catalyst and triethylaluminium (TEAL) and dicyclopentyldimethoxysilane (DCPMS) are prepared in such an amount that the weight ratio of TEAL to the solid catalyst is 18 and the weight ratio of TEAL / DCPMS is 10 at room temperature. Contacted for minutes. Prepolymerization was carried out by holding the obtained catalyst system in a suspended state in liquid propylene at 20 ° C. for 5 minutes.
The obtained prepolymer was introduced into the first-stage liquid-phase polymerization reactor to obtain a propylene homopolymer, and then the obtained polymer was introduced into the second-stage gas-phase polymerization reactor to have a common weight. The coalescence (propylene / ethylene copolymer) was polymerized. During the polymerization, the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier. The ratio of the polymerization temperature to the reactants was as follows: in the first stage reactor, the polymerization temperature and hydrogen concentration were 70 ° C. and 0.35 mol%, respectively, and in the second stage reactor, the polymerization temperature and hydrogen concentration, C2 / ( C2 + C3) had a ratio of 80 ° C., 1.13 mol%, and 0.22 mol, respectively. Further, the residence time distributions of the first and second stages were adjusted so that the amount of the copolymer component was 24 parts by weight out of 100 parts by weight of the polymer. To 100 parts by weight of the obtained polypropylene polymer, 0.2 parts by weight of BASF B225 as an antioxidant and 0.05 parts by weight of calcium stearate manufactured by Tannan Chemical Co., Ltd. as a neutralizing agent were blended. After stirring and mixing with a Henschel mixer for 1 minute, extrude with an NVC φ50 mm single-screw extruder manufactured by Nakatani Machinery Co., Ltd. at a cylinder temperature of 230 ° C., cool the strands in water, cut with a pelletizer, and pelletize the polypropylene resin composition. I got something.

The polypropylene composition thus produced is subjected to conditions of a cylinder set temperature of 230 ° C., a die set temperature of 250 ° C., and a screw rotation speed of 50 rpm using a 25 mm φ3 type 3-layer downward T-die molding machine manufactured by Thermoplastics Industry Co., Ltd. It was molded into a film with. The obtained film was evaluated by the method described later.

[Example 2]
The 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 of the first polymerization reactor was 0.13 mol%, the hydrogen concentration of the second polymerization reactor was 1.43 mol%, the polymerization pressure was adjusted at a polymerization temperature of 70 ° C., and the respective ratios were adjusted. The residence time distribution was adjusted so that The obtained propylene homopolymer was introduced into a gas phase polymerization reactor to polymerize a copolymer (propylene / ethylene copolymer) in the same manner as in Example 1.
When the molecular weight distribution is widened by multi-stage polymerization as described above, there is generally a 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 is widened. , The portion where the high molecular weight component and the low molecular weight component overlap is increased, and the dispersion failure does not become 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 the ethylene concentration of the first-stage reactor were changed to 0.48 mol% and 0.56 mol%, respectively. A film was produced from the polypropylene resin composition in the same manner as in Example 1 and evaluated.

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

[Example 5]
The polypropylene resin composition for this example was the same as in Example 4 except that the residence time distributions of the first and second stages were adjusted so that the amount of the copolymer component was 19 parts by weight out of 100 parts by weight of the polymer. Manufactured a thing. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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) of the second-stage reactor was set to a 0.28 molar ratio. A film was produced from the polypropylene resin composition in the same manner as in Example 1 and evaluated.

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

[Example 8]
Polypropylene resin composition for this example as in Example 1 except that the hydrogen concentration of the first-stage reactor was 0.47 mol% and the hydrogen concentration of the second-stage reactor was 0.83 mol%. Manufactured a thing. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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 of the first-stage reactor was 0.27 mol%. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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 of the first-stage reactor was 0.56 mol%. A film was produced from the polypropylene resin composition in the same manner as in Example 1 and evaluated.

[Example 11]
Using the polypropylene resin composition of Example 1, a multilayer film of 2 types and 3 layers having a recycled material in the process as an intermediate layer was obtained. The production conditions were the same as in Example 1 except for multi-layer extrusion molding.

[Comparative Example 1]
The 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 diisobutylphthalate 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 solid catalyst, triethylaluminium (TEAL) as the organoaluminum compound, and dicyclopentyldimethoxysilane (DCPMS) as the external electron donor compound, the weight ratio of TEAL to the solid catalyst was 20, and the weight ratio of TEAL / DCPMS was 20. The contact was carried out at 12 ° C. for 24 minutes in an amount such that the value was 10. The obtained catalyst system was prepolymerized by holding it in a suspended state in liquid propylene at 20 ° C. for 5 minutes. The obtained prepolymer is introduced into the first-stage 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-stage polymerization reactor. A copolymer was produced. During the polymerization, the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier.
The ratio of the polymerization temperature to the reactant was that the polymerization temperature and hydrogen concentration were 70 ° C. and 0.49 mol% in the first stage reactor, respectively, and the polymerization temperature and hydrogen concentration in the second stage reactor, C2 / ( C2 + C3) had a ratio of 80 ° C., 1.13 mol%, and 0.21 mol, respectively. Further, the residence time distributions of the first and second stages were adjusted so that the amount of the copolymer component was 24 parts by weight out of 100 parts by weight of the polymer.

[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 the ethylene concentration of the first-stage reactor were changed to 0.64 mol% and 0.95 mol%, respectively. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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 out of 100 parts by weight of the polymer. Manufactured a thing. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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) of the second-stage reactor was set to a 0.05 molar ratio. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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) of the second-stage reactor was set to a 0.41 molar ratio. A film was produced from the polypropylene resin composition in the same manner as in Example 1 and evaluated.

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

[Comparative Example 7]
Polypropylene resin composition for this example as in Example 1 except that the hydrogen concentration of the first-stage reactor was 0.82 mol% and the hydrogen concentration of the second-stage reactor was 0.51 mol%. Manufactured a thing. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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 of the first-stage reactor was 0.11 mol%. A film was produced from the polypropylene resin composition in the same manner as in Example 1 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 of the first-stage reactor was 1.26 mol%. A film was produced from the polypropylene resin composition in the same manner as in Example 1 and evaluated.
The results are shown in Table 1.

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

[Collection of xylene-soluble components]
2.5 g of polymer was placed in a flask containing 250 mL of o-xylene (solvent) and stirred for 30 minutes at 135 ° C. using a hot plate and a reflux device while purging nitrogen to completely dissolve the composition. After that, the mixture was cooled at 25 ° C. for 1 hour. The resulting solution was filtered using filter paper. 100 mL of the filtered filtrate was collected, transferred to an aluminum cup or the like, evaporated to dryness 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 the polymer dissolved in xylene at room temperature was determined. The weight% of the polymer dissolved in xylene with respect to all the polymers was calculated and used as the amount of xylene-soluble matter at 25 ° C.
[XSIV]
Using the above xylene-soluble component as a sample, the ultimate viscosity was measured in tetrahydronaphthalene at 135 ° C. using an Ubbelohde viscometer (SS-780-H1, manufactured by Shibayama Kagaku Kikai Seisakusho).

[Collection of xylene insoluble matter]
When the xylene-soluble component was filtered as described above, acetone was added to the residue (mixture of xylene-insoluble component and solvent) remaining on the filter paper and filtered, and then the unfiltered component was vacuumed at 80 ° C. It was evaporated to dryness in a drying oven to obtain xylene insoluble matter (XI).
[Mw and Mw / Mn of xylene insoluble matter]
Using the above xylene insoluble component as a sample, the weight average molecular weight (Mw) and the 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) and UT-807 (1) manufactured by Showa Denko KK as columns. One) and UT-806M (two) were connected in series, and a differential refractometer was used as a detector. The same solvent as the mobile phase was used as the solvent for the xylene-insoluble sample solution, and the sample was dissolved at a sample concentration of 1 mg / mL for 2 hours while shaking at a temperature of 150 ° C. to prepare a measurement sample. 500 μL of the sample solution thus obtained was injected into the column, and measurements were taken at a flow rate of 1.0 mL / min, a temperature of 145 ° C., and a data acquisition interval of 1 second. A polystyrene standard sample having a molecular weight of 580 to 7.45 million (shodex STANDARD, manufactured by Showa Denko KK) was used for column calibration, and the column was calibrated by a cubic approximation. The coefficients of Mark-Hokins are K = 1.21 × 10 ^-4 , α = 0.707 for polystyrene standard samples, and K = 1.37 × 10 ^-4 , α = 0. For polypropylene-based polymers. 75 was used.

[Extruder load]
In film molding, the pressure 5 minutes after the start of molding was measured.
[Thickness and thinness accuracy]
A film thickness of 30 μm was formed under the following conditions.
Extruder: Thermo Plastics Industry Co., Ltd. 25 mm φ3 type 3 layer downward T-die molding machine Set temperature: Cylinder 230 ° C, die 250 ° C
Pick-up machine Chill roll temperature: 30 ° C
Pick-up machine Pick-up speed: 10 m / min
Screw rotation speed: 30 rpm
With an air knife The standard deviation was calculated from the thickness of the central 200 mm width of the film formed under the above conditions measured at 10 points at equal intervals in the TD direction. The standard deviation is divided by the average thickness and shown as a percentage.
This measurement was carried out at two locations with an interval of 1 m or more in the MD direction, the standard deviation was calculated, divided by the average thickness, and shown as a percentage.
Percentage values obtained at these three locations were averaged to obtain thickness and thinness accuracy.

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

[Haze]
According to JIS K 7136, the measurement was performed at n = 3 using a haze measuring device (HM-150 type manufactured by Murakami Color Technology Research Institute Co., Ltd.).
[Fish eye]
It was measured using a fisheye counter SCANTEC 7000 of Nagase & Co., Ltd. The categories are as follows.
Small fish eye: Maximum diameter 0.1 mm or more and less than 0.2 mm Medium fish eye: Maximum diameter 0.2 to 0.5 mm

[Tension modulus]
The tensile elastic modulus in the film MD direction was measured using the AUTOcom AC-C series of manual tensile testers of TSE Co., Ltd. in accordance with JIS K7127. The conditions are as follows.
Test speed: 5 mm / min
Distance between grippers: 100 mm
Specimen type 2 (width 10 mm)
Number of tests: n = 5 (mean value is the tensile elastic modulus)

[Impact strength]
It was evaluated using a film impact tester with a constant temperature bath manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with ASTM D3420. The conditions are as follows.
Capacity: 3.0J
Pendulum tip shape: 1 inch (R; 12.7 mm, diameter; 25.4 mm) Hemisphere In-tank atmosphere: 0 ° C (± 0.4 ° C)
Number of tests: n = 16 (mean value was used as impact strength)

Claims (8)

The component (1) contains 85 to 55 parts by weight of a propylene (co) polymer containing 0 to 3.5 % by weight of ethylene-derived units, and the component (2) contains 25 to 35% by weight of ethylene-derived units. A polypropylene composition containing 15 to 45 parts by weight of a propylene-ethylene copolymer.
The following requirements:
1) Mw / Mn of the xylene-insoluble component of the composition measured by GPC is 7 or more. 2) The ultimate viscosity of the xylene-soluble component 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 minutes. 4) A polypropylene composition satisfying that the melt tension index of the composition is 1.5 or more. The polypropylene composition according to claim 1, wherein the xylene-insoluble Mw / Mn is 9 or more. The polypropylene composition according to claim 1 or 2 , wherein the xylene-soluble component has an ultimate viscosity of 2.4 to 3.8 dl / g. The polypropylene composition according to any one of claims 1 to 3 , wherein the melt flow rate is 4 to 10 g / 10 minutes. The polypropylene composition according to any one of claims 1 to 4 , which contains 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 an electron donor compound selected from magnesium, titanium, halogen, and succinate compounds as an essential component;
The polypropylene composition according to any one of claims 1 to 5 , obtained by polymerizing propylene and ethylene using a catalyst containing (B) an organoaluminum compound and (C) an external electron donor compound. A film obtained by molding the polypropylene composition according to any one of claims 1 to 6. A multilayer film including the film according to claim 7.