JP2016089012A - Method of producing film or sheet containing polypropylene composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet obtained by a polypropylene composition and excellent in transparency and cold impact resistance.SOLUTION: A method of producing a sheet or a film is provided that comprises: (I) a step of preparing a master batch composition which contains as a component (1), 75 to 86 wt.% of propylene (co)polymer containing 0 to 3 wt.% of ethylene or one or more kind of C4 to C10-α-olefin, contains as a component (2), 14 to 25 wt.% of ethylene-propylene copolymer having 65 to 85 wt.% of propylene content and contains as a component (3), a nucleus agent, and in which a melt flow rate (230°C, load:21.18 N) is 1.5 g/10 min or more and less than 5.5 g/10 min and an XSIV (intrinsic viscosity of xylene soluble part) is 1.0 to 2.2 dl/g; (II) a step of mixing the master batch composition with a composition containing as a component (4), a propylene (co)polymer containing 0 to 3 wt.% of ethylene or one or more kind of C4 to C10-α-olefin thereby preparing a polypropylene composition containing 10 to 40 wt.% of the master batch composition and 60 to 90 wt.% of the component (4); and (III) a step of biaxially stretching the polypropylene composition.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a film or sheet comprising a polypropylene composition.

  Polypropylene is useful as a food container because it has excellent physical properties and excellent hygiene. For example, it has been proposed to produce a food container by mixing a nucleating agent with polypropylene to obtain a sheet and vacuum forming the sheet (Patent Documents 1 to 5). However, the polypropylene container thus obtained has a problem that the impact resistance is lowered when it is used at a low temperature. In order to improve this, for example, it has been proposed to add an ethylene-based copolymer to polypropylene (Patent Document 6).

JP 2000-334823 A JP 59-171625 A JP 2006-193539 A JP-A-7-286007 JP-A-10-292074 Special table 2011-513528

  The inventors preliminarily studied the technology described in the patent literature, and as a result of the addition of the ethylene copolymer, the transparency is lowered. Therefore, the conventional polypropylene sheet has satisfactory transparency and cold shock resistance. I got the knowledge that I did not. In view of such circumstances, an object of the present invention is to provide a sheet obtained from a polypropylene composition, which is excellent in transparency and cold shock resistance.

The inventors have found that the above problems can be solved by using a specific polypropylene composition, and have completed the present invention. That is, the said subject is solved by the following this invention.
[1] (I) 75 to 86% by weight of propylene (co) polymer containing 0 to 3% by weight of ethylene or one or more C4 to C10-α-olefins as component (1);
14-25 wt% of an ethylene-propylene copolymer having a propylene content of 65-85 wt% as component (2); and a nucleating agent as component (3),
The melt flow rate (230 ° C., load 21.18 N) is 1.5 g / 10 minutes or more and less than 5.5 g / 10 minutes,
Preparing a master batch composition having an XSIV (intrinsic viscosity of xylene solubles) of 1.0 to 2.2 dl / g;
(II) Mixing the masterbatch composition and a composition containing a propylene (co) polymer containing 0 to 3% by weight of ethylene or one or more C4 to C10-α-olefins as component (4). Preparing a polypropylene composition containing 10 to 40% by weight of the masterbatch composition and 60 to 90% by weight of component (4);
(III) including a step of biaxially stretching the polypropylene composition,
A method for producing a sheet or film.
[2] The production method according to [1], further including a step of cooling while maintaining the surface state of the compact after biaxial stretching.
[3] The production method according to [1] or [2], wherein 0.05 to 1.0 part by weight of the nucleating agent is contained with respect to a total of 100 parts by weight of the components (1) and (2).
[4] In the step (I), propylene and ethylene or C4 to C10-α-olefin as raw materials of the component (1) and ethylene and propylene as raw materials of the component (2)
(A) a solid catalyst containing magnesium, titanium, halogen, and a succinate compound as an electron donor compound,
(B) The manufacturing method in any one of [1]-[3] including the process superposed | polymerized using the catalyst containing an organoaluminum compound and (C) external electron donor compound.
[5] The production method according to [4], wherein the polymerization step is performed using two or more reactors.
[6] A molded article having a layer made of a film or sheet produced by the production method according to any one of [1] to [5].
[7] A secondary molded body obtained by molding the molded body according to [6].

  In the present invention, a sheet is a member having a thickness of 200 μm or more, and a film is a member having a thickness of less than 200 μm. The sheet of the present invention is obtained by biaxially stretching a specific polypropylene composition at a specific temperature. Hereinafter, the present invention will be described in detail. In the present invention, “X to Y” includes values at both ends, that is, X and Y.

  The production method of the present invention includes a step I of preparing a masterbatch composition containing components (1) to (3), a step II of preparing a polypropylene composition by mixing the masterbatch composition and component (4), And Step III of biaxially stretching the polypropylene composition. Hereinafter, each step will be described.

1. Process I
In this step, a master batch composition is prepared. The masterbatch composition is 75 to 86% by weight of propylene (co) polymer containing 0 to 3% by weight of ethylene as component (1) or one or more C4 to C10-α-olefins, and propylene as component (2). The ethylene-propylene copolymer having a content of 65 to 85% by weight contains 14 to 25% by weight, and a nucleating agent is contained as component (3).

(1) Propylene (co) polymer (component 1)
The propylene (co) polymer is a propylene homopolymer or a copolymer of propylene and a copolymer of propylene and a C4 to C10-α-olefin (hereinafter also referred to as “comonomer”) of more than 0% by weight and 3% by weight or less. . The copolymer of propylene containing 1.0% by weight of ethylene 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 comonomer content is 3% by weight or less, preferably 2.8% by weight or less, and more preferably 2.5% by weight or less. When the comonomer content exceeds the upper limit value, the rigidity and the cutting property of the sheet at the time of stretching process are lowered. In addition, when the comonomer content is 3.5% by weight or more, it is difficult to produce a polymer used in the master batch composition of the present invention. The lower limit when using a comonomer is not limited, but is preferably 0.5% by weight or more, and more preferably 1.0% by weight or more. As the comonomer, ethylene or a C4-C6-α-olefin is preferable from the viewpoint of availability, and ethylene is more preferable.

(2) Propylene-ethylene copolymer (component 2)
The propylene-ethylene copolymer used in the present invention has a propylene content of 65 to 85% by weight. When the propylene content exceeds the upper limit value, impact resistance decreases, and when it is less than the lower limit value, transparency decreases. From this viewpoint, the upper limit of the propylene content is preferably 80% by weight or less, and more preferably 77% by weight or less. The lower limit of the propylene content is preferably 67% by weight or more, and more preferably 70% by weight or more.

(3) Nucleating agent (component 3)
The nucleating agent used in the present invention is an additive used for increasing the transparency by controlling the size of the crystal component in the resin to be small. The nucleating agent is not particularly limited, and those commonly used in the field may be used, but nonitol nucleating agent, sorbitol nucleating agent, phosphate ester nucleating agent, triaminobenzene derivative nucleating agent, metal carboxylate It is preferably selected from a salt nucleating agent and a xylitol nucleating agent. Examples of nonitol nucleating agents include 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol.

  Examples of the xylitol-based nucleating agent include bis-1,3: 2,4- (5 ′, 6 ′, 7 ′, 8′-tetrahydro-2-naphthaldehydebenzylidene) 1-allylxylitol, bis-1,3: 2,4- (3 ′, 4′-dimethylbenzylidene) 1-propylxylitol is exemplified.

  Examples of sorbitol nucleating agents include bis-1,3: 2,4- (4′-ethylbenzylidene) 1-allylsorbitol, bis-1,3: 2,4- (3′-methyl-4′-fluoro, -Benzylidene) 1-propylsorbitol, bis-1,3: 2,4- (3 ', 4'-dimethylbenzylidene) 1'-methyl-2'-propenylsorbitol, bis-1,3,2,4-di Benzylidene 2 ′, 3′-dibromopropylsorbitol, bis-1,3,2,4-dibenzylidene 2′-bromo-3′-hydroxypropylsorbitol, bis-1,3: 2,4- (3′-bromo -4'-ethylbenzylidene) -1-allylsorbitol, mono-2,4- (3'-bromo-4'-ethylbenzylidene) -1-allylsorbitol, bis-1,3: 2,4- (4 -Ethylbenzylidene) 1-allylsorbitol, bis-1,3: 2,4- (3 ', 4'-dimethylbenzylidene) 1-methylsorbitol, bis (p-methylbenzylidene) sorbitol, 1,3: 2,4 -Bis-o- (4-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-o- (benzylidene) -D-sorbitol, 1,3: 2,4-bis-o- (3 , 4-dimethylbenzylidene) -D-sorbitol and the like.

  Among these, commercially available nucleating agents include, for example, Millad NX8000, NX8000K containing 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol in the nonitol system, NX8000J (manufactured by Milliken Japan Co., Ltd.), RiKAFAST R-1 (manufactured by Nippon Nippon Chemical Co., Ltd.), Millad 3988 (manufactured by Milliken Japan Co., Ltd.), gel all E-200 (manufactured by Nippon Nippon Chemical Co., Ltd.), gel all MD (made by Shin Nippon Rika Co., Ltd.) etc. are mentioned.

  As phosphate nucleating agent, aluminum-bis (4,4 ′, 6,6′-tetra-tert-butyl-2,2′-methylenediphenyl-phosphate) -hydroxide, phosphoric acid-2,2′- And methylene bis (4,6-di-tert-butylphenyl) lithium salt compound. Examples of commercially available phosphate ester nucleating agents include ADK STAB NA-21 (manufactured by ADEKA Corporation) and ADK STAB NA-71 (manufactured by ADEKA Corporation).

  Examples of the triaminobenzene derivative nucleating agent include 1,3,5-tris (2,2-dimethylpropanamide) benzene. As a commercially available triaminobenzene derivative nucleating agent, IRGACEAR XT386 (made by BASF Japan Ltd.) etc. are mentioned, for example.

  Examples of the carboxylic acid metal salt nucleating agent include 1,2-cyclohexanedicarboxylic acid calcium salt. Examples of commercially available carboxylic acid metal salt nucleating agents include Hyperform HPN-20E (manufactured by Milliken Japan Co., Ltd.). In particular, in order to maintain transparency after secondary molding including heating, it is preferable to use a nonitol nucleating agent or a sorbitol nucleating agent. Here, secondary molding means compression molding or vacuum molding, etc., to a film or sheet that is a primary molded product, and processing into a molded product with a different shape, or by fusing the film or sheet together. The obtained molded body is called a secondary molded body.

(4) Amount of each component The ratio of the components (1) and (2) is (1) :( 2) = 75 to 86% by weight: 14 to 25% by weight. If the amount of the component (2) exceeds this upper limit, the rigidity of the obtained sheet or the like is lowered, and if it is 30% by weight or more, production becomes difficult. Moreover, the cold impact resistance of the sheet | seat etc. which are obtained as it is less than a minimum falls. From this viewpoint, the ratio is preferably 80 to 86% by weight: 14 to 20% by weight.

  The amount of the nucleating agent is preferably 0.05 to 1.0 part by weight based on 100 parts by weight of the total of components (1) and (2). If the amount of the nucleating agent exceeds this upper limit, the cost increases, and if it is less than this lower limit, the transparency of the obtained sheet or the like may be lowered. From this viewpoint, the blending ratio of the nucleating agent is more preferably 0.1 to 1.0, still more preferably 0.2 to 0.7 weight, with respect to 100 parts by weight of the total of the components (1) and (2). Part.

(5) Other components Further, the masterbatch composition includes olefin copolymers other than components (1) and (2), antioxidants, hydrochloric acid absorbents, heat stabilizers, light stabilizers, ultraviolet absorbers, Such as internal lubricants, external lubricants, antistatic agents, flame retardants, dispersants, copper damage inhibitors, neutralizers, plasticizers, foam inhibitors, crosslinkers, peroxides, oil extended and other organic and inorganic pigments You may add the usual additive normally used for an olefin polymer. The addition amount of each additive may be a known amount.

  In particular, it is preferable to add an olefin copolymer other than the components (1) and (2) because the impact strength is improved. Examples of the olefin copolymer include a styrene-hydrogenated butadiene block copolymer and a polypropylene thermoplastic elastomer. The addition amount is preferably 1 to 6 parts by weight with respect to 100 parts by weight of the total of components (1) and (2).

(6) Characteristics 1) 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 master batch composition is 1.5 g / 10 min or more and less than 5.5 g / 10 min. . If the value of the melt flow rate exceeds this upper limit value, the drawdown resistance at the time of processing decreases, and if it is less than the lower limit value, the torque at the time of processing increases. is there. From this viewpoint, the melt flow rate is preferably 2 to 5 g / 10 minutes.

2) XSIV
XSIV is the intrinsic viscosity of the xylene-soluble component of the polypropylene composition, and is also an index 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 1.0 to 2.2 dl / g. When XSIV exceeds the upper limit, transparency of the obtained sheet or the like is lowered. If XSIV is less than the lower limit, production becomes difficult.

(7) Production method The master batch composition may be produced by any method, but the raw material monomer of component (1) and the raw material monomer of component (2) are converted into (A) magnesium, titanium, halogen, and electron donor. It is preferable to obtain by a method including a step of polymerizing using a solid catalyst containing a succinate compound as a compound, (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, the electron donor compound is preferably 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 the same 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 to} 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, for example 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, diisobutyltrimethylsilyl 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, a cyclic succinate compound as disclosed in, for example, International Publication No. 2009/069483 can also be suitably 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.

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 It is preferable to polymerize the raw material monomer of component (1) and the raw material monomer of component (2) using two or more reactors. The polymerization may be carried out in liquid phase, gas phase or liquid-gas phase. 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.

  The addition of the nucleating agent can be performed, for example, by stirring the obtained polymer and the nucleating agent together with an antioxidant with a Henschel mixer, Brabender, etc., and then melt blending at 180 ° C. to 280 ° C. using an extruder. it can. The addition of the nucleating agent and the antioxidant may be performed using an extruder connected to a polymerization apparatus after undergoing polymerization, residual monomer removal, and a drying step.

  In particular, in the present invention, the polymerization powder and the nucleating agent may be melt-kneaded and mixed. Polymerized powder is a powdered polymer obtained after polymerization, after removing residual monomers and passing through a drying process. The polymer powder has an average particle size (by light scattering method) of 50 to 5,000 μm. By mixing the polymerization powder having a large surface area and the nucleating agent, the nucleating agent is dispersed well, and the transparency of the obtained sheet is further improved. In the present invention, a so-called nucleating agent master batch obtained by melting and kneading a high concentration nucleating agent with polypropylene may be mixed with the polypropylene resin during sheet molding.

  When the master batch composition contains the olefin copolymer as another component, the olefin copolymer and the polymer powder may be melt-kneaded and mixed.

2. Step II
In this step, the masterbatch composition and component (4), 0-3 wt% ethylene or a composition containing a propylene (co) polymer containing one or more C4-C10-α-olefins are mixed. Then, a polypropylene composition in which the ratio of both is 10 to 40% by weight: 60 to 90% by weight is prepared.

(1) Mixing method Although the method to mix is not limited, The method using kneading machines, such as an extruder, is preferable. The kneading conditions are not particularly limited, but the cylinder temperature is preferably 180 to 250 ° C. The polypropylene composition thus obtained may be in the form of a pellet, but may be obtained as a preliminary sheet by forming a T-die or the like at the tip of the extruder and forming it into a sheet shape. The mixing ratio is selected so that the ratio of the masterbatch composition to the component (4) in the resulting polypropylene composition is 10 to 40% by weight: 60 to 90% by weight. When the amount of the master batch composition exceeds the upper limit, the rigidity of the final film or sheet is lowered, and when it is less than the lower limit, the cold shock resistance of the obtained film or sheet is lowered. In this respect, the ratio is more preferably 20 to 40% by weight: 60 to 80% by weight.

(2) Composition containing propylene (co) polymer (component 4)
Component (4) used in this step is a composition containing 0 to 3% by weight of ethylene or a propylene (co) polymer containing one or more C4 to C10-α-olefins. The composition and properties of the propylene (co) polymer may be the same as or different from those of component (1). However, the comonomer composition of component (4) is preferably 1 to 3 wt% ethylene. Furthermore, the melt flow rate (230 ° C., load 21.18 N) of component (4) is preferably 1.0 to 10 g / 10 min. Examples of the component (4) other than the propylene (co) polymer include known additives such as a nucleating agent and an antioxidant. As the nucleating agent, those already described can be used, and the amount is preferably 0.05 to 1.0% by weight in the component (4). As the antioxidant or the like, a known one can be used, and the amount thereof may be within a known range. Component (4) is preferably produced by polymerizing a raw material monomer using the catalyst and melt-kneading the obtained (co) polymer together with a nucleating agent and an antioxidant.

3. Step III
(1) Biaxial stretching In this step, the polypropylene composition is biaxially stretched. As described above, it is preferable to prepare a preliminary sheet from the polypropylene composition and stretch it in the width direction and the flow direction of the preliminary sheet. Stretching in the width direction and the flow direction may be performed simultaneously, or may be performed with a time difference as described later. Usually, after a polypropylene composition is first melted with an extruder, it is extruded into a sheet form from a T-die to prepare a preliminary sheet, which is cooled and solidified with a cooling roll. Next, the obtained sheet is stretched in the machine direction through a number of heating rolls (longitudinal stretching). Subsequently, the film is stretched in the transverse direction through a heating furnace composed of a preheating part, a stretching part and a heat treatment part (lateral stretching). In compression molding, vacuum molding, or the like, which is also used as a secondary molding technique, a preliminary sheet obtained in advance is biaxially stretched to be shaped to a desired thickness or shape. Alternatively, a preliminary sheet in which a layer of the polypropylene composition and other layers are laminated may be prepared and biaxially stretched as described above. Further, as in calendar molding or inflation molding, the polypropylene composition may be biaxially stretched at the stage where the molten resin extruded from the die is solidified after being melted by an extruder. Layers other than the polypropylene composition are not particularly limited, but a propylene homopolymer, a random copolymer, a block copolymer, or a composition containing a resin other than polypropylene based on any of these polymers. It may be a layer consisting of

  In the present invention, the polypropylene composition is preferably biaxially stretched at a specific temperature Ts. In the case where the biaxial stretching process such as the longitudinal stretching and the lateral stretching is composed of a plurality of stages, it is preferable to stretch with Ts at least in the last stage. The temperature Ts is determined by a differential scanning calorimeter (DSC). Specifically, Ts is determined as follows by second-scanning the composition using DSC to obtain a melting point derived from component (1), (2) or (4).

  The second scan means that a polypropylene composition is crystallized after being melted using DSC, and is subjected to thermal analysis using DSC after being kept at room temperature for 5 minutes. Specifically, 1) the polypropylene composition was heated to the melting temperature (230 ° C.), held at that temperature for 5 minutes, cooled to 30 ° C. at a temperature lowering rate of 10 ° C./min, held for 5 minutes, and then 2 ) Heat analysis is performed up to 230 ° C. at a temperature increase rate of 10 ° C./min.

  In the polypropylene composition of the present invention, a melting point peak derived from the component (1), (2), or (4) is obtained by the thermal analysis. When the peak top temperature of the melting point on the highest temperature side derived from the component (1), (2), or (4) in the second scan in DSC of the polypropylene composition is Tm (° C.), Ts is −30 ≦ Ts A range of −Tm ≦ 10 is preferable. When component (1), (2) or (4), or all of these have a plurality of peaks, the peak top temperature on the highest temperature side is Tm.

  Whether the temperature range of Ts is a state in which most of the crystals derived from the component (1), (2), or (4) of the polypropylene composition are melted and the sheet shape can be maintained. , Partially melted. Therefore, biaxial stretching becomes difficult when the temperature during biaxial stretching exceeds the upper limit or less than the lower limit. In the case of a composition comprising a general propylene polymer and an ethylene-α-olefin copolymer, the transparency of the resulting sheet or the like is usually lowered when Ts is lower than Tm. The deterioration of transparency of the finally obtained sheet or the like is caused by the presence of many unmelted components containing high melting point crystals in any of the components (1), (2), or (4) during stretching. This is probably because the surface is uneven as a result of the melted component being stretched in a depressed state. In the present invention, as the ethylene-α-olefin copolymer, an ethylene-propylene polymer having a high propylene content and a low molecular weight (high compatibility with the propylene polymer) as in (2) is used. As a result of the fine dispersion of (2) in the propylene polymer of 1) and (4) and the influence of the depression of the melting component being reduced, excellent transparency is achieved even when the polypropylene composition is stretched at Ts lower than Tm. It is thought that a sheet or the like can be obtained. However, it is not limited to this theory. The lower limit of Ts-Tm is preferably −30 ° C. or higher, more preferably −25 ° C. or higher, and further preferably −20 ° C. or higher. Moreover, although the upper limit of Ts-Tm is 10 degrees C or less, 9 degrees C or less is more preferable.

  In particular, the polypropylene composition of the present invention is obtained by mixing a masterbatch composition with component (4). For this reason, it is thought that the dispersibility of the component (2) described above is further improved, and the transparency of the resulting film or sheet is further improved. In addition to this, by using the master batch composition, there is an advantage that various characteristics can be achieved without preparing different resin grades. For example, by changing the masterbatch ratio, the masterbatch composition may be reduced if the transparency is more important, and the masterbatch composition may be added more if the cold impact resistance is more important. Can be prepared.

4). Cooling step The molded body obtained by biaxial stretching in the above temperature range is stretched with component (2) finely dispersed in components (1) and (4), resulting in a smooth surface and high transparency. Have In this step, it is preferable to maintain the smooth surface state while cooling to maintain the transparency of the sheet or the like. Since crystals with a large size cause surface roughness, it is preferable to cool to a temperature at which crystals produced during cooling after biaxial stretching do not grow in order to maintain smoothness. Although the specific value is not limited, the cooling temperature is preferably 80 ° C. or lower, and more preferably 50 ° C. or lower. The cooling method is not particularly limited, and for example, a molded body obtained by biaxial stretching can be water-cooled or air-cooled.

5). The sheet | seat or film of this invention The sheet | seat or film obtained by this invention can be used for various uses. For example, a sheet or the like can be formed into a container by vacuum forming or the like, and a sheet or the like can be formed into a desired shape by punching. In particular, the sheet of the present invention is excellent in transparency and cold shock resistance, and has little stringing at the time of punching and excellent cutting properties, so that it is a container for ice and ice confectionery, food containers such as cooling drinks and packaging materials. Useful as.

  Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.

Analysis and evaluation were performed as follows.
(1) MFR
According to JIS K 7210, the measurement was performed under conditions of a temperature of 230 ° C. and a load of 21.18 N.
(2) XSIV
2.5 g of sample was placed in a flask containing 250 ml of o-xylene (solvent) and stirred for 30 minutes at 135 ° C. while purging with nitrogen using a hot plate and a reflux apparatus to completely dissolve the sample. . The solution was then cooled at 25 ° C. for 1 hour. Filter the resulting solution using filter paper, collect 100 ml of the filtrate, transfer to an aluminum cup, etc., evaporate to dryness at 150 ° C. while purging with nitrogen, and allow to stand at room temperature for 30 minutes to dissolve xylene. Got the minute. Using an Ubbelohde viscometer, the intrinsic viscosity was measured in 135 ° C. tetrahydronaphthalene of the xylene solubles to obtain XSIV (dl / g).

(3) Stretchability A case where no problem such as breakage occurred during stretching was evaluated as good, and a case where a problem occurred was evaluated as poor.
(4) Transparency Based on ISO 14782, the haze measurement of the sheet | seat obtained as mentioned later using the Murakami Color Research Laboratory make and HM-150 was performed, and transparency was evaluated. Table 1 shows the haze values obtained.

(5) Cold impact resistance Evaluation was made by dart impact strength at -20 ° C. The dart impact strength is a dart having a hemispherical head with a diameter of 50 mm specified in JIS K7124-1. The dart impact strength is dropped from a height of 1.50 m. The fracture energy was calculated as the warhead mass when% was destroyed.

(6) Polymer or ethylene content of each component of polymer JNM LA-400 ( ^13C resonance) manufactured by JEOL Ltd. for a sample dissolved in 1,2,4-trichlorobenzene / deuterated benzene mixed solvent The frequency was calculated from the value measured by the ¹³ C-NMR method.

(7) Differential scanning calorimetry (DSC)
Using a Perkin Elmer diamond DSC, the second scan defined above was performed and measured.

(8) Flexural modulus Measured according to JIS K7203. A test piece of 12.7 mm (width) × 4.0 mm (thickness) × 127 mm (length) was used. The test conditions were a temperature of 23 ° C., a span interval of 60 mm, and a speed of 2.0 mm / min.

(9) Productivity Judgment was made assuming continuous production of the masterbatch composition by an actual plant. Specifically, the evaluation was made as follows from the viewpoint of whether the storage tank or piping would be blocked due to stickiness or mutual adhesion of the polymer powder.
Good: When the above defects do not occur and continuous production is possible for a long time. Yes: When the above defects do not occur and continuous production is possible for a certain amount of time.

(10) Cutting property Judgment was made on the assumption of a production process in which a sheet or an original film is cut while being biaxially stretched in a continuous process. Specifically, immediately after taking out a biaxially stretched sheet or film at 140 ° C. from the biaxial stretching device, when the surface temperature of the sheet or film reaches 120 ° C., it is cut with scissors to see if it can be cut well. Evaluation was performed as follows.
Good: When it can be cut well and continuous production is possible for a long time Yes: When it can be cut well and continuous production is possible for a certain amount of time Not possible: When it is difficult to make a good cut and continuous production is difficult

[Example 1]
1. Preparation of composition (1) Solid catalyst Examples of JP2011-500907 (International Publication 2009/050045) except that the temperature of the solid catalyst used for polymerization was changed from 100 ° C to 110 ° C first. And prepared according to the description. Specifically, it was prepared as follows.

To a 500 ml four-necked 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 · 2.8C ₂ H ₅ OH (produced by operating at 3000 rpm instead of 10,000 rpm according to the method described in Example 2 of US Pat. No. 4,399,054) ), And 9.1 mmol diethyl-2,3-diisopropyl succinate. The temperature was raised to 110 ° C. and held for 120 minutes. Next, stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was siphoned off. Next, 250 ml of fresh TiCl ₄ was added, the mixture was allowed to react at 120 ° C. for 60 minutes, and the supernatant was siphoned off twice. The solid was then washed 6 times with anhydrous hexane (6 × 100 ml) at 60 ° C.

(2) Masterbatch composition 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 11, TEAL / DCPMS was contacted at 12 ° C. for 24 minutes in such an amount that the weight ratio was 10. 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 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. This corresponds to mixing (polymerization blend) of the ethylene-propylene copolymer and the propylene homopolymer from the first stage. During the polymerization, the temperature and pressure were maintained at values adjusted in each stage, and hydrogen was used as a molecular weight modifier.

The ratio of the polymerization temperature to the reactants is as follows: polymerization temperature and hydrogen concentration in the first stage reactor are 75 ° C. and 0.10 mol%, respectively, polymerization temperature, H2 / C2, C2 / C in the second stage reactor. (C2 + C3) were 80 ° C., 0.47 molar ratio, and 0.20 molar ratio, respectively. The polymer obtained by the polymerization blend is a composition comprising the following components (1) and (2).
Component (1): Propylene homopolymer 82% by weight
Component (2): ethylene-propylene copolymer containing 75% by weight of propylene 18% by weight

  Further, 100 parts by weight of the polymer powder, 0.5 parts by weight of Millad NX8000J (Nonitol, manufactured by Milliken Japan) as a nucleating agent, 0.2 parts by weight of an antioxidant (B225 manufactured by BASF), neutralization 0.05 parts by mass of an agent (calcium stearate manufactured by Tamnan Chemical Co., Ltd.) was added and mixed by stirring for 1 minute with a Henschel mixer. This mixture was extruded at a cylinder temperature of 230 ° C. using an NVC φ50 mm single screw extruder manufactured by Nakatani Machinery Co., Ltd., and the strand was cooled in water and then cut with a pelletizer to obtain a pellet-shaped master batch composition.

(3) Component (4)
The solid catalyst used for the polymerization was prepared by the method described in Example 1 of EP 6749991. The solid catalyst is obtained by supporting Ti and diisobutyl phthalate as an internal donor on MgCl ₂ by the method described in the above patent publication. The solid catalyst and triethylaluminum (TEAL) and diisopropyldimethoxysilane (DIPMS) are added in an amount such that the weight ratio of TEAL to the solid catalyst is 11 and the weight ratio of TEAL / DIPMS is 3.2 at −5 ° C. Contacted for 5 minutes. The resulting catalyst system was prepolymerized by holding it in liquid propylene in suspension for 5 minutes at 20 ° C.

  After the obtained prepolymer is introduced into the polymerization reactor, hydrogen, propylene, and ethylene are fed to set the polymerization temperature, hydrogen concentration, and ethylene concentration to 75 ° C., 0.12 mol%, and 0.45 mol%, respectively. By adjusting the pressure, a propylene-ethylene copolymer containing 1.7% by weight of ethylene was produced. Using the polymer powder, a component (4) was obtained in the same manner as in the master batch composition. Component (4) was a composition obtained by adding a nucleating agent to the polymer powder, and the MFR was 4.9 g / 10 min.

(4) Polypropylene composition 25 parts by weight of the masterbatch composition and 75 parts by weight of the component (4) were extruded at a cylinder temperature of 230 ° C. using an NVC φ50 mm single screw extruder manufactured by Nakatani Machinery Co., Ltd. After cooling, it was cut with a pelletizer to obtain a pellet-shaped polypropylene composition. Tm of the polypropylene composition measured by the above method was 165 ° C.

2. Manufacture of sheet Press molding polypropylene composition (preheating at 230 ° C for 5 minutes, repeating degassing operation between 0 and 60 MPa for 30 seconds, holding at 60 MPa for 3 minutes, then cooling at 30 ° C A plate having a thickness of 1.5 mm was obtained. This plate is cut into a size of 10.5 cm × 10.5 cm, heated at 140 ° C. for 120 seconds using a Bruckner film stretching apparatus (KARO), and simultaneously stretched in two directions at a stretching speed of 350 mm / second. The film was stretched to perform biaxial stretching of 2.3 times by 2.3 times. After stretching, the sheet was cooled as it was without being held at 100 ° C. or higher to obtain a sheet. The stretching temperature Ts was 140 ° C. The properties and composition of the sheet are shown in Table 1.

[Example 2]
In Example 1, the residence time distributions in the first and second stages were adjusted so that the amount of the component (2) in the composition was 15% by weight, and the following compositions were obtained.
Component (1): Propylene homopolymer 85% by weight
Component (2): 15% by weight of ethylene-propylene copolymer containing 75% by weight of propylene

  The same kind and amount of nucleating agent, antioxidant, neutralizing agent and 5 parts by weight of polystyrene-hydrogenated polybutadiene-polystyrene (SEBS) with respect to 100 parts by weight of the polymer powder thus obtained. A master batch composition was prepared by mixing (trade name Tuftec 1062 manufactured by Asahi Kasei Chemicals Corporation). Next, 25 parts by weight of the master batch composition and 75 parts by weight of the component (4) were mixed, and a sheet was produced and evaluated in the same manner as in Example 1.

[Example 3]
A sheet was produced and evaluated in the same manner as in Example 2 except that a polypropylene elastomer (Vistamaxx3020 manufactured by ExxonMobil Co., Ltd.) was used instead of polystyrene-hydrogenated polybutadiene-polystyrene (SEBS).

[Example 4]
A sheet was produced and evaluated in the same manner as in Example 1 except that the master batch composition having XSIV of 1.5 dl / g was prepared by changing H2 / C2 of the second-stage reactor.

[Example 5]
A sheet was produced and evaluated in the same manner as in Example 1 except that the master batch composition having XSIV of 1.8 dl / g was prepared by changing H2 / C2 of the second-stage reactor.

[Example 6]
Adjust the ethylene concentration of the raw material monomer of the first-stage reactor so that the ethylene content in component (1) is 2.5% by weight, so that the MFR of the masterbatch composition does not change A sheet was produced and evaluated in the same manner as in Example 1 except that the hydrogen concentration was adjusted.

[Example 7]
A sheet was produced and evaluated in the same manner as in Example 1 except that ADK STAB NA21 (phosphate ester-based nucleating agent NA-21, manufactured by ADEKA Corporation) was used as the nucleating agent instead of Millad NX8000J.

[Comparative Examples 1 and 2]
Change the H2 / C2 of the second-stage reactor to prepare master batch compositions with XSIV of 2.3 dl / g and 0.9 dl / g, respectively, so that the MFR of the master batch composition does not change A sheet was produced and evaluated in the same manner as in Example 1 except that the hydrogen concentration in the first reactor was adjusted.

[Comparative Examples 3 and 4]
The residence time distribution of the first stage and the second stage is such that the ratio of component (1): component (2) in the masterbatch composition is 70 wt%: 30 wt% and 87 wt%: 13 wt%, respectively. A sheet was produced and evaluated in the same manner as in Example 1 except that the hydrogen concentration in the first-stage reactor was adjusted so that the MFR of the master batch composition did not change.

[Comparative Examples 5 and 6]
A sheet was produced and evaluated in the same manner as in Example 1 except that the master batch composition with MFR of 1 g / 10 min and 6 g / 10 min was obtained by changing the hydrogen concentration in the first-stage reactor, respectively. .

[Comparative Example 7]
The ethylene concentration in the first-stage reactor is changed so that the ethylene content in component (1) is 3.5% by weight, and the MFR of the master batch composition is not changed. A sheet was produced and evaluated in the same manner as in Example 1 except that the hydrogen concentration in the reactor was adjusted.

[Comparative Example 8]
A sheet was produced and evaluated in the same manner as in Example 1, except that C2 / (C2 + C3) of the raw material monomer of the second-stage reactor was changed so that the propylene content in component (2) was 63% by weight. did.

[Comparative Example 9]
A sheet was produced and evaluated in the same manner as in Example 1, except that C2 / (C2 + C3) of the raw material monomer of the second-stage reactor was changed so that the propylene content in component (2) was 88% by weight. did.

[Comparative Example 10]
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.
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 is 10. Was contacted at 12 ° C. for 24 minutes. 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 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: polymerization temperature and hydrogen concentration in the first reactor are 70 ° C. and 0.07 mol%, respectively, polymerization temperature, H2 / C2, C2 / C in the second reactor. (C2 + C3) were 85 ° C., 0.47 molar ratio, and 0.19 molar ratio, respectively. The polymer obtained by the polymerization blend is a composition comprising the following components (1) and (2). A sheet was produced and evaluated in the same manner as in Example 1 using this composition.
Component (1): Propylene homopolymer 83% by weight
Component (2): ethylene-propylene copolymer containing 75% by weight of propylene 17% by weight

[Comparative Example 11]
A sheet was produced and evaluated in the same manner as in Example 1 except that a polypropylene composition was produced by mixing 50 parts by weight of the master batch composition and 50 parts by weight of the component (4).

  As shown in Table 1, it is clear that the sheet of the present invention is excellent in cold shock resistance, transparency and cutting properties. It is also clear that a sheet outside the range specified in the present invention cannot satisfy all these characteristics.

Claims (7)

(I) 75 to 86% by weight of propylene (co) polymer containing 0 to 3% by weight of ethylene or one or more C4 to C10-α-olefins as component (1);
14-25 wt% of an ethylene-propylene copolymer having a propylene content of 65-85 wt% as component (2); and a nucleating agent as component (3),
The melt flow rate (230 ° C., load 21.18 N) is 1.5 g / 10 minutes or more and less than 5.5 g / 10 minutes,
Preparing a master batch composition having an XSIV (intrinsic viscosity of xylene solubles) of 1.0 to 2.2 dl / g;
(II) Mixing the masterbatch composition and a composition containing a propylene (co) polymer containing 0 to 3% by weight of ethylene or one or more C4 to C10-α-olefins as component (4). Preparing a polypropylene composition containing 10 to 40% by weight of the masterbatch composition and 60 to 90% by weight of component (4);
(III) including a step of biaxially stretching the polypropylene composition,
A method for producing a sheet or film.   The manufacturing method of Claim 1 which further includes the process of cooling, maintaining the surface state of the molded object after the said biaxial stretching.   The manufacturing method of Claim 1 or 2 which contains 0.05-1.0 weight part of said nucleating agents with respect to a total of 100 weight part of said component (1) and (2). In the step (I), propylene and ethylene or C4 to C10-α-olefin, which are raw materials of the component (1), and ethylene and propylene, which are raw materials of the component (2),
(A) a solid catalyst containing magnesium, titanium, halogen, and a succinate compound as an electron donor compound,
The manufacturing method in any one of Claims 1-3 including the process superposed | polymerized using the catalyst containing (B) organoaluminum compound and (C) external electron donor compound.   The manufacturing method of Claim 4 which implements the said superposition | polymerization process using two or more reactors.   The molded object which has a layer which consists of a film or sheet manufactured by the manufacturing method in any one of Claims 1-5.   The secondary molded object formed by shape | molding the molded object of Claim 6.