JP6517560B2 - Film or sheet obtained from polypropylene composition - Google Patents

Description

  The present invention relates to films or sheets obtained from polypropylene compositions.

  Polypropylene is useful as a food container because it has excellent physical properties and is also hygienic. For example, it is proposed that a nucleating agent is mixed with polypropylene to obtain a sheet, which is vacuum-formed to produce a food container (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, it has been proposed, for example, to add an ethylene-based copolymer to polypropylene (US Pat. No. 5,677,859).

Unexamined-Japanese-Patent No. 2000-334823 JP-A-59-171625 Unexamined-Japanese-Patent No. 2006-193539 JP-A-7-286007 JP 10-292074 Special Table 2011-513528

  The inventors conducted preliminary investigations of the technology described in the patent literature, and it was found that the addition of the ethylene-based copolymer reduces the transparency, so that the conventional polypropylene-based sheet has satisfactory transparency and cold impact resistance. I found that I did not do it. In view of such circumstances, it is an object of the present invention to provide a sheet obtained from a polypropylene composition which is excellent in transparency and cold impact resistance.

The inventors have found that the above problems can be solved by biaxially orienting a specific polypropylene composition under specific temperature conditions, and completed the present invention. That is, the said subject is solved by the following this invention.
[1] Component (1) 70 to 97% by weight of a propylene-ethylene copolymer containing 1.0 to 5.0% by weight of ethylene;
Component (2) 3 to 30% by weight of an ethylene-propylene copolymer containing 70 to 90% by weight of ethylene; and component (3) a nucleating agent,
Melt flow rate (230 ° C, load 21.18 N) 1.0 to 10 g / 10 min,
A polypropylene composition having an XSIV (inherent viscosity of xylene solubles) of 0.5 to 2.0 dl / g,
A sheet or film obtained by a method comprising: biaxially orienting at a temperature Ts (° C.); and cooling the biaxially oriented shaped body while maintaining its surface state,
When the peak top temperature of the melting point on the highest temperature side derived from the component (1) or (2) in the second scan with a differential scanning calorimeter (DSC) of the polypropylene composition is Tm (° C.),
Satisfy 0 ≦ Ts−Tm ≦ 10,
Sheet or film.
[2] At least a portion of the component (1) and at least a portion of the component (2) are
(A) A solid catalyst containing magnesium, titanium, halogen, and a succinate-based compound as an electron donor compound,
The sheet or film according to [1], which is produced using a catalyst comprising (B) an organoaluminum compound, and (C) an external electron donor compound.
[3] The sheet or film according to [1] or [2], containing 0.05 to 1.0 parts by weight of the nucleating agent with respect to a total of 100 parts by weight of the components (1) and (2). 4) A composition produced by a method comprising the step of polymerizing propylene and ethylene, which are raw materials of component (1) and component (2), using two or more reactors. , The sheet or film as described in [1]-[3].
[5] The sheet or film according to [1] to [4], wherein the nucleating agent is selected from the group consisting of a sorbitol-based nucleating agent, a nonitol-based nucleating agent, and a phosphate ester-based nucleating agent.
[6] The nucleating agent is 1,3: 2,4-bis-o- (4-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-o- (3,4-dimethylbenzylidene ) -D-sorbitol, and 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol selected from [1] to [5] A sheet or film according to any one of the above [1] to [7], and a molded article having a layer comprising the sheet or film according to any one of the above [1] to [6].
[8] A secondary molded body obtained by molding the molded body according to [7].
[9] I. Component (1) 70 to 97% by weight of a propylene-ethylene copolymer containing 1.0 to 5.0% by weight of ethylene;
Component (2) 3 to 30% by weight of an ethylene-propylene copolymer containing 70 to 90% by weight of ethylene; and component (3) a nucleating agent,
Melt flow rate (230 ° C, load 21.18 N) 1.0 to 10 g / 10 min,
Preparing a polypropylene composition having an XSIV (inherent viscosity of xylene solubles) of 0.5 to 2.0 dl / g,
II. Biaxially orienting the polypropylene composition at a temperature Ts (° C.), and III. Including the step of cooling while maintaining the surface state of the molded body after the biaxial stretching;
When the peak top temperature of the melting point on the highest temperature side derived from the component (1) or (2) in the second scan in DSC of the polypropylene composition is Tm (° C.),
Satisfy 0 ≦ Ts−Tm ≦ 10,
How to make a sheet or film.
[10] The step I is
At least a portion of the component (1) and at least a portion of the component (2),
(A) A solid catalyst containing magnesium, titanium, halogen, and a succinate-based compound as an electron donor compound,
The method for producing a sheet or film according to [9], comprising the step of producing using a catalyst comprising (B) an organoaluminum compound, and (C) an external electron donor compound.

  In the present invention, the sheet is a member having a thickness of 200 μm or more, and the film is a member having a thickness of less than 200 μm. The sheet of the present invention is obtained by biaxially orienting 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 the values at both ends, ie, X and Y.

1. Polypropylene composition The polypropylene composition used in the present invention comprises (1) 70 to 97% by weight of a propylene-ethylene copolymer containing 1.0 to 5.0% by weight of ethylene and (2) 70 to 90% by weight It contains 3 to 30% by weight of an ethylene-propylene copolymer containing ethylene, and (3) a nucleating agent. The propylene-ethylene copolymer 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.

(1) Propylene-Ethylene Copolymer The propylene-ethylene copolymer contains 1.0 to 5.0% by weight of ethylene. When the content of ethylene as a comonomer is less than the lower limit value, the transparency of the obtained sheet or the like is reduced. On the other hand, when the ethylene content exceeds the upper limit value, the rigidity and the stretchability decrease. From these viewpoints, the ethylene content is more preferably 1.5 to 3.5% by weight.

(2) Ethylene-propylene copolymer The ethylene content in the ethylene-propylene copolymer is 70 to 90% by weight, preferably 72 to 90% by weight.

(3) Nucleating agent The nucleating agent is an additive used to control the size of the crystal component in the resin to a small size to enhance transparency. The nucleating agent is not particularly limited, and those generally used in the relevant field may be used, but nonitol based nucleating agents, sorbitol based nucleating agents, phosphate ester based nucleating agents, triaminobenzene derivative nucleating agents, metal carboxylates Preferably, it is selected from salt nucleating agents and xylitol nucleating agents. Examples of nonitol based nucleating agents include 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol.

  Examples of xylitol nucleating agents include bis-1,3: 2,4- (5 ′, 6 ′, 7 ′, 8′-tetrahydro-2-naphthaldehyde benzylidene) 1-allyl xylitol, bis-1,3: 2,4- (3 ', 4'-dimethylbenzylidene) 1-propyl xylitol is mentioned.

  As a sorbitol-based nucleating agent, for example, 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'-dibromopropyl sorbitol, bis-1,3,2,4-dibenzylidene 2'-bromo-3'-hydroxypropyl sorbitol, 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 them, commercially available nucleating agents such as nonyl-based milladal NX8000, NX8000K, 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol, for example. NX8000J (Moriken Japan Co., Ltd.), Sorbitol group RiKAFAST R-1 (Shin Nippon Rika Co., Ltd.), Millad 3988 (Miriken Japan Co., Ltd.), Gelall E-200 (Shin Nippon Chemical Co., Ltd.), Gelall MD (made by Shin Nippon Rika Co., Ltd.) etc. are mentioned.

  As a phosphoric acid ester-based nucleating agent, aluminum-bis (4,4 ', 6,6'-tetra-tert-butyl-2,2'-methylenediphenyl-phosphate) -hydroxide, phosphoric acid-2,2'- Methylene bis (4,6-di-tert-butylphenyl) lithium salt type compounds etc. are mentioned. Examples of commercially available phosphate ester-based nucleating agents include Adekastab NA-21 (manufactured by ADEKA Corporation), Adekastab NA-71 (manufactured by ADEKA Corporation), and the like.

  Examples of triaminobenzene derivative nucleating agents include 1,3,5-tris (2,2-dimethylpropanamido) benzene and the like. Examples of commercially available triaminobenzene derivative nucleating agents include IRGACLEAR XT 386 (manufactured by BASF Japan Ltd.).

  Examples of carboxylic acid metal salt nucleating agents include calcium 1,2-cyclohexanedicarboxylate and the like. 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 processing (heating), use of a nonitol-based nucleating agent or a sorbitol-based nucleating agent is preferable. The above nucleating agents may be used alone or in combination of two or more.

(4) Compounding ratio The compounding ratio of components (1) and (2) is (1) :( 2) = 70 to 97: 3 to 30 in weight ratio. If the amount of the component (2) exceeds this upper limit, the rigidity of the obtained sheet or the like decreases, and if it is less than the lower limit, the cold impact resistance of the obtained sheet or the like decreases. From this viewpoint, the compounding ratio of the components (1) and (2) is preferably 80 to 96: 4 to 20.

  The blending amount of the nucleating agent is preferably 0.1 to 1.0 parts by weight with respect to 100 parts by weight in total of the components (1) and (2). When the amount of the nucleating agent exceeds this upper limit, the cost is increased, and when it is less than the lower limit, the transparency of the obtained sheet or the like may be reduced. From this viewpoint, the compounding ratio of the nucleating agent is preferably 0.2 to 0.7 parts by weight with respect to 100 parts by weight in total of the components (1) and (2).

(5) Properties 1) Melt Flow Rate The melt flow rate (hereinafter also referred to as “MFR”) at 230 ° C. under a load of 21.18 N of the polypropylene composition is 1.0 to 10 g / 10 min. When the value of the melt flow rate exceeds this upper limit value, the drawdown resistance at the time of processing decreases, and when it is less than the lower limit value, the torque of the extruder at the time of processing increases. From this point of view, the melt flow rate is preferably 1.5 to 7.0 g / 10 min.

2) XSIV
XSIV is the intrinsic viscosity of the xylene solubles of the polypropylene composition and is also an indicator 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 intrinsic viscosity of the component according to a standard method. In the present invention, XSIV is 0.5 to 2.0 dl / g. When the XSIV exceeds 2.0 dl / g, the transparency of the sheet or the like obtained is lowered. When the XSIV is less than 0.5 dl / g, production becomes difficult.

(6) Other components The polypropylene resin composition of the present invention further comprises an antioxidant, hydrochloric acid absorber, heat resistant stabilizer, light stabilizer, ultraviolet absorber, internal lubricant, external lubricant, antistatic agent, flame retardant, Add conventional additives commonly used in olefin polymers such as dispersants, copper inhibitors, neutralizers, plasticizers, defoamers, crosslinkers, peroxides, oil spreads and other organic and inorganic pigments You may

2. Biaxial Stretching The biaxially stretched sheet or film of the present invention has at least one layer comprising the above-mentioned polypropylene composition. When the biaxially oriented sheet or film has a layer other than the above-mentioned polypropylene composition, the other layers are not particularly limited, but a homopolymer of propylene, a random copolymer, a block copolymer, or any of these And a composition containing a resin other than polypropylene as a main component.

  The biaxially oriented sheet or film of the present invention is preferably obtained by preparing a sheet (preliminary sheet) in advance from the above-mentioned polypropylene composition and stretching in the width direction and the flow direction of the preparatory sheet. The stretching in the width direction and the flow direction may be simultaneous, or may be performed with a time lag as described later. In a conventional method for producing a biaxially oriented polypropylene film, first, a polypropylene composition is melted by an extruder, and then extruded into a sheet from a T-die to prepare a preliminary sheet, which is then cooled and solidified by a cooling roll. Next, the obtained sheet is stretched in the longitudinal direction through a number of heating rolls (longitudinal stretching). Subsequently, it is stretched in the lateral direction through a heating furnace constituted of a preheating part, a stretching part and a heat treatment part (transverse stretching). In compression molding, vacuum molding or the like which is also used as a secondary molding method, the preliminary sheet obtained in advance is biaxially stretched to form a target thickness and shape. When the sheet or the like of the present invention has a layer other than the above-mentioned polypropylene composition, a preliminary sheet in which the layer of the above-mentioned polypropylene composition and the other layers are laminated is prepared and stretched as described above. The biaxially oriented sheet of the present invention can be produced.

  The biaxially oriented sheet or film of the present invention is obtained by melting a polypropylene composition with an extruder and then biaxially stretching it at a stage where the molten resin extruded from a die solidifies, as in calendar molding and inflation molding. Is also possible.

  In the present invention, a sheet or film is obtained by a method comprising the step of biaxially orienting a polypropylene composition at a specific temperature Ts. When the step of biaxial stretching such as the longitudinal stretching and the lateral stretching is composed of a plurality of stages, stretching is performed at Ts at least in the last stage. The temperature Ts is determined by a differential scanning calorimeter (DSC). Specifically, Ts is obtained by second scanning the composition with DSC to obtain melting points derived from the components (1) and (2), and these are determined as follows.

  The second scan refers to crystallization of the polypropylene composition after melting using DSC, holding for 5 minutes at room temperature, and then thermal analysis using DSC. Specifically, 1) The polypropylene composition is heated to a melting temperature (230 ° C.), held at that temperature for 5 minutes, cooled to 30 ° C. at a temperature decrease rate of 10 ° C./min and held for 5 minutes, 2 2.) Thermal analysis is performed by heating to 230 ° C. at a heating rate of 10 ° C./min.

  The polypropylene composition of the present invention is required to have a melting point peak derived from the component (1) or (2) by the thermal analysis. Ts satisfies 0 ≦ Ts−Tm ≦ 10 when Tm (° C.) is the peak top temperature of the melting point on the highest temperature side derived from the component (1) or (2) in the second scan of DSC of the polypropylene composition It is decided to do. When component (1) or (2) or both have a plurality of peaks, the peak top temperature at the highest temperature side among them is Tm.

  The temperature range of Ts is a state in which most of the crystals derived from the components (1) and (2) of the polypropylene composition are melted together and the sheet shape can be maintained. Therefore, if the temperature at the time of biaxial stretching exceeds the above-mentioned upper limit, biaxial stretching becomes difficult, and when it becomes less than the above-mentioned lower limit, transparency of a sheet etc. obtained will fall. The deterioration of the transparency of the finally obtained sheet etc. is caused by melting with respect to the unmelted component if a large amount of unmelted component containing high melting point crystals is present in one of the components (1) or (2) during stretching. It is considered that as a result of drawing in a state where some components are depressed, asperities are generated on the surface. In the present invention, it is considered that a sheet or the like excellent in transparency can be obtained since the polypropylene composition is stretched at the Ts. However, it is not limited to this theory. The lower limit of Ts-Tm is 0 or more, preferably 2 or more, and more preferably 3 or more. Moreover, although the upper limit of Ts-Tm is 10 or less, 9 or less is more preferable.

3. Cooling The molded product obtained by biaxial stretching in the above temperature range has a smooth surface and high transparency as a result of stretching of both components (1) and (2) in a molten state. In this process, cooling is performed while maintaining this smooth surface state, and the transparency of the sheet or the like is maintained. Since large size crystals cause surface roughness, in order to maintain smoothness, it is preferable to cool to a temperature at which crystals formed during cooling after biaxial stretching do not grow. Although the specific value is not limited, 80 degrees C or less is preferable, and, as for cooling temperature, 50 degrees C or less is more preferable. The method of cooling is not particularly limited, and, for example, the molded product obtained by biaxial stretching can be water-cooled or air-cooled.

4. Method of Producing Polypropylene Composition The polypropylene composition may be produced by any method, but in the present invention, a solid catalyst comprising (A) magnesium, titanium, a halogen, and a succinate-based compound as an electron donor compound, Preferably, at least a portion of components (1) and (2) is produced using a catalyst comprising B) an organoaluminum compound, and (C) an external electron donor compound.

(1) Component (A): Solid Catalyst Component (A) can be prepared by a known method, for example, by mutually contacting a magnesium compound, a titanium compound and an electron donor compound.

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. More specifically, titanium compounds such as titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , and Ti (O _n —C ₄ H, as titanium compounds. ₉ ) Trihalogenated alkoxy titanium such as Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl _{2 2} , dihalogenated alkoxy titanium 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 ₂ , Monohalogenated trialkoxytitaniums such as Ti (O _n -C ₄ H ₉ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , tetraalkoxy titanium such as Ti (O _n -C ₄ H ₉ ) ₄ and the like. Of these, preferred are halogen-containing titanium compounds, particularly tetra-halogenated titanium compounds, and more preferred is titanium tetrachloride.

  Examples of the magnesium compound used for the preparation of the component (A) include magnesium compounds having a magnesium-carbon bond and a magnesium-hydrogen bond, such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, Examples thereof include decyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds can be used, for example, in the form of a complex compound with an organic aluminum or the like, and may be liquid or solid. Further suitable magnesium compounds such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium halide such as magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride and the like Alkoxy magnesium halides; phenoxy magnesium chloride, allyloxy magnesium halides such as methyl phenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, alkoxy magnesium such as n-octoxy magnesium, 2-ethylhexoxy magnesium; phenoxy Magnesium, allyloxy magnesium such as dimethyl phenoxy magnesium; Magnesium Ulin acids, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

  The electron donor compounds used to prepare component (A) are generally referred to as "internal electron donors". In the present invention, the electron donor compound is preferably a succinate compound. In the present invention, a succinate compound refers to a diester of succinic acid or a diester of substituted succinic acid. The succinate compounds are described in detail below. The succinate compounds preferably used in the present invention are represented by the following formula (I).

In which the radicals R ₁ and R ₂ are identical or different from one another, C _{1 to} C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkyl, optionally containing heteroatoms The radicals R _{3 to} R ₆ are C _{1 to} C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, which are identical or different from one another and are hydrogen or optionally contain heteroatoms Groups R _{3 to} R ₆ which are arylalkyl or alkylaryl groups and which are bonded to the same or different carbon atoms may be linked together to form a ring.
R ₁ and R ₂ are preferably C _{1 to} C ₈ alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups. Particular preference is given to compounds in which R ₁ and R ₂ are selected from primary alkyls, in particular branched primary alkyls. Examples of suitable R ₁ and R ₂ groups are C ₂ -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl and neopentyl are particularly preferred.

One preferred group of compounds represented by formula (I) is 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 monosubstituted succinate compounds are diethyl-sec-butyl succinate, diethyl texyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl perihydrosuccinate, diethyl Trimethylsilyl succinate, diethyl methoxysuccinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethylphenyl 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 isopentii Succinate, diethyl (1-trifluoromethylethyl) succinate, diethylfluorenyl succinate, 1-ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyltexyl succinate, diisobutylcyclopropyl succinate , Diisobutyl norbornyl succinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilyl succinate, diisobutyl methoxy succinate, diisobutyl p-methoxyphenyl succinate, diisobutyl p-chlorophenyl succinate diisobutyl cyclohexyls Succinate, diisobutylbenzyl succinate, diisobutyl cyclohexyl methyl succinate, diisobutyl-t-butyl succine , Diisobutylisobutyl succinate, diisobutyl isopropyl succinate, diisobutyl neopentyl succinate, diisobutyl isopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenyl succinate, dineopentyl-sec- Butyl succinate, dineopentyl texisuccinate, dineopentyl cyclopropyl succinate, dineopentyl norbornyl succinate, dineopentyl perihydrosuccinate, dineopentyl trimethylsilyl succinate, dineopentyl Pentyl methoxysuccinate, dineopentyl-p-methoxyphenyl succinate, dineopentyl-p-chlorophenyl succinate, dineopentyl phenyl succinate, zine Opentylcyclohexyl succinate, dineopentyl benzyl succinate, dineopentyl cyclohexyl methyl succinate, dineopentyl-t-butyl succinate, dineopentyl isobutyl succinate, dineopentyl isopropyl succinate, Neopentyl neopentyl succinate, dineopentyl isopentyl succinate, dineopentyl (1-trifluoromethylethyl) succinate, dineopentyl fluorenyl succinate.

Another preferred group of compounds within the scope of formula (I) is a C _{1 to} 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. Particular preference is given to compounds in which two radicals other than hydrogen are attached to the same carbon atom. Specifically, it is a compound in which R ₃ and R ₄ are a group different from hydrogen, and R ₅ and R ₆ are a hydrogen atom. 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-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- Butyl succinate, diethyl-2-phenyl-2-n-butyl succinate, diisobutyl-2,2-dimethyl succinate, diisobutyl-2-ethyl-2-methyl succinate, 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-ethylsuccinate, diisobutyl-2-isopropyl-2-methylsuccinate, diisobutyl-2-tetradecyl-2-ethylsuccinate, diisobutyl-2-isobutyl-2-ethylsuccinate, diisobutyl -2- (1-trifluoro) Ethylethyl) -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 And 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 radicals different from hydrogen are bonded to different carbon atoms are also particularly preferred. Specifically, it is a compound in which R 3 and R 5 are groups different from hydrogen. In this case, R4 and R6 may be a hydrogen atom or a group different from hydrogen, but it is preferable that one of them be 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-dibenzyl succinate, Diethyl-2,3-diisopropyl succinate, Diethyl-2,3-bis (cyclohexylmethyl) ) Succinate, diethyl-2,3-di-t-butyl succinate, diethyl-2,3-diisobutyric acid 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-cyclohexylsuccinate, diethyl-2-isopentyl-3-cyclohexylsuccinate, diethyl-2-tetradecyl-3-cyclohexylmethylsuccinate, diethyl-2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl -2,3-diethyl-2-iso Ropyl succinate, diisobutyl-2,3-diisopropyl-2-methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methyl succinate, diisobutyl-2,3-dibenzyl succinate, diisobutyl-2 , 3-diisopropylsuccinate, diisobutyl-2,3-bis (cyclohexylmethyl) succinate, diisobutyl-2,3-di-tert-butylsuccinate, diisobutyl-2,3-diisobutylsuccinate, 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-isobutylsuccinate, Diisobutyl-2-tert-butyl-3-isopropyl succinate, Diisobutyl-2-isopropyl-3-cyclohexyl succinate, Diisobutyl-2-isopentyl-3- Cyclohexyl succinate, diisobutyl-2-tetradecyl-3-cyclohexyl methyl 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, zine 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-tetradecy 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-cyclohexyl methyl succinate, and dineopentyl 2-cyclohexyl 3-cyclopentyl succinate.

Of the compounds of formula (I), compounds in which some of the radicals R _{3 to} R ₆ are joined together to form a ring can also preferably be used. The compounds listed in JP-A-2002-542347 as such compounds, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- ( Ethoxyacetyl) -2,5-dimethyldimethyl cyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2 monomethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned. Besides, cyclic succinate compounds as disclosed in, for example, WO 2009/069483 can also be suitably used. As examples of other cyclic succinate compounds, the compounds disclosed in WO 2009/057747 are also preferred.

In the compounds of formula (I), when the radicals R _{3 to} R ₆ contain a heteroatom, the heteroatom is a Group 15 atom comprising nitrogen and phosphorus atoms or a Group 16 atom comprising oxygen and sulfur atoms preferable. Group _R 3 to R ₆ are Examples of the compound containing a Group 15 atom include compounds disclosed in JP-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.

(2) Component (B): Organic Aluminum Compound Examples of the organic aluminum compound as the component (B) include the following.
Trialkylaluminum such as triethylaluminum, tributylaluminum etc.
Trialkenyl Aluminum such as Triisopropenyl Aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide;

Partially alkoxylated alkyl aluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 or the like;
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide;
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;

Partially halogenated alkylaluminums such as alkylaluminum dihalogenides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide and the like;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride and the like;
Partially alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide and the like.

(3) Component (C): Electron Donor Compound The electron donor compound of component (C) is generally referred to as "external electron donor". As such an electron donor compound, an organosilicon compound is preferable. The following may be mentioned as preferred organosilicon compounds.

  Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethylsilane Dimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxye Silane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyl Liethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyl Triethoxysilane, Vinyltriethoxysilane, t-butyltriethoxysilane, Texyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlor Triethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornane trimethoxy Orchid, 2-norbornane triethoxysilane, 2-norbornane methyl dimethoxysilane, ethyl silicate, butyl silicate, trimethyl phenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, Dimethyl tetraethoxy disiloxane.

  Among them, ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-Butylpropyldimethoxysilane, t-butyl t-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl (perhydroisoquinoline 2--2-) ) Dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropenyloxy) phenylsilane, thexyltrimethoxysilane, vinyltriethoxysilane, phenyltrie Xysilane, phenyltrimethoxysilane, vinyltributoxysilane, 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, Phenyltriethoxysilane, bis-p-tolyldimethoxy Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornane triethoxysilane, 2-norbornane methyldimethoxysilane, diphenyldiethoxysilane, methyl (3, 3, 3-trifluoropropyl) dimethoxymethane Silane, ethyl silicate and the like are preferred.

(4) Polymerization A polypropylene composition is produced by polymerizing propylene and ethylene as raw materials of component (1) and ethylene and propylene as raw materials of component (2) using two or more reactors. Is preferred.

The polymerization may be carried out in the liquid phase, in the gas phase or in the 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. Chain transfer agents (e.g. hydrogen or ZnEthyl ₂₎ may be used molecular weight modifier, well known in the art, such as.

  Moreover, as a method of obtaining the polypropylene composition of this invention, the method of performing using the polymerization vessel which has a gradient of a monomer density | concentration or superposition | polymerization conditions is mentioned. In such a polymerization vessel, for example, one in which at least two polymerization regions are connected can be used to polymerize monomers by gas phase polymerization. Specifically, in the presence of a catalyst, monomers are supplied and polymerized in a polymerization region consisting of a rising pipe, and monomers are supplied and polymerized in a falling pipe connected to the rising pipe, and a rising pipe and a falling pipe The polymer product is recovered while circulating The 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 than the gas mixture present in the riser is introduced into the downcomer. As the above-mentioned polymerization method, for example, the method described in JP-A-2002-520426 can be applied.

  Component (1) or component (2) can also be obtained by polymerizing the raw material monomers using a metallocene catalyst or a half metallocene catalyst by a known method (for example, the method described in WO 2006/102155). It can be manufactured.

  The addition of the nucleating agent is carried out, for example, by stirring the polymer obtained by polymerization and the nucleating agent together with the antioxidant with a Henschel mixer, Brabender or the like, and then melt blending at 180 ° C. to 280 ° C. using an extruder. be able to. The addition of a nucleating agent and an antioxidant may be carried out using a connected extruder after undergoing polymerization, residual monomer removal and drying steps.

  In particular, in the present invention, the polymer powder and the nucleating agent may be melt-kneaded and mixed. The polymer powder is a powdery polypropylene obtained after polymerization, after removing residual monomers and drying. The polymerized powder has an average particle size (by light scattering) of 50 to 5,000 μm. By mixing the polymer powder having a large surface area and the nucleating agent, the dispersion of the nucleating agent becomes good, and the transparency of the obtained sheet is further improved. In the present invention, a so-called master batch obtained by melt-kneading a high concentration nucleating agent with polypropylene may be mixed with a polypropylene resin at the time of sheet forming.

5. Applications The sheet or film of the present invention can be formed into a desired shape and used for various applications. For example, the sheet or the like of the present invention is useful as a packaging material, a container material, particularly a food container. For example, a sheet or the like can be formed into a container by vacuum forming or the like. Since the obtained container is excellent in transparency and cold impact resistance, it is useful as a container for ice and frozen desserts and a container for cooled beverages.

EXAMPLES The present invention will be further described based on examples but the present invention is not limited thereto.
1. Preparation of Polymer (1) Solid Catalyst An Example of JP 2011-500907 A (International Publication 2009/050045) except that the temperature at which the temperature of the solid catalyst used in the polymerization was first changed from 100 ° C. to 110 ° C. Prepared as described in Specifically, it was prepared as follows.

250 ml of TiCl ₄ was introduced at 0 ° C. into a 500 ml four necked round bottom flask purged with nitrogen. With stirring, 10.0 g of fine spherical MgCl ₂ .2.8 C ₂ H ₅ OH (manufactured according to the method described in Example 2 of US Pat. No. 4,399,054, operating at 3000 rpm instead of 10000 rpm) And 9.1 mmol of diethyl-2,3-diisopropylsuccinate were added. The temperature was raised to 110 ° C. and held for 120 minutes. Stirring was then stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off. Next, the following operation was repeated twice. 250 ml of fresh TiCl ₄ was added, the mixture was reacted at 120 ° C. for 60 minutes, and the supernatant was siphoned off. The solid was washed 6 times with anhydrous hexane (6 × 100 ml) at 60 ° C.

(2) Polymer A
Using the above solid catalyst, triethylaluminum (TEAL) as an organoaluminum compound, and dicyclopentyldimethoxysilane (DCPMS) as an external electron donor compound, the weight ratio of TEAL to solid catalyst is 11, and the weight ratio of TEAL / DCPMS is 10 The solution was brought into contact for 24 minutes at 12 ° C. in an amount such that The resulting catalyst system was prepolymerized by holding it in suspension in liquid propylene at 20 ° C. for 5 minutes.

  The resulting 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-ethylene copolymer, and ethylene is produced in the second polymerization reactor. -A propylene copolymer was produced. This corresponds to mixing (polymerization blending) of the ethylene-propylene copolymer and the propylene-ethylene copolymer from the first stage. During the polymerization, hydrogen was used as a molecular weight modifier while maintaining the temperature and pressure at the values adjusted in each stage. Also, by adjusting the residence time distributions of the first and second stages, the proportion of the polymer obtained in each stage was controlled.

  The polymerization temperature and the molar ratio of reactants are as follows: in the first reactor, the polymerization temperature, hydrogen concentration and ethylene concentration are 75 ° C., 0.21 mol% and 0.71 mol%, respectively, in the second reactor The polymerization temperature was H2 / C2 and C2 / (C2 + C3) were 80 ° C., 0.64 molar ratio and 0.71 molar ratio, respectively. The polymer obtained by the polymerization blend is a polypropylene composition comprising the following component (1) and component (2).

Component (1): Propylene-ethylene copolymer containing 3.0% by weight of ethylene 78% by weight
Component (2): ethylene-propylene copolymer containing 23% by weight of propylene 22% by weight

  Furthermore, 0.5 parts by weight of Millad NX 8000 J (nonitol type, manufactured by Milliken Japan Co., Ltd.) as a nucleating agent is added to 100 parts by weight of the polymer powder, and 0.2 parts by weight of BASF B225 as an antioxidant As a neutralizing agent, 0.05 parts by weight of calcium stearate manufactured by Tannan Chemical Co., Ltd. was added, and mixed by stirring with a Henschel mixer for 1 minute. This mixture is extruded at a cylinder temperature of 230 ° C. using an NVC φ50 mm single screw extruder manufactured by Nakatani Machinery Co., Ltd., and the strands are cooled in water and then cut by a pelletizer to obtain a pelletized propylene resin composition. It was A. Polymer A is a polypropylene composition containing a nucleating agent.

(3) Polymer B1
The solid catalyst used for the polymerization was prepared by the method described in Example 1 of EP 674991. 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-mentioned patent publication. The solid catalyst, triethylaluminum (TEAL) and diisopropyldimethoxysilane (DIPMS) in an amount such that the weight ratio of TEAL to solid catalyst is 11 and the weight ratio of TEAL / DIPMS is 3.2 at -5 ° C The contact was made for 5 minutes. The resulting catalyst system was prepolymerized by holding it in suspension in liquid propylene at 20 ° C. for 5 minutes.

  After introducing the obtained prepolymer into a polymerization reactor, hydrogen, propylene and ethylene are fed, and the polymerization temperature, hydrogen concentration and ethylene concentration are made 75.degree. C., 0.12 mol% and 0.45 mol%, respectively. By adjusting the pressure, a propylene ethylene copolymer was produced. The polymer is component (1) and is a copolymer of polypropylene containing 1.7% by weight of ethylene. A polymer B1 was obtained in the same manner as the polymer A using the powder of the polymer. The polymer B1 is a composition in which a nucleating agent is added to the component (1).

(4) Polymer B2
The polymer B2 is a polymer except that 100 parts by weight of the polymer contains 0.25 parts by weight of Millad 3988 (sorbitol, manufactured by Milliken Japan Co., Ltd.) instead of 0.5 parts by weight of the Millad NX 8000 J as a nucleating agent. It is a composition having the same composition as B1.

(5) Polymer C
Component (1) polypropylene homopolymer was prepared using a prepolymer prepared in the same manner as the prepolymer used in the polymerization of polymer B1, except that DCPMS was used instead of DIPMS as the external electron donor. And Component (2) The ethylene-propylene copolymer was subjected to multistage polymerization to produce a polymerization blend. In the first reactor, the polymerization temperature and hydrogen concentration are 70 ° C and 0.10 mol%, and in the second reactor, the polymerization temperature, hydrogen concentration and C2 / (C2 + C3) are 85 ° C and 1.13, respectively. The polymerization pressure was adjusted while the molar ratio was 0.48 molar ratio. Also, by adjusting the residence time distributions of the first and second stages, the proportion of the polymer obtained in each stage was controlled. The polymer C obtained by the said polymerization blend is a polypropylene composition which consists of the following component (1) and a component (2). A polymer powder was prepared in the same manner as polymer A except that no nucleating agent was added.
Component (1): homopolymer of propylene 80% by weight
Component (2): ethylene-propylene copolymer containing 51.5% by weight of propylene 20% by weight
The compositions of the polymers thus prepared are summarized in Table 1.

2. Production of sheet Press molding of polypropylene composition (preheated for 5 minutes at 230 ° C., repeated depressurization between 0 and 60 MPa for 30 seconds, held for 30 minutes under 60 MPa, followed by cooling at 30 ° C. A press was held for 3 minutes to obtain a 1.5 mm thick plate. This plate is cut to a size of 10.5 cm × 10.5 cm, heated at a temperature shown in Table 2 for 120 seconds using a Bruckner film stretching apparatus (KARO), and simultaneously stretched at a stretching speed of 350 mm / sec. The film was stretched in two directions and biaxially stretched 2.3 times × 2.3 times. After stretching, it was cooled to obtain a sheet.

3. Analysis and evaluation (1) MFR
According to JIS K 7210, the temperature was measured at 230 ° C. under a load of 21.18 N.
(2) XSIV
2.5 g of the sample was placed in a flask containing 250 ml of o-xylene (solvent) and stirred for 30 minutes with a nitrogen purge at 135 ° C. using a hot plate and a reflux apparatus to completely dissolve the sample . The solution was then cooled to 25 ° C. for 1 hour. The solution obtained is filtered using filter paper, and 100 ml of filtrate is collected, transferred to an aluminum cup etc., evaporated to dryness at 150 ° C. while purging with nitrogen, and allowed to stand at room temperature for 30 minutes for xylene solubility I got a minute. The intrinsic viscosity was measured in 135 ° C. tetrahydronaphthalene of the xylene solubles using a Ubbelohde viscometer to obtain XSIV (dl / g).

(3) Stretchability A case where no problem such as breakage occurred during drawing was evaluated as good, and a case where a problem occurred was evaluated as defective.
(4) Transparency According to ISO 14782, haze was measured on the sheet obtained as described above using HM-150 manufactured by Murakami Color Research Laboratory, Inc. to evaluate the transparency. At the same time, liquid paraffin (Liquid Paraffin Cat. No. 32033-00, manufactured by Kanto Chemical Co., Ltd.) is applied to both sides of the sheet with a brush in order to exclude the influence of irregularities of the sheet surface derived from forming and cooling conditions, Haze measurement was performed. The former was defined as "all haze" and the latter as "internal haze". Moreover, in order to see the contribution of the unevenness | corrugation of a sheet | seat surface, "external haze"("allhaze"-"internalhaze") was defined.

(5) Cold impact resistance Type D2 small square plate specified in JIS K7152 was prepared. Subsequently, this plate was punched to prepare an A-shaped test piece specified by JIS K7216. The embrittlement temperature was measured according to JIS K 7216 using the test piece to evaluate cold impact resistance. The lower the embrittlement temperature, the better the cold impact resistance.

(6) Ethylene Content of Polymer or Each Component of Polymer A sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene, JNM LA-400 ( ¹³ C resonance, manufactured by JEOL Ltd. It calculated from the value measured by < ¹³ > C-NMR method using the frequency of 100 MHz.
(7) Differential scanning calorimetry (DSC)
The second scan defined above was performed using a Perkin Elmer diamond DSC, and measurements were taken.

Example 1
25% by weight of polymer A and 75% by weight of polymer B1 are mixed and kneaded using a 15 mmφ single-screw extruder manufactured by Thermoplastics Industry Co., Ltd. (kneading temperature 200 ° C.) to obtain polypropylene composition pellets Obtained. The resulting pellets were press molded to produce a 10.5 cm × 10.5 cm × 1.5 mm t plate. The section of the plate was heated at a rate of 20 ° C./min under nitrogen atmosphere using Perkin Elmer Diamond DSC and kept at 230 ° C. for 5 minutes. Then, the temperature was lowered to 30 ° C. at 20 ° C./min. After holding at 30 ° C. for 5 minutes, the temperature was raised at 20 ° C./minute for a second scan to measure the melting point Tm on the highest temperature side derived from the component (1) and the component (2). The Tm was 152 ° C. From this value, the temperature Ts at the time of biaxial stretching was set to 157 ° C. This Ts satisfies 0 ≦ Ts−Tm ≦ 10. As described above, the flat plate of the polypropylene composition was biaxially stretched at 157 ° C., and then immersed in ice water to rapidly cool the sheet. The sheet was evaluated, and as shown in Table 2, it was confirmed to have excellent transparency and cold impact resistance.

Example 2
As a polypropylene composition, 35 wt% of polymer A and 65 wt% of polymer B1 were mixed and biaxially stretched in the same process as in Example 1 to obtain a sheet. Similar to Example 1, it was confirmed to have excellent transparency and cold impact resistance.

[Example 3]
As a polypropylene composition, 45% by weight of polymer A and 55% by weight of polymer B1 were mixed and biaxially stretched in the same process as in Example 1 to obtain a sheet. Similar to Example 1, it was confirmed to have excellent transparency and cold impact resistance.

Example 4
As a polypropylene composition, 85% by weight of polymer A and 15% by weight of polymer B1 were mixed and biaxially stretched in the same process as in Example 1 to obtain a sheet. Similar to Example 1, it was confirmed to have excellent transparency and cold impact resistance.

[Example 5]
Polymer A was used alone as a polypropylene composition, and a plate of 10.5 cm × 10.5 cm × 1.5 mm t was produced by press molding. Thereafter, the sheet was obtained by biaxial stretching in the same process as in Example 1. Similar to Example 1, it was confirmed to have excellent cold impact resistance.

Comparative Examples 1 to 5
A sheet was produced and evaluated in the same manner as in Examples 1 to 5 except that the polypropylene composition was biaxially stretched at 150 ° C. to obtain a sheet. The resulting sheet was significantly less transparent.

Comparative Example 6
A sheet was obtained and evaluated in the same manner as in Example 1 except that the polymer B2 was used alone as the polypropylene composition. The obtained sheet was extremely inferior in cold impact resistance.

Comparative Example 7
The experiment was carried out in the same manner as in Example 1 except that the polymer C was used alone as the polypropylene composition. However, it could not be stretched and a sheet could not be obtained.

Comparative Example 8
The experiment was performed in the same manner as in Comparative Example 7 except that the stretching temperature was set to 162 ° C. Although a sheet could be obtained, the sheet was significantly less transparent.
Comparative Example 9
The experiment was performed in the same manner as Comparative Example 7 except that the stretching temperature was 168 ° C. Although 0 ≦ Ts−Tm ≦ 10 was satisfied, and a sheet could be obtained, the sheet was extremely inferior in transparency.

Comparative Example 10
After biaxially stretching, a sheet was produced and evaluated in the same manner as in Example 2 except that the film was held at 130 ° C. for 2 minutes and then air cooled to room temperature. As a result of the increase in surface asperities evaluated by the external haze, the sheet was remarkably inferior in transparency.

Comparative Example 11
The experiment was conducted in the same manner as in Example 2 except that the stretching temperature was 164 ° C. However, it could not be stretched and a sheet could not be obtained.

  From the above, it is clear that the sheet of the present invention is excellent in transparency and cold impact resistance.

Claims (11)

Component (1) 70 to 97% by weight of a propylene-ethylene copolymer containing 1.0 to 5.0% by weight of ethylene;
Component (2) 3 to 30% by weight of an ethylene-propylene copolymer containing 70 to 90% by weight of ethylene; and component (3) a nucleating agent,
Melt flow rate (230 ° C, load 21.18 N) 1.0 to 10 g / 10 min,
A polypropylene composition having an XSIV (inherent viscosity of xylene solubles) of 0.5 to 2.0 dl / g,
A sheet or film obtained by a method comprising: biaxially orienting at a temperature Ts (° C.); and cooling the biaxially oriented shaped body while maintaining its surface state,
When the peak top temperature of the melting point on the highest temperature side derived from the component (1) or (2) in the second scan with a differential scanning calorimeter (DSC) of the polypropylene composition is Tm (° C.),
Satisfy 0 ≦ Ts−Tm ≦ 10,
Sheet or film. At least a portion of the component (1) and at least a portion of the component (2) are
(A) A solid catalyst containing magnesium, titanium, halogen, and a succinate-based compound as an electron donor compound,
The sheet or film according to claim 1, which is produced using a catalyst comprising (B) an organoaluminum compound, and (C) an external electron donor compound.   The sheet or film according to claim 1 or 2, wherein 0.05 to 1.0 parts by weight of the nucleating agent is contained with respect to a total of 100 parts by weight of the components (1) and (2).   The polypropylene composition is a composition produced by a method including the step of polymerizing propylene and ethylene which are raw materials of component (1) and component (2) using two or more reactors. The sheet or film according to any one of Items 1 to 3.   The sheet or film according to any one of claims 1 to 4, wherein the nucleating agent is selected from the group consisting of a sorbitol-based nucleating agent, a nonitol-based nucleating agent, and a phosphate ester-based nucleating agent.   The nucleating agent is 1,3: 2,4-bis-o- (4-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-o- (3,4-dimethylbenzylidene) -D The method according to any one of claims 1 to 5, which is selected from the group consisting of -sorbitol and 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol. Sheet or film.   The molded object which has a layer which consists of a sheet | seat or a film in any one of Claims 1-6.   The secondary molded object formed by shape | molding the molded object of Claim 7. I. Component (1) 70 to 97% by weight of a propylene-ethylene copolymer containing 1.0 to 5.0% by weight of ethylene;
Component (2) 3 to 30% by weight of an ethylene-propylene copolymer containing 70 to 90% by weight of ethylene; and component (3) a nucleating agent,
Melt flow rate (230 ° C, load 21.18 N) 1.0 to 10 g / 10 min,
Preparing a polypropylene composition having an XSIV (inherent viscosity of xylene solubles) of 0.5 to 2.0 dl / g,
II. Biaxially orienting the polypropylene composition at a temperature Ts (° C.), and III. Including the step of cooling while maintaining the surface state of the molded body after the biaxial stretching;
When the peak top temperature of the melting point on the highest temperature side derived from the component (1) or (2) in the second scan in DSC of the polypropylene composition is Tm (° C.),
Satisfy 0 ≦ Ts−Tm ≦ 10,
How to make a sheet or film. Said process I is
At least a portion of the component (1) and at least a portion of the component (2),
(A) A solid catalyst containing magnesium, titanium, halogen, and a succinate-based compound as an electron donor compound,
Comprising a process comprising (B) an organoaluminum compound, and (C) a catalyst comprising an external electron donor compound,
The manufacturing method of the sheet | seat or film of Claim 9. The manufacturing method according to claim 9 or 10, wherein the step of cooling includes cooling the molded body to 80 ° C or less.