200400224 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關由聚丙烯樹脂組成物所構成之澆鑄薄膜 。詳言之係有關由含具有特定組成分布之二甲苯可溶分之 聚丙烯樹脂組成物所構成之澆鑄薄膜。更詳言之係有關透 明性優越，低溫下之耐衝擊性及耐熱性•剛性均優越之澆 鑄薄膜。又本發明亦係有關柚皮狀、落袋強度及耐結塊性 均優越之容器。 本申請案係本諸日本特願2002-135752及特願 2003-125360者，取其記載之內容爲本說明書之一部份。 【先前技術】 使用聚丙烯之成形品其經濟性優越而廣泛使用於各種 領域。 然而，一般使用聚丙烯單聚物之成形品雖具有高剛性 ，但反之其耐衝擊性，特別是低溫下之耐衝擊性變差。 因此，爲提昇耐衝擊性而有許多提案，例如可例舉如 ，先製造丙烯均聚物後再製造乙烯-丙烯共聚物彈性體之 丙烯嵌段共聚物。使用該丙烯系嵌段共聚物之成形品由於 耐衝擊性優越，而可廣泛使用於汽車、家電領域等各產業 領域。 然而，該丙烯系嵌段共聚物雖然低溫下之耐衝擊性' 剛性優越，但透明性甚差，不適用於要求透明性之用途’ 而有用途受限之缺點。 -5- (2) (2)200400224 因此針對解決該缺點而進行種種檢討，例如’日本特 開平6-93 06 1號公報、特開平6-3 1 3 04 8號公報、特開平 7-2 86020號公報及特開平8-2723 8號公報揭示結晶性聚丙 烯與聚丙烯共聚物彈性體其個別之黏度，控制其黏度比及 其含量之丙烯嵌段共聚物。 然而，此等之中其耐衝擊性與剛性之平衡及透明性均 不足，此外使用此等於薄膜領域時有熱封強度不足之問題 。再者，由此類薄膜所構成之容器有產生柚皮狀而不佳， 且落袋強度低，耐結塊性差等問題。 本發明乃爲解決前述問題，其目的係提供低溫下之耐 衝擊性與剛性之平衡及透明性均優越，且熱封強度亦優越 之澆鑄薄膜。 又，本發明之另一目的係提供澆鑄薄膜之製造方法， 及使用澆鑄薄膜所構成之容器，該容器爲柚皮狀被抑制且 落袋強度、耐結塊性優越者。 【發明內容】 本發明人等爲解決前述習知技術之問題，針對聚丙烯 樹脂組成物之二甲苯可溶分之組成分布銳意進行檢討之結 果，發現具有特定組成分布之二甲苯可溶分之聚丙烯樹脂 共聚物，不僅低溫下之耐衝擊性與剛性之平衡及透明性均 優越，且作成薄膜時其熱封強度亦優越而完成本發明。 亦即本發明之澆鑄薄膜係由含有（A)聚丙烯成分 50-80質量％與（B)丙烯與乙烯及/或碳數4至12之α· -6 - (3) (3)200400224 儲煙之共聚物彈性體成分5 0 · 2 0質量％之組成物所構成， 其特徵爲該組成物係： 融體流速爲0.1-15.0g/分鐘之範圍、 上述（B )共聚物彈性體成分中源自丙烯之單元爲 5 0 · 8 5質量％、且 二甲苯可溶分Xs能滿足下列（I)至（V)之條件者 〇 (I )丙烯含量Fp爲5 0-8 5質量％。 (II)二甲苯可溶分Xs之特性黏度[77]XS爲1.4-5dL/g 。 (III )特性黏度[7? ]xs與二甲苯不溶分xi之特性黏 度[]Xi之比爲 〇·7·1·5。 （ IV )以雙觀測模式（two sight model)定義之高丙烯含量成分之丙烯含量（Pp)爲 60質量％以上 95質量％以下，低丙烯含量成分之丙烯含 量（)爲20質量％以上60質量％以下。 (V )以雙觀測模式定義之高丙烯含量成分之丙烯含 量（Pp)與低丙烯含量成分之丙烯含量（P’p)、高丙烯 含量成分在上述Fp中所佔之比例（Pfl )及低丙烯含量成 分在上述Fp中所佔之比例（1-Pn )能滿足以下之式（1 ) 及式（2 ):200400224 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a casting film composed of a polypropylene resin composition. Specifically, it relates to a cast film composed of a polypropylene resin composition containing a xylene soluble component having a specific composition distribution. More specifically, it relates to a cast film which is superior in transparency, impact resistance at low temperatures, heat resistance and rigidity. The present invention also relates to a container which is excellent in pomelo peel shape, bag dropping strength, and blocking resistance. This application is based on Japanese Patent Application No. 2002-135752 and Japanese Patent Application No. 2003-125360. The content of this application is part of this specification. [Prior art] Molded products using polypropylene are widely used in various fields because they are economically superior. However, although a molded product using a polypropylene monopolymer generally has high rigidity, its impact resistance, in particular, impact resistance at low temperatures is deteriorated. Therefore, there are many proposals for improving the impact resistance. For example, for example, a propylene homopolymer may be produced first, and then a propylene block copolymer of an ethylene-propylene copolymer elastomer may be produced. The molded product using this propylene-based block copolymer is widely used in various industrial fields such as automobiles and home appliances because of its excellent impact resistance. However, although this propylene-based block copolymer is superior in impact resistance at low temperatures, it has excellent rigidity, but has poor transparency, and is not suitable for applications requiring transparency ', and has the disadvantage of limited use. -5- (2) (2) 200400224 Therefore, various reviews have been conducted to address this shortcoming, such as' Japanese Patent Laid-Open No. 6-93 06 No. 1, Japanese Patent Laid-Open No. 6-3 1 3 04 8, Japanese Patent Laid-Open No. 7-2 Publication No. 86020 and Japanese Patent Application Laid-Open No. 8-2723 No. 8 disclose propylene block copolymers in which crystalline polypropylene and polypropylene copolymer elastomers have individual viscosities, and their viscosity ratios and contents are controlled. However, among them, the balance of impact resistance and rigidity and transparency are insufficient, and in addition, when this is used in the film field, there is a problem of insufficient heat seal strength. Furthermore, containers made of such films have problems such as poor pomelo peel, low bag drop strength, and poor blocking resistance. The present invention is to solve the aforementioned problems, and its object is to provide a cast film which is excellent in balance of impact resistance and rigidity at low temperatures, has excellent transparency, and has excellent heat seal strength. Another object of the present invention is to provide a method for producing a cast film, and a container formed by using the cast film. The container is one having suppressed pomelo peel shape and excellent bag drop strength and blocking resistance. [Summary of the Invention] In order to solve the problems of the conventional technology described above, the inventors conducted an intensive review on the composition distribution of xylene solubles in polypropylene resin compositions, and found that xylene solubles with specific composition distribution The polypropylene resin copolymer not only has excellent balance of impact resistance and rigidity and transparency at low temperature, but also has excellent heat-sealing strength when it is made into a film, and completed the present invention. That is, the casting film of the present invention is composed of (A) polypropylene component 50-80 mass% and (B) propylene and ethylene and / or carbon number 4 to 12 α · -6-(3) (3) 200400224 storage The smoke copolymer elastomer component is composed of a composition of 50 to 20% by mass, and is characterized in that the composition is: a melt flow rate in a range of 0.1 to 15.0 g / min, and the (B) copolymer elastomer component The unit derived from propylene is 50.85% by mass, and the xylene solubles Xs can satisfy the following conditions (I) to (V). (I) The propylene content Fp is 5 0-8 5 mass%. . (II) The intrinsic viscosity of the xylene solubles Xs [77] XS is 1.4-5dL / g. (III) The ratio of the intrinsic viscosity [7?] Xs to the intrinsic viscosity [] Xi of the xylene-insoluble component xi is 0.7 · 1.5. (IV) The propylene content (Pp) of the high propylene content component defined by the two sight model is 60 mass% to 95 mass%, and the propylene content () of the low propylene content component is 20 mass% to 60 mass %the following. (V) The propylene content (Pp) of the high propylene content component and the propylene content (P'p) of the low propylene content component, the proportion of the high propylene content component (Pfl), and the low The proportion (1-Pn) of the propylene content component in the above-mentioned Fp can satisfy the following formulas (1) and (2):
Pp/P'p^ 1.90 ........... ( 1 ) 2.00<Pfl/ ( 1 -Pfi ) <6.00 .......... ( 2 ) 此種澆鑄薄膜特別是低溫下之耐衝擊性與剛性之平衡 及透明性均優越，此外其熱封強度亦甚爲優越。因而可使 (4) (4)200400224 用於以汽車、家電領域爲首，更廣泛之用途。 又，二甲苯可溶分Xs之丙烯含量Fp以60質量％以 上爲宜。藉由使二甲苯可溶分Xs之丙烯含量Fp大於60 質量％，可進一步提高澆鑄薄膜之透明性與熱封強度。 又，以二甲苯不溶分Xi之曲折率爲1.490-1.510，二 甲苯可溶分Xs之曲折率爲1.470-1.490之範圍爲宜。藉由 使二甲苯不溶分Xi之曲折率及二甲苯可溶分Xs之曲折率 落於特定範圍內，可使澆鑄薄膜之透明性、耐衝擊性、剛 性及耐熱性達到更高次元之平衡。 又，本發明澆鑄薄膜之製造方法，其特徵係使用金屬 濾器將上述組成物於熔融狀態下過濾後再成形者。 此處，上述金屬纖維濾器以使用依據JIS B 8 3 5 6之過 濾精確度爲5至150#m者爲宜。 又本發明之積層體其特徵爲具有選自鋁箔、金屬蒸鍍 薄膜層、氧化矽蒸鍍薄膜層、偏氯乙烯樹脂層、乙烯-乙 酸乙烯酯共聚物樹脂鹼化物樹脂層、聚醯胺樹脂層、聚酯 樹脂層、聚碳酸酯樹脂層及氧氣吸收劑層之至少一層與本 發明澆鑄薄膜所構成之層者。 又’本發明之容器係以使用本發明之澆鑄薄膜爲其特 徵。又’本發明之容器係以使用本發明之積層體爲其特徵 。此種容器係抑制柚皮狀且落袋強度、耐結塊性均優越。 【實施方式】 本發明之聚丙烯樹脂組成物係含有（A )聚丙烯成分 -8 - (5) (5)200400224 與（B )共聚物彈性體成分之組成物。 本發明中（A)聚丙烯成分係選自丙烯單聚物或丙烯 與乙烯及/或碳數4至12之α-烯烴之共聚物及此等之混 合物者。此處，碳數4至12之α-烯烴可使用1-丁烯、1-戊烯、1-己烯、1_庚烯、1-辛烯、1-癸烯、4-甲基-1-戊烯 等之任一者。此等聚合物可單獨使用亦可2種以上混合使 用。 但是，本發明中（A )聚丙烯成分係指源自丙烯之單 元爲95質量％以上者，而此等共聚成分之含量爲5.0質量 %，更好爲〇·1至3.5質量％者。乙烯及/或碳數4至12之 α -烯烴之含量若大於5質量％，則成形品之剛性及耐熱性 顯著降低而不佳。 此等聚合物例如可使用周知之齊格勒納塔系觸媒或芳 環烯金屬觸媒，依據周知聚合方法製造者。 (A )聚丙烯成分在特別要求剛性與耐熱性之情況下 ，以丙烯單聚物爲佳。又，在特別要求耐衝擊性與透明性 之情況下，以丙烯與乙烯及/或α -烯烴之共聚物爲佳。 (Α)聚丙烯成分之特性黏度[;?]以2.0-4.8dL/g爲宜 ，更好爲2.5-4.5dL/g，最好爲2.8-4.0dL/g之範圍。特性 黏度[7?]超過4.8dL/g時，則有成形時擠出不良與成形品 透明性低下之問題。又，特性黏度[7?]小於2.0dL/g時， 雖無成形時擠出不良與成形品透明性低下之問題，但有製 品之剛性及耐衝擊性降低之問題。 本發明中（B )共聚物彈性體成分爲丙烯與乙烯及/或 -9- (6) (6)200400224 碳數4至1 2之α -烯烴之共聚物彈性體成分。構成共聚物 彈性體成分之碳數4至1 2之α -烯烴可使用任意者，具體 例示如1 - 丁烯、卜戊烯、1 ·己烯、1 -庚烯、卜辛烯、1 -癸 烯、4_甲基-1-戊烯等。 本發明中（Β )共聚物彈性體成分係指源自丙烯之單 元爲50-85質量％者，較好爲55-85質量％，更好爲55-80 質量％。超過 8 5質量％則低溫下之耐衝擊性不足，小於 5 〇質量％則有透明性降低且熱封強度亦降低之情況。 本發明中之聚丙烯樹脂組成物係含有上述（A )聚丙 烯成分5 0- 8 0質量％與（B )共聚物彈性體成分50-20質量 %。於本發明之組成物中，若（B )共聚物彈性體成分之 含量小於20質量％則耐衝擊性變差，若超過50質量％則 剛性與耐熱性變差。（B )共聚物彈性體成分之含量較好 在4 5 -20質量％之範圍，更好爲40-23質量％之範圍。 本發明之聚丙烯樹脂組成物，其融體流速（下文簡稱 爲M RF )爲0.1-1 5.0 g/ΙΟ分鐘之範圍，就成形品之透明性 、剛性及耐衝擊性之觀點而言以0.5-10.0 g/ΙΟ分鐘之範圍 較佳，0.7-7.0g/10分鐘之範圍更佳。MRF小於0.1g/10分 鐘時，以擠壓機混鍊時或成形時會有各成分分散不佳或吐 出不良之情況，結果有成形品之耐衝擊性、剛性或透明性 降低之問題。又，MRF超過15.0g/10分鐘時，有耐衝擊 性或透明性降低之問題。又，MRF係依據JIS K7210，於 2 3 0°C，2.16kg荷重下測定之値。 本發明之聚丙烯樹脂組成物，係含有20-5 0質量％之 -10· (7) (7)200400224 二甲苯可溶分Xs。二甲苯可溶分Xs以20-45質量％之範 圍較佳，23-40質量％之範圍更佳。 上述二甲苯可溶分之丙烯含量Fp爲50-85質量％， 以60- 8 0質量％爲佳。特別是超過6〇質量％更佳，以65-8 0質量％更佳，再更佳爲7 0 - 8 0質量％之範圍，最佳爲 70-78質量％。二甲苯可溶分之丙烯含量若小於5〇質量％ 則透明性低下，此外作成薄膜時其熱封強度亦低下。又， 丙烯含量Fp超過80質量％時，低溫下之耐衝擊性降低。 本發明之聚丙烯樹脂組成物中二甲苯可溶分之特性黏 度[C]Xs爲1.4-5.0dL/g之範圍，較好爲2.0-4.5dL/g之範 圍，更好爲2.5-4.0dL/g之範圍。特性黏度[77]XS若超過 5 .OdL/g，則雖能提高耐衝擊性但其透明性降低。又，特 性黏度[7? ]Xs若小於1.4dL/g，則因耐衝擊性降低而不佳 〇 本發明之聚丙烯樹脂組成物中，聚丙烯樹脂組成物之 二甲苯可溶分之特性黏度[7? ]XS與二甲苯不溶分Xi之特 性黏度[W ]Xi之比爲0.7-1.5之軔圍，以0.7-1.3之範圍較 佳，0.8-1.2之範圍更佳。該比値質若小於0.7則雖能提高 透明性但低溫下之耐衝擊性降低，若超過1 · 5則透明性降 低。 二甲苯可溶分之曲折率以1.470- 1.490爲宜，較好爲 1.470-1.485，更好爲1.473-1.485。二甲苯可溶分之曲折 率大於1.490時，雖透明性提昇但耐衝擊性降低。又，小 於1.470時雖耐衝擊性提昇但透明性降低。 -11 - (8) (8)200400224 又，二甲苯不溶分之曲折率以1.490- 1.5 1 0爲宜，較 好爲1.493-1.505，更好爲1.495-1.503之範圍。二甲苯不 溶分之曲折率小於1.490時，雖透明性及耐衝擊性提昇， 但剛性及耐熱性降低。另一方面，若大於1 · 5 1 0則剛性及 耐熱性提昇但耐衝擊性易降低。 於上述二甲苯可溶分Xs中，依據雙觀測模式定義之 高丙烯含量成分之丙烯含量Pp與低丙烯含量成分之丙烯 含量P’p、高丙烯含量成分在前述Fp所佔之比例Pfl及低 丙烯含量成分在前述Fp所佔之比例（1-Pfl )爲滿足式（1 )及式（2)者：Pp / P'p ^ 1.90 ........... (1) 2.00 < Pfl / (1 -Pfi) < 6.00 .......... (2) This type of casting The film has excellent impact resistance, rigidity balance and transparency at low temperature, and its heat seal strength is also very good. Therefore, (4) (4) 200400224 can be used in a wider range of applications, including automotive and home appliances. The propylene content Fp of the xylene solubles Xs is preferably 60% by mass or more. By making the propylene content Fp of the xylene soluble Xs greater than 60% by mass, the transparency and heat-sealing strength of the cast film can be further improved. Further, it is preferable that the tortuosity ratio of the xylene-insoluble component Xi is 1.490 to 1.510, and the tortuosity ratio of the xylene-soluble component Xs is 1.470 to 1.490. By making the tortuosity of the xylene insoluble Xi and the tortuosity of the xylene soluble Xs fall within a specific range, the transparency, impact resistance, rigidity, and heat resistance of the cast film can reach a higher-order balance. The method for producing a cast film according to the present invention is characterized by using a metal filter to filter the above-mentioned composition in a molten state and then forming it. Here, it is preferable that the above-mentioned metal fiber filter has a filtration accuracy of 5 to 150 #m in accordance with JIS B 8 3 5 6. The laminated body of the present invention is characterized in that it has a material selected from the group consisting of aluminum foil, metal vapor-deposited film layer, silicon oxide vapor-deposited film layer, vinylidene chloride resin layer, ethylene-vinyl acetate copolymer resin alkali compound resin layer, and polyamide resin At least one layer of a layer, a polyester resin layer, a polycarbonate resin layer, and an oxygen absorber layer, and a layer composed of the cast film of the present invention. The container of the present invention is characterized by using the cast film of the present invention. Also, the container of the present invention is characterized by using the laminated body of the present invention. This type of container is excellent in suppressing pomelo peel and has bag dropping strength and blocking resistance. [Embodiment] The polypropylene resin composition of the present invention is a composition containing (A) polypropylene component -8-(5) (5) 200400224 and (B) copolymer elastomer component. (A) The polypropylene component in the present invention is selected from the group consisting of a propylene monopolymer or a copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbons and a mixture thereof. Here, as the α-olefin having 4 to 12 carbon atoms, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1 can be used. -Any of pentene and the like. These polymers may be used alone or in combination of two or more. However, in the present invention, the (A) polypropylene component means a unit derived from propylene of 95% by mass or more, and the content of these copolymerization components is 5.0% by mass, and more preferably from 0.1 to 3.5% by mass. When the content of ethylene and / or α-olefin having 4 to 12 carbons is more than 5% by mass, the rigidity and heat resistance of the molded product are significantly reduced and unfavorable. These polymers can be produced according to a known polymerization method using, for example, a known Ziegler-Natta catalyst or an aromatic metal catalyst. (A) When rigidity and heat resistance are particularly required for a polypropylene component, a propylene monopolymer is preferred. When impact resistance and transparency are particularly required, a copolymer of propylene with ethylene and / or an α-olefin is preferred. (Α) The intrinsic viscosity [;?] Of the polypropylene component is preferably 2.0-4.8 dL / g, more preferably 2.5-4.5 dL / g, and most preferably 2.8-4.0 dL / g. When the viscosity [7?] Exceeds 4.8dL / g, there are problems of poor extrusion during molding and low transparency of the molded product. In addition, when the intrinsic viscosity [7?] Is less than 2.0 dL / g, although there is no problem of poor extrusion during molding and low transparency of the molded product, there is a problem of reduced rigidity and impact resistance of the product. The (B) copolymer elastomer component in the present invention is a copolymer elastomer component of propylene and ethylene and / or -9- (6) (6) 200400224 α-olefin having 4 to 12 carbon atoms. Any α-olefin having 4 to 12 carbon atoms constituting the elastomer component of the copolymer may be used. Specific examples include 1-butene, pentene, 1.hexene, 1-heptene, bucinene, 1- Decene, 4-methyl-1-pentene, etc. The (B) copolymer elastomer component in the present invention refers to a unit derived from propylene in an amount of 50 to 85% by mass, preferably 55 to 85% by mass, and more preferably 55 to 80% by mass. If it exceeds 85% by mass, the impact resistance at low temperature is insufficient, and if it is less than 50% by mass, transparency may decrease and heat seal strength may decrease. The polypropylene resin composition in the present invention contains the above-mentioned (A) polypropylene component of 50 to 80% by mass and (B) a copolymer elastomer component of 50 to 20% by mass. In the composition of the present invention, if the content of the (B) copolymer elastomer component is less than 20% by mass, impact resistance is deteriorated, and when it exceeds 50% by mass, rigidity and heat resistance are deteriorated. The content of the (B) copolymer elastomer component is preferably in the range of 45 to 20% by mass, more preferably in the range of 40 to 23% by mass. The polypropylene resin composition of the present invention has a melt flow rate (hereinafter abbreviated as M RF) in the range of 0.1 to 5.0 g / 10 minutes, and from the viewpoint of transparency, rigidity, and impact resistance of the molded product, it is 0.5. A range of -10.0 g / 10 minutes is preferable, and a range of 0.7-7.0 g / 10 minutes is more preferable. When the MRF is less than 0.1 g / 10 minutes, the components may be poorly dispersed or discharged badly when mixed with an extruder or during molding, and as a result, the impact resistance, rigidity, or transparency of the molded product may be reduced. When the MRF exceeds 15.0 g / 10 minutes, there is a problem that the impact resistance or transparency is reduced. The MRF is measured in accordance with JIS K7210 at 230 ° C and a load of 2.16 kg. The polypropylene resin composition of the present invention contains 20-50% by mass of -10 · (7) (7) 200400224 xylene soluble Xs. The xylene solubles Xs is preferably in the range of 20 to 45% by mass, and more preferably in the range of 23 to 40% by mass. The propylene content Fp of the xylene solubles is 50 to 85% by mass, and more preferably 60 to 80% by mass. In particular, it is more preferably more than 60% by mass, more preferably 65 to 80% by mass, even more preferably 70 to 80% by mass, and most preferably 70 to 78% by mass. If the propylene content of the xylene soluble content is less than 50% by mass, the transparency is low, and the heat-sealing strength is also low when a film is formed. When the propylene content Fp exceeds 80% by mass, the impact resistance at low temperatures decreases. The intrinsic viscosity [C] Xs of the xylene solubles in the polypropylene resin composition of the present invention is in the range of 1.4-5.0 dL / g, preferably in the range of 2.0-4.5 dL / g, more preferably 2.5-4.0 dL / g range. If the intrinsic viscosity [77] XS exceeds 5.0 OdL / g, the impact resistance is improved but the transparency is reduced. In addition, if the intrinsic viscosity [7?] Xs is less than 1.4dL / g, the impact resistance is not good. The polypropylene resin composition of the present invention has an intrinsic viscosity of xylene soluble content of the polypropylene resin composition. [7?] The intrinsic viscosity of XS and xylene-insoluble Xi [W] The ratio of Xi to the range of 0.7-1.5 is preferable, and the range of 0.7-1.3 is preferable, and the range of 0.8-1.2 is more preferable. If the specific gravity is less than 0.7, the transparency can be improved, but the impact resistance at low temperatures is reduced, and if it exceeds 1.5, the transparency is reduced. The tortuosity of the xylene solubles is preferably 1.470-1.490, more preferably 1.470-1.485, more preferably 1.473-1.485. When the tortuosity of xylene solubles is greater than 1.490, the transparency is improved but the impact resistance is reduced. When it is less than 1.470, the impact resistance improves but the transparency decreases. -11-(8) (8) 200400224 Also, the tortuosity of the xylene insoluble content is preferably 1.490-1.5 1 0, more preferably 1.493-1.505, and more preferably 1.495-1.503. When the xylene insoluble tortuosity is less than 1.490, the transparency and impact resistance are improved, but the rigidity and heat resistance are reduced. On the other hand, if it is more than 1 · 5 10, rigidity and heat resistance are improved, but impact resistance is liable to decrease. In the above xylene solubles Xs, the propylene content Pp of the high propylene content component and the propylene content P'p of the low propylene content component, and the proportion Pfl of the high propylene content component in the aforementioned Fp and low are defined according to the dual observation mode. The proportion (1-Pfl) of the propylene content component in the aforementioned Fp is one that satisfies the formulas (1) and (2):
Pp/Pfp^ 1.90 ........... ( 1 ) 2.00<Pfi/ ( 1-Pfi ) <6.00 .......... ( 2 )。Pp / Pfp ^ 1.90 ........... (1) 2.00 < Pfi / (1-Pfi) < 6.00 .......... (2).
Pp/P’p 小於 1·90 時，或 Pfl/ ( 1-Pfl )小於 2.00 時， 由於二甲苯可溶分與二甲苯不溶分之介面強度降低而使熱 封強度降低。又’ Pf】/ ( 1-Ρη )大於6.00時，雖上述介面 強度提高但剛性及耐衝擊性降低。上述不等式係表示二甲 苯可溶分組成分布之指標，上述式（1)爲由前述2個活 性點生成成分之組成差之大小，而前述式（2 )爲有關由 前述2個活性點生成之成分生成量之大小。 又，高丙烯含量成分之丙烯含量（Pp)爲60質量％ 以上95質量％以下，較好爲65-90質量％，更好爲70-90 質量％。丙烯含量成分之丙烯含量（P ’ p )爲2 0質量％以 上60質量％以下，較好爲25-55質量％，更好爲30-50質 量％ 〇 •12- (9) (9)200400224 有關雙觀測模式其定義係陳述於Η. N. Cheng,應用 聚合物科學期刊（Journal of Applied Polymer Science) ’弟 卷’弟 1639-1650 ( 1988)。亦即，假定丙燃優 先聚合之活性點（P )與乙烯優先聚合之活性點（P，）2點 ，此2活性點中之反應槪率，亦即，以丙烯含量Pp及Pp’ 與’丙烯優先聚合之活性點（P )在活性點點全體之比例 Pn爲參數，使用表1之槪率方程式，使與實際之13C-N M R圖譜之相對強度及該槪率方程式成爲一致，藉由使 上述3個參數最適化即可求得。如此求得之Ρρ、Ρρ，及Pfl ，與丙烯含量Fp係滿足下式（3)之關係。When Pp / P’p is less than 1.90, or when Pfl / (1-Pfl) is less than 2.00, the heat seal strength is lowered because the interface strength of xylene solubles and xylene insolubles decreases. When 'Pf] / (1-Pη) is more than 6.00, the rigidity and impact resistance of the interface are improved, although the interface strength is improved. The above inequality is an index indicating the distribution of the soluble component of xylene. The above formula (1) is the difference in composition of the components generated from the two active points, and the foregoing formula (2) is related to the component generated from the two active points. The amount of component production. The propylene content (Pp) of the high propylene content component is 60% by mass or more and 95% by mass or less, preferably 65-90% by mass, and more preferably 70-90% by mass. The propylene content (P'p) of the propylene content component is 20% by mass or more and 60% by mass or less, preferably 25-55% by mass, and more preferably 30-50% by mass 〇 • 12- (9) (9) 200400224 The definition of the dual observation model is stated in Η. N. Cheng, 'Journal of Applied Polymer Science' 'Young' 1639-1650 (1988). That is, it is assumed that there are two active points (P) of propylene combustion preferential polymerization and active points (P,) of ethylene preferential polymerization, and the reaction ratio in these two active points, that is, the propylene content Pp and Pp 'and' The ratio Pn of the active point (P) of propylene preferential polymerization to the entire active point is used as a parameter, and the rate equation of Table 1 is used to make the relative intensity of the actual 13C-NMR spectrum and the rate equation consistent. The above three parameters can be obtained by optimization. The thus obtained Pρ, Pρ, and Pfl and the propylene content Fp satisfy the relationship of the following formula (3).
Fp = Pp X Pfi + Ppf χ ( l_Pfl ) .......... ( 3 )Fp = Pp X Pfi + Ppf χ (l_Pfl) .......... (3)
Pp及Pp’較好爲滿足下式（4 )，更好爲滿足下式（5 )者。 1 .95 S Pp/P，p ^ 2.40 .......... ( 4 ) 1.95^ Pp/P'p ^ 2.35 .......... ( 5 )Pp and Pp 'preferably satisfy the following formula (4), and more preferably satisfy the following formula (5). 1 .95 S Pp / P, p ^ 2.40 .......... (4) 1.95 ^ Pp / P'p ^ 2.35 .......... (5)
Pn/ ( 1-Pn )較好爲滿足下式（6 )，更好爲滿足下 式（7)者。 2.50^ Pfi/ ( l-pfl) <5.50......... ( 6) 3.00^ Pfi/ ( 1-Pfl ) <5.〇〇......... ( 7 ) 又’ Pp、Pp’、Fp及Pfl可依據13C_NMR圖譜之統計 解析而求得。 (10)200400224 雙觀側模式之槪率方程式 Pp2xPfi + P5P2x(1 - Pfi) (―2Pp3+ 2Pp2)xPn + (― 2Ρ，ρ3+ 2Ρ’ρ2)χ(1 - Ρη) (2Pp3 — 4Pp2+ 2Ρρ)χΡη + (2P，p3 — 4P，p2+ 2Ρ，ρ)χ(1 — Pn) (Pp3 — 2Pp2 + Pp)xPfl + (P，p3 — 2P，p2 + P，p)x(l - Pfl) (Pp4- 4Pp3+ 3Pp2)xPf, + (P'p4- 4Pp3+ 3P,p2)x(1 - Pfl) (—2Pp4+ 6Pp3 — 6Pp2+ 2Pp)xPf, + ( — 2P’p4+ 6P、3- 6P’p2+ 2P’p)x(l - Pf丨） (Pp4 — 5Pp3+ 9Pp2 — 7Pp+ 2)xPr丨 + (P，p4- 5P’p3+ 9P’p2 — 7P，p+ 2)x(l — Pf丨） Pp3xPf. + Pfp3x(I - Pfl) (2Pp3 - 4Pp2+ 2Pp)xPf, + (2P’p3 - 4P，p2+ 2P，p)x(l - Pf丨） (—Pp3+ 2Pp2)xPfl + ( — P，p3+ P，p2)x(l — Pfl) 訊號 (1 )S a a (2) S a r (3) S a δ (4) T 5 (5 (5) S r r + Ύ β δ (6) S r δ (7) S (5 (5 (8) T/3 /3 (9) S β δ (l〇)S/S /3 14- (11) (11)200400224 以下例舉（B )成分爲丙烯·乙烯共聚物彈性體之情況 說明上述方法。 第1圖爲典型丙烯-乙烯共聚物彈性體的13c-nmr圖 言普’該圖譜爲連接鏈分布（乙烯與丙烯並列方式）不同之 1〇個1相異波峰。該連接鏈之名稱記述於巨分子（ Macrom〇iecules)，第 10 卷，第 5 3 6·5 44 頁，1 9 7 7，命 名如第2圖。若假定此種連接鏈爲共聚之反應機制，則可 用反應槪率之積表示。因而，以全體之波峰強度爲1時各 (1 )至（1 0 )之波峰相對強度，係以反應槪率及各觀測 之存在比爲參數，依據伯勞利（Bernoull )統計法可作爲 槪率方程式表現。（1 )爲S α α時，丙烯單元以符號P、 乙烯單元以符號Ε表示，則取自其之連接鏈爲[ρρρρ]、 [ΡΡΕΕ]、[ΕΡΡΕ]3種，此等各自分別以反應槪率表示，其 基部相合。其餘（2 )至（1 〇 )之波峰亦可用相同方法建 立方程式，則可求得使此等1 0個方程式與實際測定之波 峰強度最爲接近之參數’亦即藉由使前述Ρρ、Ρρ，及Pfl最 適化即可求得。最適化之際，進行回歸計算至最小自乘法 所得波峰強度之測定値與表1所示各式所得之理論値之餘 差成爲1 X 1 (Γ5以下。進行此種回歸計算之計算法等，例 如Η · N· CHENG ’應用聚合物科學期刊，第3 5卷，第 1 63 9- 1 6 5 0 ( 1 9 8 8 )所記載者。 繼之說明本發明中聚丙烯樹脂組成物之製造方法。本 發明之聚丙烯樹脂組成物之製造方法並無特別限制，可採 用公知之方法。例如，使用帶狀混合機、鼓狀混合機、韓 -15- (12) (12)200400224 蘇氏混合機等將（A)成分與（B)成分混合後，於17〇_ 280 t：，較好於190-26(rc之溫度下，以捏和機、混合輥 、班伯理混合機、單軸或雙軸擠壓機等加以融熔混鍊即可 製得。 又’本發明之聚丙嫌樹脂組成物亦可爲使（A )成分 與（B)成分以多段聚合方法於一個聚合系內製造而得者 。此外’亦可爲使（A)成分與（B)成分以多段聚合方 法於一個聚合系內製造後，另外再添加（A)成分及/或（ B )成分而得者。 上述聚丙烯成分（A)及/或共聚物彈性體成分（b) 可依據公知方法製造。具體而言，使用齊格勒觸媒或芳環 烯金屬觸媒使丙烯聚合或使丙烯與其他烯烴共聚即可製得 。齊格勒觸媒可例舉如三氯化鈦系觸媒或鎂負載型鈦觸媒 。鎂負載型觸媒系可例舉如由（a )鈦、鎂、鹵爲必須成 分之固體觸媒成分、（b )有機鋁化合物及（c )電子供給 性化合物構成之觸媒系。此等揭示於日本特開昭 5 7 - 63 3 1 0號、特開昭5 7-63 3 1 1號、特開昭5 8- 8 3 006號、 特開昭5 8 - 1 3 8 7 0 8號、特開昭62-205 07號、特開昭 61-296006號、特開平2-229806號、特開平2-33103號、 特開平2-707 08號各公報等。又，此等亦可作爲各成分製 造時先行使少量烯烴聚合之預備聚合觸媒使用。 製造本發明之（B)成分時，只要能充分滿足本發明 中組成物規定之製造條件即可，並無特別限制，可具體例 示如以下之方法。 -16- (13) (13)200400224 1.使用上述觸媒中可獲得組成分布、立體規則性分 布或分子量分布較廣泛之聚合物的觸媒以製造（B)成分 之方法。 2 ·以使組成分布體規則性分布或分子量分布較 廣泛之條件調製上述觸媒之方法，亦即改變電子供給性化 合物或有機鋁化合物之使用量，同時使用以數種電子供給 性化合物調製之觸媒製造而（B )成分之方法。 3 ·以使組成分布、立體規則性分布或分子量分布成 爲較廣泛之聚合條件之製造方法，亦即（一）藉由多階段 聚合並改變各階段溫度、單體組成比等聚合條件而製造（ B )成分之方法、（二）藉由一般所得之聚合物組成使組 成分布改變’調節共聚物彈性體之組成以獲得如目的組成 分布，而製造（B)成分之方法。 4·使用數種藉由芳環烯金屬觸媒等獲得之具有均勻 組成分布且丙烯含量不同之各成分之方法。 使用依據此等方法製造之（B )成分，即可容易地獲 得_h述二甲苯可溶分之組成分布經調節之聚丙烯成分樹脂 組成物。 製造上述各成分時，係採用於己烷、庚烷、燈油等鈍 性烴或丙嫌等液態α -烯烴溶劑之存在下進行淤漿聚合、 ^狀聚合或溶液聚合或氣相聚合等聚合方法，於室溫至 200°C ’較好於30至150°C之溫度範圍，0.2至5.0MPa壓 力範圍下進行。聚合步驟中反應器可適當使用該項技術領 域中常用者’例如可使用攪拌層型反應器、流動床型反應 -17- (14) (14)200400224 器、循環式反應器’以連續式，半分批式、分批式之任一 方法進行。又’聚合時例如可藉由添加氫等而調節所得聚 合物之分子量。 本發明之聚丙烯樹脂組成物中，在不損及本發明目的 之範圍內，可配合其他樹脂或添加劑等。此等其他添加劑 可例示如抗氧化劑、耐候性安定劑、帶電防止劑、滑劑、 抗結塊劑、防霧劑、染料、顏料、油、蠟等。 本發明之薄膜係以T印模法等使本發明之聚丙烯樹脂 組成物成形而得之澆鑄薄膜。該澆鑄薄膜可以單體形式使 用，亦可與其他材料積層後使用。 本發明薄膜之製造方法係以將上述聚丙烯樹脂組成物 於融熔狀態使用金屬纖維濾器過濾後，以各種薄膜成形法 成形者爲佳。 本發明中所用之金屬纖維濾器可例舉如金屬絲網濾器 、燒結金屬絲網濾器、多孔性金屬濾器、金屬纖維燒結濾 器及將此等濾器適當組合者。金屬纖維濾器係以依據JIS B8356過濾精密度爲5-150/zm者爲佳，20-120//m者更 佳，40- 1 00 // m者特佳。過濾精密度小於5 // m時擠出成 形時之壓力易上升，有損及成形性之可能，依據情況亦有 融熔樹脂之剪切發熱變激烈並產生氣體之情形。另一方面 若大於1 5 0 // m則有難以表現改良柚皮狀效果之傾向’且 澆鑄薄膜中易產生膠化微粒。金屬纖維濾器之形狀可例舉 如管形濾器、橋形圓筒濾器、葉碟形濾器、刮板形圓筒濾 器等。此等之中就柚皮狀改良效果、耐壓力及過濾面積2 -18- (15) (15)200400224 點而言以葉碟形濾器爲佳。金屬纖維濾器可使用購自曰本 精線股份有限公司「商品名：尼龍濾器」及富士濾器工業 股份有限公司「商品名：富士金屬纖維濾器」者。 上述金屬纖維濾器以設置於T印模成形機等薄膜成形 機之擠壓機與模頭之間爲佳，以融熔樹脂通過金屬濾器部 後隨即通過模頭之設置爲佳，設置於模頭附近更佳。設置 於擠壓機之金屬纖維濾器部之溫度以 200-2 8 (TC爲佳， 220-2 60 °C更佳。溫度小於20(TC則改良柚皮狀之效果不 足，亦容易發生擠壓壓力上升之情形。另一方面，若超過 2 8 0 °C則不僅樹脂劣化，改良柚皮狀之效果亦降低。 此等薄膜成形機中特別是使用T印模成形機，就所得 澆鑄薄膜之膜厚精確度優異、收縮率、強度等物性之各向 異性小及薄膜衝擊強度高等方面而言較佳。 本發明之積層體係於本發明之薄膜上，積層至少一層 選自鋁箔、金屬蒸鍍膜、氧化矽蒸鍍膜、偏氯乙烯樹脂層 、乙烯-乙酸乙烯酯共聚物樹脂鹼化物樹脂層、聚醯胺樹 脂層、聚酯樹脂層、聚碳酸酯樹脂層及氧氣吸收劑層之層 者。該等層之中，偏氯乙烯樹脂、乙烯·乙酸乙烯酯共聚 物鹼化物爲有效之氣體障避層。又，氧氣吸收劑層可例舉 如含氧化鐵之層等。 本發明之積層體係使用週知乾式層壓成形機等，經由 黏著劑’或以不經由黏著劑之共擠壓法、乾式層壓法及擠 壓層壓法，將上述之層積層即可獲得。 本發明之容器係使用本發明之薄膜或積層體者。容器 -19- (16) (16)200400224 可例舉將2片薄膜或積層體四方位熱封之袋狀容器、直立 袋等具自立性之袋狀容器等。包裝容器爲例如將2片薄膜 或積層體四方位，於溫度1 8 0 - 2 5 0 °C下進行熱封0.2 · 1 0秒 即可製作。 本發明之容器可適用爲食品等之加熱殺菌包裝容器。 特別是本發明之樹脂組成物及由其構成之薄膜及包裝容器 ，即使用於裝入以習用包裝容器裝袋時容易產生柚皮狀之 咖哩、五目御飯之原料、牛肉、豬肉及雞肉等油性食品進 行蒸煮殺菌處理時’仍爲不產生柚皮狀而外觀優越之容器 〇 又，本發明所謂之加熱殺菌係指將導致食品腐敗主要 原因之微生物滅菌之方法，雖視對象細菌而異，但一般係 於6 0 - 1 3 5 °C之溫度範圍下進行。此種以加熱殺菌中溫度 1 〇 0 °C以上之加熱蒸氣及熱水爲主體利用溫熱之方法即謂 蒸煮殺菌，爲不損及內容物之味道·風味以高溫短時間處 理之方法。 實施例 下文以實施例詳細說明本發明，但本發明並非限定於 此等者。 又，諸物性之測定方法如下。 熔體流速之測定：依據JIS K7210，於溫度23(rc，荷 重2 1 6 0 g之條件下測定。 13C-NMR 之測定（算出 Pp、Pp’及 Pfl ): -20- (17) 200400224 以日本電子製之JNM-GSX400測定（測定模ϊ 去偶合法，脈衝寬：8 . 〇 # s、脈衝反覆時間3.0 s、積 :1 0 0 0 0次、測定溫度：丨2 〇 °C、內部標準：六甲基二 、溶劑：1，2，4一三氯苯/苯_d6(容量比3/1)、試 :0.1g/ml)，依據該統計解析依前述計算方法求得 及 P f 1。 二甲苯可溶分X S之測定： 將樣品2 · 5 g放入鄰二甲苯2 5 0 m 1中，於加熱 並升溫至沸騰溫度，經3 0分鐘以上使完全溶解。 完全溶解後，於攪拌下放冷至1 0 0 °C以下，再於維; 之恆溫槽內保持2小時。然後用濾紙濾出析出之成 甲苯不溶分Xi )。繼之將濾液於加熱及氮氣流下 甲苯，經乾燥即可獲得二甲苯可溶分Xs。 丙烯含量之測定： 以上述13C-NMR之結果算出。 特性黏度之測定： 於癸烷中，1 3 5 °C下測定。 曲折率之測定： 分別將二甲苯可溶分Xs及二甲苯不溶分Xi壓 (23(TC下預熱5分鐘，脫氣30秒，6MPa下加壓 ，於30°C加壓下冷卻3分鐘）而製造厚度5 0- 8 0 // 膜。所得薄膜經常溫下24小時狀態調整後，以使 酸乙酯作爲中間液之阿塔克（Atac )公司製阿貝丨 )曲折計進行測定。 式：質子 分次數 矽氧烷 料濃度 Pp、Pp 下攪拌 確認已 W 2 5°c 分（二 餾除二 縮成形 1分鐘 m之薄 用水楊 Abbey -21 - (18) (18)200400224 (A)成分與（B)成分之製造： 依據下述以多段聚合之第1階段製造（A )成分，再 繼續以第2階段製造（B )共聚物彈性體成分。該等各成 分之物性値示於表2及3。 [PP-1之製造] 固體觸媒之調製 於氮大氣中，1 2 (TC下使5 6.8 g無水氯化鎂完全溶解 於100g無水乙醇、50 0ml日本出光興產（股）製之凡士 林油「CP15N」及5 00ml日本信越矽酮（股）製之矽酮油 「KF9 6」中。使用日本特殊機化工業（股）製之TK均質 機，於2 (TC將該混和物以5 0 0 0迴轉/分鐘攪拌2分鐘。於 維持攪捽同時不超過〇 °C之條件下，將其移至2公升無水 庚烷中。所得之白色固體以無水庚烷充分洗淨並於室溫下 真空乾燥，再於氮氣流下使部分脫乙醇化。將所得之 MgCl2· 1.2C2H5OH之球狀固體30g懸濁於200ml無水庚 烷中。於0°C及攪拌下以1小時之時間將5 00ml四氯化鈦 滴至其中，繼之加熱至40 °C並添加4.96g苯二甲酸二異丁 酯，並以約1小時升溫至100 °C。於1〇〇 °C反應2小時後 ’趁熱過濾並收集固體部分。然後，於該反應物中添加 5〇〇ml四氯化鈦並攪拌後，於120°C下反應1小時。反應 終了後，再度趁熱過濾並收集固體部分，以60 °C之己烷 1.0公升洗滌7次、以室溫之己烷1.0公升洗滌3次而獲 得固體觸媒。測定所得固體觸媒成分中之鈦含有率爲2 · 3 6 -22- (19) (19)200400224 質量％。 1) 預備聚合 於氮氣中，將500ml正庚院、6.0g三乙基絕、0.99g 環己基甲基二甲氧矽烷及l〇g上述所得之聚合觸媒投入3 公升之壓力釜中，於〇至5°c之溫度範圍下攪拌5分鐘。 繼之將欲聚合之丙烯供應至壓力釜內其量爲每lg聚合觸 媒投入1 〇 g丙烯，於〇至5 °c之溫度範圍進行預備聚合1 小時。所得之預備聚合觸媒以5 00ml正庚烷洗滌3次，並 用於以下之聚合。 2) 主聚合 第1階段：（A )聚丙烯成分之製造 於氮氣中，將2.0g上述方法製得之預備聚合固體觸 媒、11.4g三乙基鋁、1.88g環己基甲基二甲氧矽烷投入 內容積60公升且附有攪拌機之壓力釜中，繼之裝入18 kg 丙烯、對丙烯爲5 000mol ppm之氫氣，升溫至70°C並進 行聚合1小時。1小時後，去除未反應之丙烯以終結聚合 反應。 第2階段：（B )丙烯-乙烯共聚物彈性體之製造 如上述於第1階段聚合終結後，去除液態丙烯，於溫 度 7 5°C下，以2.2Nm3/小時之量供給丙烯/乙烯=26/74 ( 質量比）之混和氣體，並以對乙烯、丙烯及氫之合計量成 爲40，OOOmol ppm之量供給氫氣，聚合60分鐘。40分 鐘後去除未反應之氣體以終結反應。結果獲得6.6kg聚合 物。 -23- (20) (20)200400224 [PP-2之製造] 第2階段：（B )丙烯-乙烯共聚物彈性體之製造時， 除所供給之氫氣係使其使用量成爲5 0 ’ 0 0 0 m 01 P P m外， 與PP-1之製造同樣地進行聚合。結果獲得6.3kg聚合物 [PP-3之製造] 第2階段：（B )丙烯-乙烯共聚物彈性體之製造時’ 除所供給之氫氣係使其使用量成爲20 ’ 〇〇〇m〇l ppm外’ 與PP1之製造同樣地進行聚合。結果獲得5.8kg聚合物。 [PP_4之製造] 第1階段：（A )聚丙烯成分之製造 於氮氣中，將2.0g以PP-1方法調製之預備聚合固體 觸媒、11.4g三乙基鋁、1.88g環己基甲基二甲氧矽烷投 入內容積60公升且附有攪拌機之壓力釜中，繼之裝入 1 8kg丙烯、120L乙烯、對丙烯爲65 00m〇1 ppm之氫氣， 升溫至701：並進行聚合1小時。1小時後，去除未反應之 丙烯。 第2階段：（B )丙烯-乙烯共聚物彈性體之製造 除供給之氫氣成爲40，000m〇1 ppm並聚合40分鐘外 ，係與PP-1之製造同樣地進行聚合。結果獲得5.7kg聚 合物。 -24 - (21) (21)200400224 [PP-5之製造] 於第2階段中’除使供給之丙嫌/乙儲混和氣體之質 量比爲26/74，氫氣成爲30，000m〇l PPm並進行聚合45 分鐘外，與PP-1之製造同樣地進行聚合。結果獲得6」kg 聚合物。 [PP-6之製造] 於PP-1之製造中’除使丙烯/乙烯混和氣體之質量比 爲5 0/5 0外同樣地進行聚合。 [PP-7之製造] 於P P -1之製造中，除使丙烯/乙烯混和氣體之質量比 爲3 8 / 6 2外，同樣地進行聚合。 [PP-8及PP-9之製造] 以由氯化鎂上載持四氯化鈦之固體觸媒、有機銘化合 物及電子供給性化合物構成之觸媒，製造表3所示之比較 例3、4之聚丙烯樹脂組成物。 [PP-10之製造]Pn / (1-Pn) preferably satisfies the following formula (6), and more preferably satisfies the following formula (7). 2.50 ^ Pfi / (l-pfl) < 5.50 ......... (6) 3.00 ^ Pfi / (1-Pfl) < 5.〇〇 ......... (7 ) And 'Pp, Pp', Fp and Pfl can be obtained based on the statistical analysis of 13C_NMR spectrum. (10) 200400224 The rate equation of the dual viewing mode Pp2xPfi + P5P2x (1-Pfi) (―2Pp3 + 2Pp2) xPn + (― 2P, ρ3 + 2P'ρ2) χ (1-Ρη) (2Pp3 — 4Pp2 + 2Pρ) χρη + (2P, p3 — 4P, p2 + 2P, ρ) χ (1 — Pn) (Pp3 — 2Pp2 + Pp) xPfl + (P, p3 — 2P, p2 + P, p) x (l-Pfl) (Pp4- 4Pp3 + 3Pp2) xPf, + (P'p4- 4Pp3 + 3P, p2) x (1-Pfl) (—2Pp4 + 6Pp3 — 6Pp2 + 2Pp) xPf, + (— 2P'p4 + 6P, 3- 6P'p2 + 2P'p) x ( l-Pf 丨) (Pp4 — 5Pp3 + 9Pp2 — 7Pp + 2) xPr 丨 + (P, p4- 5P'p3 + 9P'p2 — 7P, p + 2) x (l — Pf 丨) Pp3xPf. + Pfp3x (I-Pfl) (2Pp3-4Pp2 + 2Pp) xPf, + (2P'p3-4P, p2 + 2P, p) x (l-Pf 丨) (—Pp3 + 2Pp2) xPfl + (— P, p3 + P, p2) x (l — Pfl) Signal (1) S aa (2) S ar (3) S a δ (4) T 5 (5 (5) S rr + Ύ β δ (6) S r δ (7) S (5 (5 (8) T / 3/3 (9) S β δ (10) S / S / 3 14- (11) (11) 200400224 The above method will be described by exemplifying the case where the component (B) is a propylene · ethylene copolymer elastomer. Figure 1 is a 13c-nmr pictorial representation of a typical propylene-ethylene copolymer elastomer. (Parallel method of ethylene and propylene) 10 different 1-phase peaks. The names of the linking chains are described in Macromolecules, vol. 10, pp. 5 3 6 · 5 44, 1 9 7 7, The nomenclature is as shown in Figure 2. If this connection chain is assumed to be a copolymerization reaction mechanism, it can be expressed by the product of the reaction rate. Therefore, the relative intensity of each of the peaks (1) to (1 0) when the peak intensity of the whole is 1. It is based on the reaction rate and the existence ratio of each observation as parameters, and can be expressed as the rate equation according to Bernoull statistical method. (1) When S α α, the propylene unit is represented by the symbol P and the ethylene unit is represented by the symbol Ε If it is expressed, the connection chains taken from it are [ρρρρ], [PPPEE], and [EPPEE], which are each expressed by the reaction rate and their bases are consistent. The remaining peaks of (2) to (10) can also use the same method to establish equations, and then the parameters that make these 10 equations closest to the actual measured peak intensities can be obtained, that is, by making the aforementioned pρ, pρ , And Pfl can be obtained by optimization. At the time of the optimization, the remaining difference between the peak intensity measurement obtained by the regression calculation to the minimum self-multiplication method and the theoretical values obtained from the various formulas shown in Table 1 becomes 1 X 1 (Γ5 or less. The calculation method to perform such regression calculation, etc., For example, Η · N · CHENG 'Journal of Applied Polymer Science, Vol. 35, No. 1 63 9-650 (1908). Next, the production of the polypropylene resin composition in the present invention will be described. Method. The manufacturing method of the polypropylene resin composition of the present invention is not particularly limited, and a known method can be adopted. For example, a belt mixer, a drum mixer, Han-15- (12) (12) 200400224 Su Shi Mixer (A) component and (B) component are mixed at a temperature of 170-280 t :, preferably at a temperature of 190-26 (rc), using a kneader, a mixing roller, a Banbury mixer, A uniaxial or biaxial extruder can be prepared by melting and mixing the chain. The polypropylene resin composition of the present invention can also be used to make the (A) component and (B) component in a polymerization system by a multi-stage polymerization method. Internally produced. In addition, 'the component (A) and the component (B) may be polymerized in a multi-stage polymerization method. It can be obtained by adding the component (A) and / or (B) separately after production in the polymerization system. The polypropylene component (A) and / or copolymer elastomer component (b) can be produced according to a known method. Specifically, In other words, Ziegler catalysts or aromatic metal catalysts can be used to polymerize propylene or copolymerize propylene with other olefins. Ziegler catalysts can be exemplified by titanium trichloride catalysts or magnesium-supported catalysts. Titanium catalysts. Examples of magnesium-supported catalyst systems include (a) solid catalyst components consisting of titanium, magnesium, and halogen as essential components, (b) organoaluminum compounds, and (c) electron-donating compounds. These are disclosed in Japanese Patent Laid-Open No. 5 7-63 3 1 0, Japanese Patent Laid-Open No. 5 7-63 3 1 1, Japanese Patent Laid-Open No. 5 8- 8 3 006, Japanese Patent Laid-Open No. 5 8-1 3 8 7 0 8; JP 62-205 07; JP 61-296006; JP 2-229806; JP 2-33103; JP 2-707 08; etc. These can also be used as preliminary polymerization catalysts for the polymerization of a small amount of olefins during the production of each component. When the component (B) of the present invention is produced, as long as it satisfies the composition in the present invention sufficiently The specified manufacturing conditions are sufficient, and there is no particular limitation, and the following methods can be specifically exemplified. -16- (13) (13) 200400224 1. The composition distribution, three-dimensional regularity distribution, or molecular weight distribution obtained by using the above catalyst can be obtained. A method for producing (B) component by using a wide range of polymer catalysts. 2 · A method for modulating the above-mentioned catalysts under the condition that the composition distribution body has a regular distribution or a broad molecular weight distribution, that is, changing an electron-donating compound or an organoaluminum The amount of the compound used is a method of producing the component (B) using a catalyst prepared by using several kinds of electron-donating compounds. 3 · A manufacturing method that makes composition distribution, stereoregularity distribution, or molecular weight distribution into a wider range of polymerization conditions, that is, (a) manufacturing by multi-stage polymerization and changing polymerization conditions such as temperature and monomer composition ratio in each stage ( B) The method of the component, (2) The method of manufacturing the component (B) by adjusting the composition of the copolymer elastomer to obtain the desired composition distribution by changing the composition distribution of the polymer composition generally obtained. 4. A method of using several components each having a uniform composition distribution and different propylene contents obtained by an aromatic metal catalyst or the like. By using the component (B) manufactured according to these methods, a polypropylene component resin composition having a composition distribution adjusted for the xylene soluble content described above can be easily obtained. In the production of each of the above components, polymerization methods such as slurry polymerization, superposition polymerization, solution polymerization, or gas phase polymerization are carried out in the presence of inert hydrocarbons such as hexane, heptane, kerosene, or liquid α-olefin solvents such as propane. , At a temperature ranging from room temperature to 200 ° C, preferably from 30 to 150 ° C, and under a pressure range from 0.2 to 5.0 MPa. The reactor used in the polymerization step may be appropriately used in the technical field. For example, a stirred layer type reactor, a fluidized bed type reaction -17- (14) (14) 200400224 reactor, and a circulation type reactor may be used in a continuous type. Either semi-batch or batch method. During the polymerization, the molecular weight of the obtained polymer can be adjusted, for example, by adding hydrogen or the like. The polypropylene resin composition of the present invention may be blended with other resins or additives, as long as the object of the present invention is not impaired. These other additives may be exemplified by antioxidants, weather-resistant stabilizers, antistatic agents, slip agents, anti-caking agents, anti-fog agents, dyes, pigments, oils, waxes, and the like. The film of the present invention is a cast film obtained by molding the polypropylene resin composition of the present invention by a T-die method or the like. This cast film can be used as a single body or laminated with other materials. The method for producing the film of the present invention is preferably one in which the above-mentioned polypropylene resin composition is filtered in a molten state using a metal fiber filter and then formed by various film forming methods. The metal fiber filter used in the present invention may be exemplified by a metal mesh filter, a sintered metal mesh filter, a porous metal filter, a metal fiber sintered filter, and a suitable combination of these filters. The metal fiber filter is preferably a filter with a precision of 5-150 / zm according to JIS B8356, a 20-120 // m is more preferable, and a 40- 1 00 // m is particularly good. When the filtration precision is less than 5 // m, the pressure during extrusion is likely to rise, which may damage the moldability. Depending on the situation, the shear heat of the molten resin may become intense and gas may be generated. On the other hand, if it is larger than 1 5 0 // m, there is a tendency that it is difficult to express an improved pomelo-like effect ', and gel particles are liable to be generated in the cast film. Examples of the shape of the metal fiber filter include a tubular filter, a bridge-shaped cylindrical filter, a leaf-shaped filter, and a scraper-shaped cylindrical filter. Among these, a leaf dish filter is preferred in terms of the improvement effect of pomelo peel, pressure resistance, and filtration area 2 -18- (15) (15) 200400224. As the metal fiber filter, "Brand Name: Nylon Filter" purchased from Fuji Seiki Co., Ltd. and "Brand Name: Fuji Metal Fiber Filter" purchased from Fuji Filter Industry Co., Ltd. can be used. The above-mentioned metal fiber filter is preferably installed between the extruder and the die of a film forming machine such as a T-die forming machine, and the molten resin passes through the metal filter section and then passes through the die. Better nearby. The temperature of the metal fiber filter set in the extruder is 200-2 8 (TC is better, 220-2 60 ° C is better. If the temperature is less than 20 (TC, the effect of improving pomelo peel is insufficient, and it is easy to squeeze. When the pressure rises. On the other hand, if it exceeds 280 ° C, not only the resin deteriorates, but the effect of improving the pomelo peel shape is also reduced. In particular, T-die molding machines are used in these film forming machines. Excellent film thickness accuracy, low anisotropy of physical properties such as shrinkage and strength, and high film impact strength etc. The laminated system of the present invention is on the film of the present invention, and at least one layer of the laminated layer is selected from the group consisting of aluminum foil and metal deposited film , Silicon oxide film, vinylidene chloride resin layer, ethylene-vinyl acetate copolymer resin alkali resin resin layer, polyamide resin layer, polyester resin layer, polycarbonate resin layer and oxygen absorber layer. Among these layers, vinylidene chloride resin and ethylene · vinyl acetate copolymer alkali compound are effective gas barrier layers. In addition, the oxygen absorber layer can be exemplified by a layer containing iron oxide. The laminated system of the present invention use It is known that dry laminating machines and the like can be obtained by laminating the above-mentioned layers through an adhesive agent or a co-extrusion method, a dry lamination method, and an extrusion lamination method without passing through an adhesive agent. The container of the present invention is used For the film or laminated body of the present invention. Container-19- (16) (16) 200400224 For example, a self-supporting bag-shaped container such as a two-layer heat-sealed bag-shaped container or a stand-up bag can be used. The packaging container can be produced by heat-sealing at a temperature of 180-250 ° C for 0.2 · 10 seconds, for example, by arranging two pieces of film or laminated body in four directions. The container of the present invention can be used for heating foods, etc. Sterilized packaging containers. In particular, the resin composition of the present invention, and the film and packaging container made of the resin composition, are easy to produce pomelo-like curry, raw ingredients of Gougemi rice, beef, pork even when used in conventional packaging containers. When cooking and sterilizing oily foods such as chicken and chicken, 'it is still a container that does not produce pomelo-like skin and has an excellent appearance. Moreover, the so-called heat sterilization in the present invention refers to a method of sterilizing microorganisms that will cause food spoilage. Bacteria vary, but it is generally carried out at a temperature range of 60-135 ° C. This method of using warm steam and hot water with a temperature of more than 100 ° C during heating and sterilization as the main body is called Retort sterilization is a method of short-term treatment at high temperature without compromising the taste and flavor of the contents. EXAMPLES The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these. In addition, the measurement methods of various physical properties are as follows Measurement of melt flow rate: Measured at 23 (rc, load 2 16 0 g) in accordance with JIS K7210. Measurement of 13C-NMR (calculate Pp, Pp ', and Pfl): -20- (17) 200400224 Measured by JNM-GSX400 made by Japan Electronics Co., Ltd. (Measuring mode decoupling method, pulse width: 8. 〇 # s, pulse repetition time 3.0 s, product: 100 000 times, measurement temperature: 丨 2 〇 ° C, Internal standard: hexamethyldi, solvent: 1,2,4-trichlorobenzene / benzene_d6 (capacity ratio 3/1), test: 0.1g / ml), based on the statistical analysis and obtained according to the aforementioned calculation method and P f 1. Measurement of xylene solubles X S: Put 2.5 g of sample in o-xylene 250 m 1, heat and raise to boiling temperature, and completely dissolve over 30 minutes. After it is completely dissolved, let it cool to below 100 ° C under stirring, and then keep it in the thermostatic bath for 2 hours. Then, the precipitated matter was filtered out with a filter paper, and the toluene-insoluble matter Xi) was obtained. Then, the filtrate is heated under a stream of toluene under nitrogen and dried to obtain xylene solubles Xs. Measurement of propylene content: Calculated from the results of the 13C-NMR. Determination of intrinsic viscosity: Measured in decane at 1 3 5 ° C. Measurement of tortuosity: Xylene soluble Xs and xylene insoluble Xi pressure (23 (TC preheated for 5 minutes, degassed for 30 seconds, pressurized at 6 MPa, and cooled at 30 ° C for 3 minutes) ) To produce a film with a thickness of 50-800. The obtained film is usually adjusted for 24 hours at room temperature, and then measured with an Abbe Co., Ltd. made by Atac Inc. using ethyl acid as an intermediate liquid. Formula: Number of proton fractions Siloxane concentration Pp, Pp Stirring and confirming that it has been W 2 5 ° c (three-minute thinning with two-distillation removal and two-shrinkage forming for 1 minute) Abbey -21-(18) (18) 200400224 (A ) And (B) component manufacturing: According to the following, the first stage (A) component is produced by multi-stage polymerization, and then the second stage (B) copolymer elastomer component is produced. The physical properties of these components are shown Tables 2 and 3. [Production of PP-1] Preparation of solid catalyst in nitrogen atmosphere, 1 2 (5 6.8 g of anhydrous magnesium chloride was completely dissolved in 100 g of absolute ethanol, 50 ml of Idemitsu Kosan (stock) at TC Vaseline oil "CP15N" made by Japan and 500 ml of silicone oil "KF9 6" made by Shin-Etsu Silicone Co., Ltd .. Using a TK homogenizer made by Japan Special Chemical Industry Co., Ltd. The contents were stirred at 5000 revolutions / minute for 2 minutes. While maintaining the stirring while not exceeding 0 ° C, it was transferred to 2 liters of anhydrous heptane. The obtained white solid was thoroughly washed with anhydrous heptane and It was dried under vacuum at room temperature, and then partially deethanolized under a stream of nitrogen. The obtained MgCl2 · 1.2C2H5OH spheres 30 g of a solid was suspended in 200 ml of anhydrous heptane. 500 ml of titanium tetrachloride was dropped into the solution at 0 ° C under stirring for 1 hour, followed by heating to 40 ° C and adding 4.96 g of diphthalic acid. Isobutyl ester, and the temperature was raised to 100 ° C in about 1 hour. After reacting at 100 ° C for 2 hours, the solid portion was filtered while hot. 500 ml of titanium tetrachloride was added to the reaction After stirring, the reaction was performed at 120 ° C for 1 hour. After the reaction was completed, the solid portion was again filtered while hot, and washed 7 times with 1.0 liter of hexane at 60 ° C and 3 times with 1.0 liter of hexane at room temperature. A solid catalyst was obtained. The titanium content of the obtained solid catalyst component was determined to be 2 · 3 6 -22- (19) (19) 200 400 224% by mass. 1) Preliminarily polymerized in nitrogen, 500 ml of Zheng Geng Yuan, 6.0 g of triethyl absolute, 0.99 g of cyclohexylmethyldimethoxysilane and 10 g of the polymerization catalyst obtained above were put into a 3 liter autoclave and stirred for 5 minutes at a temperature range of 0 to 5 ° C. The propylene to be polymerized was supplied into the autoclave in an amount of 10 g of propylene per lg of the polymerization catalyst, and the temperature was in the range of 0 to 5 ° c. The preliminary polymerization was performed for 1 hour. The obtained preliminary polymerization catalyst was washed 3 times with 500 ml of n-heptane and used for the following polymerizations. 2) The first stage of the main polymerization: (A) Production of polypropylene components in nitrogen, 2.0 g The pre-polymerized solid catalyst prepared by the above method, 11.4 g of triethylaluminum, and 1.88 g of cyclohexylmethyldimethoxysilane were put into a pressure autoclave with a volume of 60 liters and a stirrer, followed by charging 18 kg of propylene, For propylene, 5 000 mol ppm of hydrogen was heated to 70 ° C and polymerization was performed for 1 hour. After 1 hour, unreacted propylene was removed to terminate the polymerization reaction. The second stage: (B) propylene-ethylene copolymer elastomer production. As mentioned above, after the end of the first stage of polymerization, the liquid propylene is removed, and at a temperature of 75 ° C, propylene / ethylene is supplied in an amount of 2.2 Nm3 / hour = The mixed gas of 26/74 (mass ratio) is supplied to hydrogen in an amount of 40,000 mol ppm to the total amount of ethylene, propylene and hydrogen, and polymerized for 60 minutes. After 40 minutes, the unreacted gas was removed to terminate the reaction. As a result, 6.6 kg of a polymer was obtained. -23- (20) (20) 200400224 [Manufacture of PP-2] Stage 2: (B) In the production of propylene-ethylene copolymer elastomer, the amount of hydrogen used is 5 0 '0 in addition to the supplied hydrogen Except for 0 0 m 01 PP m, polymerization was performed in the same manner as in the production of PP-1. 6.3kg results obtained polymer [manufactured of PP-3] Stage 2: (B) a propylene - the production of elastomeric ethylene copolymers 'in addition to the hydrogen gas supply system as used in an amount so as to become 20' 〇〇〇m〇l Except for ppm, polymerization was performed in the same manner as in the production of PP1. As a result, 5.8 kg of a polymer was obtained. [Production of PP_4] Stage 1: (A) Production of polypropylene components in nitrogen, 2.0g of prepolymerized solid catalyst prepared by PP-1 method, 11.4g of triethylaluminum, 1.88g of cyclohexylmethyl Dimethoxysilane was put into a 60-liter inner pressure autoclave with a stirrer, followed by charging 18 kg of propylene, 120 L of ethylene, and 65 00 m1 ppm of hydrogen to propylene. The temperature was raised to 701: and polymerization was performed for 1 hour. After 1 hour, unreacted propylene was removed. Second stage: (B) Production of propylene-ethylene copolymer elastomer Except that the supplied hydrogen gas was 40,000 mOl ppm and polymerized for 40 minutes, polymerization was performed in the same manner as in the production of PP-1. As a result, 5.7 kg of a polymer was obtained. -24-(21) (21) 200400224 [Manufacturing of PP-5] In the second stage, 'the mass ratio of the supplied mixed C / B storage gas was 26/74, and the hydrogen gas was 30,000 m PP l Polymerization was performed for 45 minutes, and polymerization was performed in the same manner as in the production of PP-1. As a result, 6 "kg of polymer was obtained. [Production of PP-6] In the production of PP-1 ', polymerization was performed in the same manner except that the mass ratio of the propylene / ethylene mixed gas was 50/50. [Production of PP-7] In the production of PP-1, polymerization was performed in the same manner except that the mass ratio of the propylene / ethylene mixed gas was 3 8/62. [Production of PP-8 and PP-9] A catalyst composed of a solid catalyst, an organic compound, and an electron-donating compound on which titanium tetrachloride was supported on magnesium chloride was produced in Comparative Examples 3 and 4 shown in Table 3. Polypropylene resin composition. [Manufacture of PP-10]
TiCl4[C6H4 ( CO〇iC4H9) 2]之調製 於含19g四氯化鈦之己烷1.0公升之溶液中’於維持 溫度0 °C下以約3 0分鐘滴加2 7.8 g苯二甲酸二異丁醋 -25- (22) (22)200400224 :C6H4 ( COOi-C4H9 ) 2。滴加終了後升溫至40°C並反應30 分鐘。反應終了後，收集固體部分以5 0 0 m 1己院洗 5次 而獲得目的物。 固體觸媒之調製 將 P P -1之製造方法所得之固體觸媒 2 0 g懸濁於 3 0 0ml甲苯中，於溫度25°C添加以上所得之TiCl4[C6H4 ( COO i C4H9 ) 2]並攪拌1小時，趁熱過濾並收集固體部分。 然後，將該反應物以90°C之甲苯500ml洗滌3次、以室 溫之己烷5 00ml洗滌3次。所得固體觸媒成分中之鈦含有 率爲1 . 7 8質量％。 預備聚合 於充滿氮氣其內容積爲3公升之壓力釜中，投入 5 0 0ml正庚烷、6.0g三乙基鋁、3.98g二環戊基二甲氧矽 烷及1 〇g上述所得之聚合觸媒，於0至5 °C之溫度範圍下 攪拌5分鐘。繼之，將欲聚合之丙烯供應至壓力釜內其量 爲每lg聚合觸媒投入l〇g丙烯，於0至5°C之溫度範圍 進行預備聚合1小時。所得之預備聚合固體觸媒以500ml 正庚烷洗滌3次，供以下之聚合用。 聚合 第1階段：均聚丙烯之製造 於氮氣中，將2.0g上述方法製得之預備聚合固體觸 •26- (23) (23)200400224 媒、11.4g三乙基鋁、6.84g二環戊基二甲氧矽烷投入內 容積60公升且附有攪拌機之壓力釜中，繼之裝入18 kg丙 嫌與對丙嫌爲1.4mol%之氫氣，升溫至70°C並進行聚合1 小時。1小時後，去除未反應之丙烯。 第2階段：丙烯-乙烯共聚物彈性體之製造 經上述第1階段聚合後，於溫度75 °C下，以2.2Nm3/ 小時之量供給丙烯/乙烯=40/60 (質量比）之混和氣體， 並以20NL/小時之速度供給氫氣，共聚40分鐘。40分鐘 後去除未反應之氣體以終結反應。 聚丙樹脂組成物及薄膜之製造 [實施例1] 於100質量份以上所得之PP-1中，添加0.30質量份 酚系抗氧化劑、〇. 1質量份硬脂酸鈣並以韓蘇式混合器於 室溫混合3分鐘。以螺紋口徑4 0mm之擠壓機（中谷V S K 型4 0mm擠壓機）於圓筒溫度設定於21 0°C下將該組成物 混鍊而獲得組成物之顆粒。 繼之，使用附設T印模之擠壓機（東芝機械社製擠壓 機，雙梯板螺旋，螺紋徑6 5 m m，L / D 2 6 · 2、鑄模溫度2 6 0 °C，圓筒溫度2 6 0 °C )，將該顆粒以螺旋迴轉速8 0 r p m ’ 牽引速度12m/秒，冷卻輥溫度50°C之條件下製膜’使成 形爲厚度約70#m之薄膜。 [實施例2-5比較例1-5] -27- (24) (24)200400224 於實施例1中除分別使用表2或3記載之物替代ρρ· 1以外，其餘同樣進行，而製造樹脂組成物及薄膜。 對上述貫施例1- 5、比較例1 - 5所得之各薄膜，測定 熱封強度、薄膜衝擊性（低溫衝擊強度）、拉伸彈性率（ 楊氏模量）、透明性。結果示於表2及3。測定方法如下 熱封強度： 將積層有黏著樹脂之厚度60微米之PET薄膜與上述 聚丙嫌樹脂組成物製薄膜重疊之物，以使該聚丙烯樹脂組 成物薄膜爲內側2組重疊，使用帖斯特（Test )產業公司 製之熱封機進行熱封（熱封條之寬度爲5 mm，熱封溫度 爲160 °C及170 °C，於0.2 MPa下加壓1秒，對成形時之樹 脂流動方向（MD，moving direction)爲直角方向）爲垂 直方向。 於室溫下經4 8小時狀態調整後，經熱封之薄膜取寬 度l5mm作爲試樣，以夾盤間距50mm，拉伸速度3 00mm/ 分之速度對熱封部位以打開1 80 °C之方向施予拉伸荷重至 熱封部位斷裂爲止，求取其間之平均強度。以該平均強 度7點之平均値作爲熱封強度。 薄膜衝擊之測定（低溫衝擊強度）： 將薄膜作成l〇cm X lm大小之試樣’於-5 °C之恆溫 室內放置2小時。然後於該恆溫室內，於（股）東洋精機 -28- (25) (25)200400224 製作所製之薄膜衝擊試驗機裝設半徑1 /2英吋之衝擊芯， 一個試樣進行1 〇次試驗’測定衝擊能量。此等衝擊能量 之値除以薄膜厚度，以其1 〇點之平均値爲薄膜衝擊並以 其作爲耐衝擊性之尺度。 拉伸彈性率（楊氏模量）： 依據JIS K7127之方法，以試樣寬度20mm，夾盤間 距2 5 0mm，拉伸速度5mm/分之條件，針對成形時之樹脂 流動方向測定。 透明性： 依據JIS K7 105之方法，測定總濁度。 200400224 (N嗽 實施例6 Ippii之第1階段 1- 〇 〇 ΡΡΠ之第2階段 70.0 00 〇 Ό (Ν VO rn s (N 寸· 81.9 37.2 2.20 4.01 1.479 73.0 1.17 58.0 57.0 12.3 740 卜 η 實施例5 PP5之第1階段 〇 PP5之第2階段 65.0 wn (N 〇 m CM s rn 80.5 42.4 § 3.22 1.479 71.5 s 48.0 55.0 00 ON 800 (Ν m 實施例4 PP4之第1階段 (N 〇〇 PP4之第2階段 65.0 (N (N rn 24.6 〇 (N o iT) (N 3.09 1.479 71.5 1.10 53.0 55.9 12.0 580 <N (N 實施例3 PP3之第1階段 〇 〇 PP3之第2階段 70.0 00 〇 26.2 s rn — 82.5 37.3 2.21 3.97 1.479 73.4 ο 58.8 57.9 Ο) 750 00 實施例2 ! PP2之第1階段 〇 〇 PP2之第2階段 70.0 〇 (N 27.2 寸 s <N 82.5 38.4 2.15 3.60 1.479 72.9 0.79 63.7 61.8 10.7 630 實施例1 PP1之第1階段 〇 〇 PP1之第2階段 70.0 〇 m (N 29.6 s m· m rn 81.8 36.7 2.23 4.72 1.479 73.9 0.92 58.8 58.8 12.2 640 質量％ 質量％ 質量％ 質量％ g/10m in 質量％ [7?]Xi 屈折率 bO 質量％ 質量％ (Pp/P，p) Pfl/(1-Pfl) 屈折率 質量％ [v]Xs/[v]X\ N/15min N/15mm J/mm MPa 乙烯含量 構成量 丙烯含量 構成量 融體流速 Xs含有量 [7?]XS ·〇 丙烯含量 熱封強度160°C 熱封強度丨70°C 低溫衝擊強度 楊氏模量md 總濁度 g -30- 200400224 e漱TiCl4 [C6H4 (CO〇iC4H9) 2] was prepared in a 1.0 liter solution of hexane containing 19 g of titanium tetrachloride, and 2 7.8 g of diisophthalic acid was added dropwise at a maintenance temperature of 0 ° C over about 30 minutes. Butanate-25- (22) (22) 200400224: C6H4 (COOi-C4H9) 2. After the dropwise addition was completed, the temperature was raised to 40 ° C and the reaction was allowed to proceed for 30 minutes. After the reaction was completed, the solid portion was collected and washed 5 times at 500 m 1 to obtain the target substance. Preparation of solid catalyst 20 g of the solid catalyst obtained by the manufacturing method of PP-1 was suspended in 300 ml of toluene, and the TiCl4 [C6H4 (COO i C4H9) 2] obtained above was added at a temperature of 25 ° C and stirred. After 1 hour, the hot portion was filtered and the solid portion was collected. Then, the reaction was washed three times with 500 ml of toluene at 90 ° C and three times with 500 ml of hexane at room temperature. The titanium content of the obtained solid catalyst component was 1.7 mass%. Preliminarily polymerize in a 3 liter autoclave filled with nitrogen, and put 500 ml of n-heptane, 6.0 g of triethylaluminum, 3.98 g of dicyclopentyl dimethoxysilane, and 10 g of the polymerization catalyst obtained above. Medium, and stirred at a temperature range of 0 to 5 ° C for 5 minutes. Next, propylene to be polymerized was supplied to the autoclave in an amount of 10 g of propylene per lg of polymerization catalyst, and preliminary polymerization was performed at a temperature range of 0 to 5 ° C for 1 hour. The obtained preliminary polymerization solid catalyst was washed three times with 500 ml of n-heptane for the following polymerization. The first stage of polymerization: the production of homopolypropylene in nitrogen, and 2.0 g of the pre-polymerized solid prepared by the method described above. 26- (23) (23) 200400224 medium, 11.4 g of triethylaluminum, 6.84 g of dicyclopentane Dimethoxysilane was put into a 60-liter inner pressure autoclave with a stirrer, followed by charging 18 kg of hydrogen and 1.4 mole% of hydrogen to hydrogen, heating to 70 ° C and polymerizing for 1 hour. After 1 hour, unreacted propylene was removed. Stage 2: Production of propylene-ethylene copolymer elastomer After the above stage 1 polymerization, at a temperature of 75 ° C, a propylene / ethylene = 40/60 (mass ratio) mixed gas is supplied. And supply hydrogen at a rate of 20 NL / hour for 40 minutes. After 40 minutes, the unreacted gas was removed to terminate the reaction. Production of polypropylene resin composition and film [Example 1] To PP-1 obtained by 100 parts by mass or more, 0.30 parts by mass of a phenolic antioxidant and 0.1 part by mass of calcium stearate were added, and a Korean-Soviet mixer was used. Mix at room temperature for 3 minutes. An extruder with a thread diameter of 40 mm (Nakatani VS K-type 40 mm extruder) was mixed with the composition at a cylinder temperature of 21 ° C to obtain pellets of the composition. Next, use an extruder with a T die (extruder manufactured by Toshiba Machinery Co., Ltd., double stair screw, thread diameter 65 mm, L / D 2 6 · 2, mold temperature 2 60 ° C, cylinder The temperature is 2 60 ° C), and the particles are formed into a film having a thickness of about 70 # m at a spiral return speed of 80 rpm ', a pulling speed of 12m / sec, and a cooling roller temperature of 50 ° C. [Example 2-5 Comparative Example 1-5] -27- (24) (24) 200400224 In Example 1, except that the items described in Table 2 or 3 were used in place of ρρ · 1, the rest were performed in the same manner, and resin was produced. Composition and film. For each of the films obtained in the foregoing Examples 1 to 5, and Comparative Examples 1 to 5, heat seal strength, film impact resistance (low temperature impact strength), tensile elastic modulus (Young's modulus), and transparency were measured. The results are shown in Tables 2 and 3. The measurement method is as follows. The heat-sealing strength is as follows: A PET film having a thickness of 60 μm laminated with an adhesive resin and a film made of the polypropylene resin composition described above are overlapped, so that the polypropylene resin composition film is overlapped on the inner two groups, and Ties are used. Heat sealing machine manufactured by Test Industry Co., Ltd. (sealing strip width is 5 mm, heat sealing temperature is 160 ° C and 170 ° C, press at 0.2 MPa for 1 second, and the resin flows during molding The direction (MD, moving direction) is perpendicular. After adjusting for 48 hours at room temperature, the heat-sealed film was taken as a sample with a width of 15 mm, and the heat-sealed part was opened at a speed of 300 mm / min with a chuck pitch of 50 mm and a stretching speed of 300 mm / min. The tensile load was applied in the direction until the heat-sealed part was broken, and the average strength was calculated. The average strength of 7 points of this average strength was taken as the heat seal strength. Measurement of film impact (low-temperature impact strength): The film was made into a sample of 10 cm X lm 'and placed in a constant-temperature room at -5 ° C for 2 hours. Then in this constant temperature room, install a shock core with a radius of 1/2 inches in a film impact tester manufactured by Toyo Seiki-28- (25) (25) 200400224 Manufacturing Co., Ltd., and perform a test of 10 times on one sample. Determination of impact energy. The 値 of these impact energies is divided by the thickness of the film, and the average 値 of 10 points is taken as the impact of the film and it is used as a measure of the impact resistance. Tensile elastic modulus (Young's modulus): Measured in accordance with the method of JIS K7127 with a sample width of 20 mm, a chuck distance of 250 mm, and a tensile speed of 5 mm / minute. Transparency: The total turbidity was measured according to the method of JIS K7 105. 200400224 (Example 6 Phase 1 of Ippii 1-〇〇ΡΡΠ 2nd stage 70.0 00 〇 Ό (N VO rn s (N inch 81.9 37.2 2.20 4.01 1.479 73.0 1.17 58.0 57.0 12.3 740 η Example 5 1st stage of PP5 0 2nd stage of PP5 65.0 wn (N 0m CM s rn 80.5 42.4 § 3.22 1.479 71.5 s 48.0 55.0 00 ON 800 (Nm Example 4 1st stage of PP4 (N0 2 stage 65.0 (N (N rn 24.6 〇 (N o iT) (N 3.09 1.479 71.5 1.10 53.0 55.9 12.0 580 < N (N Example 3 Phase 1 of PP3 〇PP3 Phase 2 70.0 00 〇26.2 s rn — 82.5 37.3 2.21 3.97 1.479 73.4 ο 58.8 57.9 Ο) 750 00 Example 2! Phase 2 of PP2 〇〇Phase 2 of PP2 70.0 〇 (N 27.2 inch s < N 82.5 38.4 2.15 3.60 1.479 72.9 0.79 63.7 61.8 10.7 630 Example 1 Phase 1 of PP1. Phase 2 of PP1. 70.0 mm (N 29.6 sm · m rn 81.8 36.7 2.23 4.72 1.479 73.9 0.92 58.8 58.8 12.2 640 mass% mass% mass% g / 10m in Mass% [7?] Xi Inflection rate bO Mass% Mass% (Pp / P, p) Pfl / (1-Pfl) Discount mass% [v] Xs / [v] X \ N / 15min N / 15mm J / mm MPa Ethylene content composition amount Propene content composition amount Melt flow rate Xs content [7?] XS · 〇 Propene content heat seal strength 160 ° C heat seal strength 丨 70 ° C low temperature impact strength Young's modulus md total turbidity g -30- 200400224 e
比較例5 PP10之第I階段 〇 § PP10之第2階段 62.0 〇 m 〇 36.2 Ο rn 1.502 VD ri 69.6 34.8 2.00 o 1.470 35.3 13.9 340 3 比較例4 PP9之第I階段 § PP9之第2階段 ΓΝί 27.6 ON (Ν 1.498 〇v oo 44.5 2.00 6.45 1.488 00 0.72 (N 480 ο 比較例3 PP8之第I階段 〇 % PP8之第2階段 68.6 〇 (Ν’ I 37.9 (Ν rn s 呀 (N 80.5 44.8 3.19 1.480 0.75 37.3 40.2 13.9 340 比較例2 PP7之第I階段 〇 〇 PP7之第2階段 57.0 〇 一· 26.5 s IT) <N rn 74.4 m C) 1.473 61.2 33.0 37.0 18.9 540 m 比較例I PP6之第I階段 〇 § PP6之第2階段 44.0 (Ν 17.3 VO CN s wn — 67.6 37.6 g 1.469 57.0 1.73 53.9 54.9 10.4 790 o 質量％ 質量％ 質量％ 質量％ g/lOmin 質量％ U]Xi 屈折率 dL/g 質量％ 質量％ (Pp/p，p) Pfl/(1-Pfl) 屈折率 質量％ [^]Xs/[7?]Xi N/15mm N/15mm J/mm MPa 乙_含量 I構成量 丙烯含量 構成量 融體流速 Xs含有量 mxs Cl 丙錄含量 熱封強度160°C 熱封強度170°C 低溫衝擊強度 楊氏模量md 總濁度 S -31 - (28) (28)200400224 [PP_1 1之製造] 1) 預備聚合 於氮氣中，將500ml正庚烷、6.0g三乙基鋁、〇.99g 環己基甲基二甲氧矽烷及l〇g上述所得之聚合觸媒（ = [PP-1之製造]中所述之固體觸媒）投入3公升之壓力釜 中，於〇至5°C之溫度範圍下攪拌5分鐘。繼之將欲聚合 之丙烯供應至壓力釜內其量爲每1g聚合觸媒投入l〇g丙 烯，於0至51之溫度範圍進行預備聚合1小時。所得之 預備聚合觸媒以5 00ml正庚烷洗滌3次’並用於以下之聚 合。 2) 主聚合 於設定70 °C之第1環形聚合反應器中，將依據上述 方法製得之預備聚合固體觸媒以l〇g/小時、三乙基鋁以 5 7 g/小時、環己基甲基二甲氧矽烷以 9.4g/小時、丙烯以 90 kg/小時及氫氣以 21 .6g/小時之速度供給並於期間同時 進合聚合，以製造（A)聚丙烯成分。從由第1聚合反應 器排出之混合物去除液態丙烯後，將混合物供給至設定於 75 °C之第 2聚合反應器中。同時以乙烯/丙烯=2 6/74 (質 量比）之混和氣體2.2Nm3/小時、以氫氣4g/小時之速度 供應至第2聚合反應器並一邊進行氣相聚合5 0小時，以 製造（B )丙烯-乙烯共聚物彈性體。自第2聚合反應器排 出之組成物中去除未反應之丙烯而得目的組成物。 [實施例6] -32- (29) (29)200400224 使用韓蘇式混合器，將於室溫下將〇. 1 〇質量份酚系 抗氧化劑、〇.〇5質量份硬脂酸鈣添加至100質量份上述所 得之PP-1 1中之混合物，連續供給至螺紋口徑65mm之擠 壓機以圓筒溫度設定於2 3 (TC，混鍊而獲得組成物之顆粒 〇 薄膜成形機係使用裝備有口徑1 15mm 0及口徑65mm 0之擠壓機，鑄模寬3,4 00mm，模唇寬0.8 mm、區段供料 方式之東芝機械社製T印模成形機，擠出機與T印模間 配置裝有8 0片日本精線公司製「商品名：納絲龍濾器（ Naslon filter) -NF12D (依據 JIS B 8 3 5 6 之精密度 40// m )」之金屬纖維濾器。 上述顆粒於擠壓機成融熔狀態，使融熔狀態之樹脂通 過金屬纖維濾器供給至溫度2 3 0 °C之T印模，以冷卻溫度 5 〇 °C之條件成形爲厚度7 0 // m之薄膜。 對實施例6所得之薄膜，測定熱封強度、薄膜衝擊性 (低溫衝擊強度）、拉伸彈性率（楊氏模量）、透明性。 測定結果示於表2。此外對下列項目進行評估其結果示於 表4 〇 結塊強度之測定： 切取10 cm X 10cm大小之薄膜將其重疊，使荷重 l〇kg ’於溫度5(TC之大氣下放置24小時。繼之使用拉伸 試驗機（歐忍特克（ORIENTEC )公司製天夕龍（ Tensilon) CUT- 5 00 )測定以5 00mm/分鐘之剝離速度將結 -33- (30) 200400224 塊之薄膜全面剝離時之強度，以該強度7點之平 結塊強度（g/l〇〇cm2)。結塊強度大者意味其結 重。 蒸煮處理 將厚度12/im之聚酯薄膜、厚度9//m之銘 並以使各薄膜與鋁箔間之聚胺酯系接著劑層之厚 // m之乾氏層積法加以積層，製得積層體。將該 15 cm X 18cm)以使上述薄膜爲鄰接狀2片重 圍3面以熱封寬度8 mm，溫度230 °C、壓力0. 封時間2秒之條件製作熱封包裝袋，測定熱封部 強度（蒸煮處理前之熱封強度）。於該包裝袋內 蒸煮食品味之素（股）製「青椒肉絲」5 0公克 物，將開口面與其他三面同樣熱封而製作由包裝 容器。使用曰本（股）日販製作所製RCS-4 0T 1 2 1 °C蒸煮3 0分鐘。測定蒸煮處理後容器熱封部 強度，並以目視法進行柚皮評估。 又，製作僅將沙拉油同樣裝入包裝袋之容器 水與沙拉油之混合比率（體積比）爲9:；[之混合 入包裝袋之容器。該等容器以相同條件進行蒸煮 測定蒸煮處理後容器熱封部位之熱封強度。 柚皮之評估： 柚皮狀態係以目視法，依下列5階段法評估 均値作爲 塊情形嚴 箔依序， 度成爲2 積層體（ 疊，將周 3MPa、熱 位之熱封 裝入市售 作爲內容 袋構成之 ，於溫度 位之熱封 ，以及將 液同樣裝 處理，並 經蒸煮處 -34 - (31) (31)200400224 理後之包裝袋表層之凹凸狀態（柚皮狀）之發生狀態。 1:完全未觀察到產生柚皮狀。 2:雖觀察到若干不明顯之凹凸柚皮狀但仍屬耐用。 3：雖見到產生相當多之不明顯凹凸柚皮狀但仍屬耐 用。 4:包裝袋全面見到淸楚之凹凸柚皮狀已不耐用。 5:包裝袋全面見到嚴重的凹凸柚皮狀已不耐用。 落袋強度試驗： 將180公克水裝入以上述方法製作之15 cm X 18cm 包裝袋內製作調理包。繼之以與上述相同之方法及條件進 行蒸煮處理。將所得之3 0個調理包於0 °C之大氣下自 1.2m高度落至水平之狀態反覆落下，求得至30個調理包 之一半即15個破損之次數（F50 )。 [實施例7] 除了金屬纖維濾器係使用裝設8 0片日本精線公司製 納絲龍濾器-NF 1 4D以外，與實施例6同樣進行。 [實施例8] 除了以網目20/60/120/60/20網眼之師網替代金屬纖 維濾器以外，與實施例6同樣進行。 [比較例6 ] -35- (32) (32)200400224 除了使用比較例1之樹脂以外，與實施例6同樣進行 上述實施例7至8、比較例6之測定結果示於表4。 表4 實施例6 實施例7 實施例8 比較例6 柚皮狀評價 1 2 4 4 熱封強度 (N/15mm 寬） 蒸煮前 83 80 76 85 蒸煮後青椒肉絲 72 67 65 51 蒸煮後沙拉油 71 68 64 58 蒸煮後混合液 68 65 62 48 落袋強度(F50) 48 42 38 3 結塊強度(g/l〇〇cm2) 50 55 65 160 由表2及表3可知，本實施例由聚丙烯樹脂組成物所 成之薄膜，其熱封強度、薄膜衝擊性（低溫衝擊強度）、 拉伸彈性率（楊氏模量）、透明性爲平衡性甚高者。 然而，於（B )共聚物彈性體成分中源自丙烯之單元 較少的比較例1其透明性低。又，不能滿足（2 )式下限 之比較例2，及不能滿足（1 )式下限之比較例3其熱封 強度低。此外，Xs之丙烯含量Fp多但不能滿足（2 )式 上限之比較例4其熱封強度及耐衝擊強度低。不能滿足（ 2 )式下限之比較例5其熱封強度低。 由表4可知，依據本實施例之容器，因抑制柚皮狀之 -36· (33) (33)200400224 產生而外觀優異，蒸煮前後之熱封強度變化小且落袋強度 優越，耐結塊性優越。 【圖示之簡單說明】 第1圖係示丙烯-乙烯聚合物彈性體之13c-nmr圖譜 之一例。 第2圖係示連接鏈由來之各碳原子之名稱。 產業上之利用可能性 如上所述，本發明之澆鑄薄膜特別是於低溫下之耐衝 擊性與剛性之平衡及透明性優越，且其熱封強度亦優越。 因而以汽車或家電領域爲首，可利用於更廣泛範圍之用途 〇 特別是，藉由使二甲苯可溶分Xs之丙烯含量Fp超過 60質量％可更進一步提高透明性及熱封強度。 又，藉由使二甲苯不溶分Xi之曲折率及二甲苯可溶 分Xs之曲折率落於特定範圍內，可使透明性、耐衝擊性 、剛性及耐熱性達到更高次元之平衡。 此外，本發明之容器係可抑制柚皮狀，且落袋強度、 耐結塊性優越者。 -37-Comparative Example 5 Phase I of PP10 0 § Phase 2 of PP10 62.0 〇 〇36.2 〇 rn 1.502 VD ri 69.6 34.8 2.00 o 1.470 35.3 13.9 340 3 Comparative Example 4 Phase I of PP9 § Phase 2 of PP9 ΓΝί 27.6 ON (N 1.498 〇v oo 44.5 2.00 6.45 1.488 00 0.72 (N 480 ο Comparative Example 3 Phase 8 of PP8 0% Phase 2 of PP8 68.6 〇 (N 'I 37.9 (N rn s Yeah (N 80.5 44.8 3.19 1.480 0.75 37.3 40.2 13.9 340 Comparative Example 2 Phase I of PP7 〇PP7 Phase 2 57.0 〇 26.5 s IT) < N rn 74.4 m C) 1.473 61.2 33.0 37.0 18.9 540 m Comparative Example I PP6 Phase I Stage 0§ 2nd stage of PP6 44.0 (N 17.3 VO CN s wn — 67.6 37.6 g 1.469 57.0 1.73 53.9 54.9 10.4 790 o mass% mass% mass% mass% g / lOmin mass% U] Xi inflection rate dL / g mass % Mass% (Pp / p, p) Pfl / (1-Pfl) mass of inflection rate [^] Xs / [7?] Xi N / 15mm N / 15mm J / mm MPa B_content I composition amount propylene content composition Melt flow velocity Xs content mxs Cl Acrylic content Heat seal strength 160 ° C Heat seal strength 170 ° C Low temperature impact strength Modulus md Total turbidity S -31-(28) (28) 200 400 224 [Production of PP_1 1] 1) Preliminarily polymerize in nitrogen, 500 ml of n-heptane, 6.0 g of triethylaluminum, 0.99 g of cyclohexyl Methyldimethoxysilane and 10 g of the polymerization catalyst obtained above (= the solid catalyst described in [Manufacture of PP-1]) were put into a 3 liter autoclave at a temperature range of 0 to 5 ° C Stir for 5 minutes. Next, supply the propylene to be polymerized into the autoclave in an amount of 10 g of propylene per 1 g of the polymerization catalyst, and perform preliminary polymerization at a temperature range of 0 to 51 for 1 hour. Wash 3 times with 5,000 ml of n-heptane and use it for the following polymerizations. 2) The main polymerization is performed in a first ring polymerization reactor set at 70 ° C. The pre-polymerized solid catalyst prepared according to the above method is 10 g. Per hour, triethylaluminum at 57 g / hour, cyclohexylmethyldimethoxysilane at 9.4 g / hour, propylene at 90 kg / hour, and hydrogen at a rate of 21.6 g / hour and fed simultaneously during the period Polymerization to produce (A) polypropylene components. After the liquid propylene was removed from the mixture discharged from the first polymerization reactor, the mixture was supplied to a second polymerization reactor set at 75 ° C. At the same time, a mixed gas of ethylene / propylene = 2 6/74 (mass ratio) 2.2Nm3 / hour and hydrogen gas at a rate of 4g / hour were supplied to the second polymerization reactor and gas phase polymerization was carried out for 50 hours to produce (B ) Propylene-ethylene copolymer elastomer. The target composition was obtained by removing unreacted propylene from the composition discharged from the second polymerization reactor. [Example 6] -32- (29) (29) 200400224 Using a Korean-Soviet mixer, 0.1 mass part of phenolic antioxidant and 0.05 mass part of calcium stearate will be added at room temperature. 100 parts by mass of the PP-1 1 mixture obtained above was continuously fed to an extruder with a screw diameter of 65 mm and the cylinder temperature was set at 2 3 (TC, mixed to obtain the pellets of the composition. The film forming machine was used Equipped with an extruder with a caliber of 1 15mm 0 and a caliber of 65mm 0, a mold width of 3,400 mm, a die lip width of 0.8 mm, and a section feeding method made by Toshiba Machinery Co. The mold room is equipped with 80 pieces of metal fiber filters made by Nippon Seisen Co., Ltd. with a "trade name: Naslon filter-NF12D (precision 40 // m according to JIS B 8 3 5 6)". The granules are melted in the extruder, and the molten resin is supplied to the T stamp at a temperature of 230 ° C through a metal fiber filter, and formed into a thickness of 7 0 // m under a cooling temperature of 50 ° C. The film obtained in Example 6 was measured for heat seal strength, film impact resistance (low temperature impact strength), and tensile elasticity. Young's modulus) and transparency. The measurement results are shown in Table 2. In addition, the following items were evaluated and the results are shown in Table 4: Measurement of the agglomeration strength: Cut a 10 cm X 10 cm film and overlap it to make the load l 〇kg 'Let it stand at a temperature of 5 ° C for 24 hours. Then use a tensile tester (Tensilon CUT- 5 00 manufactured by ORIENTEC) to measure it at 500 mm / min. The peeling speed will be the strength of the knot-33- (30) 200400224 piece of film when it is completely peeled, and the flat cake strength (g / 100cm2) of 7 points at this strength. The larger cake strength means the cake weight. Cooking The polyester film with a thickness of 12 / im and the thickness of 9 // m are processed by the dry lamination method with a thickness of // m of the polyurethane-based adhesive layer between each film and the aluminum foil to obtain a laminated body. The 15 cm X 18 cm) was used to make the above-mentioned film into a contiguous shape. Two sheets were surrounded by three sides with a heat-sealing width of 8 mm, a temperature of 230 ° C, and a pressure of 0. The sealing time was 2 seconds, and the heat-sealing was measured. Strength (heat-sealing strength before steaming). Steamed food-flavored ingredients (stocks) made in this package " "Pepper shredded pork" is 50 grams, and the open side is sealed with the other three sides to make a packaging container. Use RCS-4 0T 1 2 1 ° C for 30 minutes. Measure the cooking process The strength of the heat-sealed part of the rear container was evaluated visually with pomelo peel. In addition, the mixing ratio (volume ratio) of container water and salad oil in which only the salad oil was also packed in the packaging bag was 9 :; Container for bags. These containers were cooked under the same conditions. The heat-sealing strength of the heat-sealed parts of the containers after the cooking process was measured. Evaluation of pomelo peel: The condition of pomelo peel is visually evaluated in accordance with the following five-stage method. As a block case, the order of the foils is strict, and the degree becomes 2 laminates. The structure of the bag is heat-sealed at the temperature level, and the liquid is filled and treated in the same way, and after the cooking place -34-(31) (31) 200400224, the uneven state (the pomelo peel) of the surface of the packaging bag is generated. 1: No pomelo-like appearance was observed at all. 2: Although some inconspicuous irregular pomelo-like shapes were observed, it was durable. 3: Although considerable inconspicuous pomelo-like shapes were observed, it was durable. 4 : The bag is full of embossed pomelo peel, which is no longer durable. 5: The bag is full of embossed pomelo peel, which is not durable. Falling bag strength test: Put 180 grams of water in the above method A conditioning bag is made in a 15 cm X 18cm packaging bag. Then, the same method and conditions as above are used for cooking. The 30 conditioning bags obtained are repeatedly dropped from a height of 1.2m to a level in an atmosphere of 0 ° C. Drop to get half of the 30 conditioning packages That is, 15 times of damage (F50). [Example 7] The same procedure as in Example 6 was carried out except that a metal fiber filter was equipped with 80 pieces of Naslon filter-NF 1 4D manufactured by Nippon Seisen Co., Ltd. Example 8] Except replacing the metal fiber filter with a mesh of 20/60/120/60/20 mesh, the same procedure as in Example 6. [Comparative Example 6] -35- (32) (32) 200400224 Except for use The measurement results of Examples 7 to 8 and Comparative Example 6 were performed in the same manner as in Example 6 except for the resin of Comparative Example 1. The results are shown in Table 4. Table 4 Example 6 Example 7 Example 8 Comparative Example 6 Pomelo peel evaluation 1 2 4 4 Heat-sealing strength (N / 15mm width) Before cooking 83 80 76 85 Steamed green pepper pork after cooking 72 67 65 51 Salad oil after cooking 71 68 64 58 Mixture after cooking 68 65 62 48 Bag dropping strength (F50) 48 42 38 3 Caking strength (g / 100cm2) 50 55 65 160 As can be seen from Tables 2 and 3, the film made of the polypropylene resin composition in this example has heat-sealing strength and film impact resistance (low temperature). (Impact strength), tensile elasticity (Young's modulus), and transparency are those with high balance. However, (B) copolymer elastomers Comparative Example 1, which has fewer units derived from propylene in the body composition, has lower transparency. Further, Comparative Example 2, which does not satisfy the lower limit of formula (2), and Comparative Example 3, which does not satisfy the lower limit of formula (1), have heat seal strength In addition, Comparative Example 4 in which Xs has a large propylene content Fp but fails to satisfy the upper limit of formula (2) has low heat seal strength and impact strength. Comparative Example 5 which does not satisfy the lower limit of formula (2) has low heat seal strength. As can be seen from Table 4, the container according to this embodiment has excellent appearance because it suppresses the generation of pomelo-36 · (33) (33) 200400224, the heat-sealing strength change before and after cooking is small, the bag-falling strength is superior, and it is resistant to agglomeration Sex is superior. [Brief description of the figure] Fig. 1 shows an example of a 13c-nmr spectrum of a propylene-ethylene polymer elastomer. Figure 2 shows the names of each carbon atom from the origin of the connecting chain. Industrial Applicability As described above, the cast film of the present invention is excellent in balance and transparency of impact resistance and rigidity, particularly at low temperatures, and has excellent heat seal strength. Therefore, it can be used in a wider range of applications, such as in the field of automobiles and home appliances. In particular, transparency and heat-sealing strength can be further improved by increasing the propylene content Fp of the xylene solubles Xs to more than 60% by mass. Moreover, by making the tortuosity of xylene insoluble Xi and the tortuosity of xylene soluble Xs fall within a specific range, transparency, impact resistance, rigidity, and heat resistance can reach a higher-order balance. In addition, the container of the present invention is capable of suppressing pomelo peel, and is superior in bag dropping strength and blocking resistance. -37-