TW201919900A - Polypropylene-based laminate film - Google Patents

Polypropylene-based laminate film Download PDF

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TW201919900A
TW201919900A TW107131723A TW107131723A TW201919900A TW 201919900 A TW201919900 A TW 201919900A TW 107131723 A TW107131723 A TW 107131723A TW 107131723 A TW107131723 A TW 107131723A TW 201919900 A TW201919900 A TW 201919900A
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polypropylene
heat
film
layer
molecular weight
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TW107131723A
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TWI835744B (en
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木下理
山田浩司
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日商東洋紡股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

To provide a heat-sealable stretched polypropylene laminate film which has a low shrinkage rate at 150 DEG C comparable to the shrinkage rate of PET and a high rigidity. A polypropylene-based laminate film which comprises a substrate layer (A), said substrate layer (A) being formed of a polypropylene resin satisfying requirements 1) to 4), and a heat seal layer (B) formed of a polyolefin-based resin, said heat seal layer (B) being laminated on one or both faces of the substrate layer, wherein the lower limit of the plane orientation coefficient of the film is 0.0125. 1) The lower limit of the mesopentad fraction is 96%. 2) The upper limit of the content of comonomer(s) other than propylene is 0.1 mol%. 3) The ratio [mass-average molecular weight (Mw)/number-average molecular ratio (Mn)] is 3.0-5.4 inclusive. 4) The melt flow rate (MFR) measured at 230 DEG C and 2.16 kgf is 6.2-9.0 g/10 min inclusive.

Description

聚丙烯系積層膜 Polypropylene laminated film

本發明係關於一種具有熱封性之聚丙烯系積層膜。進一步詳細而言，係關於一種用於包裝用途之具有優異之熱封強度的聚丙烯系積層膜。更詳細而言，本發明係關於一種熱封性優異之聚丙烯系積層膜，可適用於需要高溫下之尺寸穩定性或高剛性之各種領域且耐熱性、機械特性亦優異。 The present invention relates to a polypropylene-based laminated film having heat-sealability. More specifically, it relates to a polypropylene-based laminated film having excellent heat-sealing strength for packaging applications. More specifically, the present invention relates to a polypropylene-based laminated film having excellent heat-sealability, which is applicable to various fields requiring dimensional stability or high rigidity at high temperatures, and is also excellent in heat resistance and mechanical properties.

以往使用了聚丙烯之延伸膜已汎用於食品或各種商品的包裝用、電絕緣用、表面保護膜等廣泛的用途，其中一種係有著需要熱封性的用途。以往作為具有熱封性之聚丙烯系積層膜而言，通常使用於聚丙烯系樹脂經積層低熔點的聚烯烴系樹脂而共擠出之積層聚丙烯系樹脂膜。 In the past, stretch films using polypropylene have been widely used in foods, various products for packaging, electrical insulation, and surface protection films. One of them has applications requiring heat sealability. Conventionally, as a polypropylene-based laminated film having heat-sealability, a polypropylene-based resin film in which a polypropylene-based resin is co-extruded by laminating a low-melting polyolefin-based resin is generally used.

作為這種可熱封膜之一，係提出有於150℃具有相當於PET(聚對苯二甲酸乙二酯；polyethylene terephthalate)之低收縮率且在高溫下可熱封的延伸聚丙烯積層膜(例如參照專利文獻1)。 As one of such heat-sealable films, an extended polypropylene laminate film having a low shrinkage equivalent to PET (polyethylene terephthalate) at 150 ° C and heat-sealable at high temperatures has been proposed. (For example, refer to Patent Document 1).

然而，該膜也在機械特性有待改善的餘地。 However, the film also has room for improvement in mechanical properties.

[先前技術文獻] [Prior technical literature]

[專利文獻] [Patent Literature]

專利文獻1：WO2015/0126165號手冊。 Patent document 1: WO2015 / 0126165.

本發明之課題係以以往之技術作為背景。亦即，提供一種聚丙烯系積層膜，係用於包裝用途之具有優異之熱封強度。 The subject of the present invention is based on the conventional technology. That is, a polypropylene-based laminated film is provided, which has excellent heat-sealing strength for packaging applications.

為了達成所述目的，本發明人致力研究的結果，完成了本發明。 In order to achieve the stated object, the present inventors have devoted themselves to the results of research and completed the present invention.

亦即，本發明之聚丙烯系積層膜，係由基材層(A)以及熱封層(B)所構成；前述基材層(A)之構成層之聚丙烯樹脂係滿足下述1)至4)的條件；前述熱封層(B)係由積層於該基材層的單面或是雙面之聚烯烴系樹脂所構成；膜的面配向係數的下限為0.0125： That is, the polypropylene-based laminated film of the present invention is composed of a base material layer (A) and a heat-sealable layer (B); the polypropylene resin of the constituent layer of the base material layer (A) satisfies the following 1) To 4); the aforementioned heat-sealing layer (B) is composed of a polyolefin resin laminated on one or both sides of the substrate layer; the lower limit of the surface alignment coefficient of the film is 0.0125:

1)中五單元組(Meso Pentad)分率的下限為96%。 1) The lower limit of the Meso Pentad score is 96%.

2)丙烯以外的共聚單體量的上限為0.1mol%。 2) The upper limit of the amount of comonomers other than propylene is 0.1 mol%.

3)質量平均分子量(Mw)/數平均分子量(Mn)為3.0以上、5.4以下。 3) The mass average molecular weight (Mw) / number average molecular weight (Mn) is 3.0 or more and 5.4 or less.

4)於230℃、2.16kgf所測定之熔體流動速率(Melt mass-flow rate；MFR)為6.2g/10min以上、9.0g/10min以下； 這種情況下，較佳係膜的縱向方向以及橫向方向的150℃之熱收縮率為8%以下。 4) Melt mass-flow rate (MFR) measured at 230 ° C and 2.16kgf is 6.2g / 10min or more and 9.0g / 10min or less; In this case, it is preferable that the thermal shrinkage of the film at 150 ° C. in the longitudinal direction and the transverse direction is 8% or less.

此外，這種情況下，較佳係MD方向(Machine Direction；機械方向)的楊氏模數為2.1GPa以上、TD方向(Transverse Direction；橫斷方向)的楊氏模數為3.7GPa以上。 In this case, the Young's modulus in the MD direction (Machine Direction) is preferably 2.1 GPa or more, and the TD direction (Transverse Direction; the Young's modulus of 3.7 GPa or more.

再者，較佳係將熱封層(B)面彼此重疊而以140℃進行1秒鐘熱板密封所獲得之10mm寬度的試驗片的180度剝離強度為8.0N/15mm以上。 Furthermore, it is preferable that the 180-degree peel strength of a 10-mm-width test piece obtained by overlapping the heat-sealable layer (B) surfaces with each other and hot-plate sealing at 140 ° C for 1 second is 8.0 N / 15 mm or more.

再者，這種情況下，較佳係構成熱封樹脂(B)之聚烯烴系樹脂為丙烯無規共聚物以及/或是丙烯嵌段共聚物。 In this case, the polyolefin-based resin constituting the heat-sealing resin (B) is preferably a propylene random copolymer and / or a propylene block copolymer.

藉由本發明，使用於包裝用途優異，且非常適於熱封加工。 According to the present invention, it is excellent in packaging applications and is very suitable for heat sealing processing.

然後，例如藉由將熱封溫度設定為高溫，可加大製袋加工之生產線速度等，並提高生產性。此外，藉由提高熱封溫度，亦可提高熱封強度。 Then, for example, by setting the heat-sealing temperature to a high temperature, the production line speed of bag-making processing can be increased, and productivity can be improved. In addition, the heat-sealing strength can be increased by increasing the heat-sealing temperature.

然後，可適用於需要高溫下之尺寸穩定性或高剛性之各種領域，例如可在進行蒸煮等高溫處理時抑制袋的變形量。進而可薄膜化。 Then, it can be applied to various fields requiring dimensional stability or high rigidity at high temperature, for example, it is possible to suppress the amount of deformation of the bag during high-temperature processing such as cooking. Furthermore, it can be made into a thin film.

本發明係關於一種具有熱封性之聚丙烯系積層膜。更詳細而言，係關於一種用於包裝用途之具有優異之充分的熱封強度的聚丙烯系積層膜。 The present invention relates to a polypropylene-based laminated film having heat-sealability. More specifically, it relates to a polypropylene-based laminated film having excellent sufficient heat-sealing strength for packaging applications.

本發明的聚丙烯系積層膜的特徵係在於用於基材層(A)之聚丙烯樹脂的分子量分布狀態。 The polypropylene-based laminated film of the present invention is characterized by the molecular weight distribution state of the polypropylene resin used in the substrate layer (A).

本發明的聚丙烯系積層膜，係由基材層(A)以及熱封層(B)所構成；前述基材層(A)之構成層之聚丙烯樹脂係滿足下述1)至4)的條件；前述熱封層(B)係由積層於該基材層的單面或是雙面之聚烯烴系樹脂所構成；膜的面配向係數的下限為0.0125： The polypropylene-based laminated film of the present invention is composed of a base material layer (A) and a heat-sealable layer (B); the polypropylene resin of the constituent layer of the base material layer (A) satisfies the following 1) to 4) Conditions; the aforementioned heat-sealing layer (B) is composed of a polyolefin resin laminated on one or both sides of the substrate layer; the lower limit of the surface alignment coefficient of the film is 0.0125:

1)中五單元組分率的下限為96%。 1) The lower limit of the composition ratio of the middle five units is 96%.

2)丙烯以外的共聚單體量的上限為0.1mol%。 2) The upper limit of the amount of comonomers other than propylene is 0.1 mol%.

3)質量平均分子量(Mw)/數平均分子量(Mn)為3.0以上、5.4以下。 3) The mass average molecular weight (Mw) / number average molecular weight (Mn) is 3.0 or more and 5.4 or less.

4)於230℃、2.16kgf所測定之熔體流動速率(MFR)為6.2g/10min以上、9.0g/10min以下。 4) The melt flow rate (MFR) measured at 230 ° C and 2.16 kgf is 6.2g / 10min or more and 9.0g / 10min or less.

進而以下將詳細說明。 Further details will be described below.

(基材層(A)) (Substrate layer (A))

用於本發明的基材層(A)之聚丙烯樹脂，係可使用將乙烯以及/或是碳數4以上的α-烯烴以0.5莫耳%以下共聚之聚丙烯樹脂。這種共聚聚丙烯樹脂亦包含在本發明的聚丙烯樹脂(以下稱為聚丙烯樹脂)。共聚成分較佳係0.3莫耳%以下，更佳係0.1莫耳%以下，尤佳係不包含共聚成分之完全均聚丙烯樹脂。 As the polypropylene resin used in the substrate layer (A) of the present invention, a polypropylene resin in which ethylene and / or α-olefin having 4 or more carbon atoms are copolymerized at 0.5 mol% or less can be used. Such a copolymerized polypropylene resin is also included in the polypropylene resin of the present invention (hereinafter referred to as a polypropylene resin). The copolymerization component is preferably 0.3 mol% or less, more preferably 0.1 mol% or less, and particularly preferably a completely homopolypropylene resin that does not include a copolymerization component.

乙烯以及/或是碳數4以上的α-烯烴若共聚超過0.5莫耳%，則結晶性或剛性可能過低，高溫下之熱收縮率可能變大。亦可摻合使用這樣的樹脂。 When ethylene and / or an α-olefin having 4 or more carbon atoms are copolymerized to more than 0.5 mol%, the crystallinity or rigidity may be too low, and the thermal shrinkage at high temperatures may be increased. Such a resin may be blended and used.

聚丙烯樹脂的立體規則性的指標之以13C-NMR(carbon-13 nuclear magnetic resonance；碳-13核磁共振)測定之中五單元組分率(〔mmmm〕%)較佳係96%至99.5%。更佳係97%以上，又 更佳係98%以上。若基材層(A)的聚丙烯的中五單元組分率小，則可能有結晶的熔點變低，彈性模數以及高溫下之耐熱性不充分之虞。99.5%為實際的上限。 The index of the three-dimensional regularity of polypropylene resin is determined by 13C-NMR (carbon-13 nuclear magnetic resonance). The five-unit composition ratio ((mmmm)%) is preferably 96% to 99.5%. . More than 97%, and More than 98%. When the pentad fraction of the polypropylene of the base material layer (A) is small, the melting point of crystals may be lowered, and the elastic modulus and heat resistance at high temperatures may be insufficient. 99.5% is the actual upper limit.

此外，分子量分布的指標的Mw/Mn，聚丙烯樹脂則較佳係3.0至5.4。更佳係3.0至5.0，又更佳係3.2至4.5，尤佳係3.3至4.0。 The Mw / Mn, which is an index of molecular weight distribution, is preferably 3.0 to 5.4 for the polypropylene resin. More preferred is 3.0 to 5.0, more preferred is 3.2 to 4.5, and even more preferred is 3.3 to 4.0.

若構成基材層(A)之聚丙烯樹脂整體的Mw/Mn為5.4以下，則高分子量成分雖然存在，但傾向高分子量成分的量變少且熱收縮率變小。若高分子量成分存在，則雖然有促進低分子量成分的結晶化的一面，但分子彼此的纏結變強，即便結晶性高但仍成為使熱收縮率變大的因素。 When the Mw / Mn of the entire polypropylene resin constituting the base material layer (A) is 5.4 or less, the high-molecular-weight component is present, but the amount of the high-molecular-weight component tends to be small and the heat shrinkage ratio is small. When a high-molecular-weight component is present, although the crystallization of the low-molecular-weight component is promoted, the entanglement of molecules becomes stronger, and even if the crystallinity is high, it becomes a factor that increases the thermal shrinkage rate.

此外，若構成基材層(A)之聚丙烯樹脂整體的Mw/Mn為5.4以下，則傾向分子量非常低的低分子量成分變多且彈性模數變小。若分子量非常低的低分子量成分存在，雖然分子彼此的纏結變弱，可在低延伸應力下延伸，結晶性變高，但亦是使彈性模數降低的因素。 In addition, when the Mw / Mn of the entire polypropylene resin constituting the base material layer (A) is 5.4 or less, low-molecular-weight components tending to have a very low molecular weight tend to increase and the elastic modulus decrease. When a low molecular weight component having a very low molecular weight is present, although the entanglement of the molecules becomes weak, it can be stretched under a low elongation stress, and the crystallinity becomes high, but it is also a factor that reduces the elastic modulus.

若構成本發明的基材層(A)之聚丙烯樹脂整體的Mw/Mn小於3.0，則製膜變得困難。Mw係指質量平均分子量，Mn係指數平均分子量。 When the Mw / Mn of the entire polypropylene resin constituting the base material layer (A) of the present invention is less than 3.0, film formation becomes difficult. Mw means mass average molecular weight, and Mn is index average molecular weight.

聚丙烯樹脂的質量平均分子量(Mw)較佳係180,000至500,000。Mw的下限更佳係190,000，又更佳係200,000，Mw的上限更佳係320,000，又更佳係300,000，尤佳係250,000。 The mass average molecular weight (Mw) of the polypropylene resin is preferably 180,000 to 500,000. The lower limit of Mw is more preferably 190,000, and more preferably 200,000. The upper limit of Mw is more than 320,000, more preferably 300,000, and even more preferably 250,000.

聚丙烯樹脂的數平均分子量(Mn)較佳係20,000至200,000。 Mn的下限更佳係30,000，又更佳係40,000，尤佳係50,000，Mn的上限更佳係80,000，又更佳係70,000，尤佳係60,000。 The number average molecular weight (Mn) of the polypropylene resin is preferably 20,000 to 200,000. The lower limit of Mn is more preferably 30,000, more preferably 40,000, particularly preferably 50,000, and the upper limit of Mn is more preferably 80,000, more preferably 70,000, and even more preferably 60,000.

測定構成基材層(A)之聚丙烯樹脂整體的凝膠滲透層析法(Gel Permeation Chromatography；GPC)累計曲線的情況，分子量10萬以下的成分的量的下限較佳係35質量%，更佳係38質量%，又更佳係40質量%，尤佳係41質量%，最佳係42質量%。 When measuring the cumulative curve of Gel Permeation Chromatography (GPC) of the entire polypropylene resin constituting the base material layer (A), the lower limit of the amount of components having a molecular weight of 100,000 or less is preferably 35% by mass, more The best line is 38% by mass, the better line is 40% by mass, the particularly good line is 41% by mass, and the best line is 42% by mass.

另一方面，GPC累計曲線下之分子量10萬以下的成分的量的上限較佳係65質量%，更佳係60質量%，又更佳係58質量%，尤佳係56質量%，最佳係55質量%。若為上述範圍則延伸變得容易，厚度不均變小，延伸溫度或熱固定溫度容易提高且可將熱收縮率抑制得更低。 On the other hand, the upper limit of the amount of components with a molecular weight of 100,000 or less under the cumulative GPC curve is preferably 65% by mass, more preferably 60% by mass, even more preferably 58% by mass, and even more preferably 56% by mass. Department of 55 mass%. If it exists in the said range, extending | stretching becomes easy, thickness unevenness will become small, extending | stretching temperature or heat setting temperature will become easy to raise, and a heat shrinkage rate can be suppressed low.

測定構成基材層(A)之聚丙烯樹脂整體的凝膠滲透層析法(GPC)累計曲線的情況，分子量1萬以下的成分的量的下限較佳係1質量%，更佳係1.5質量%。 When the gel permeation chromatography (GPC) cumulative curve of the entire polypropylene resin constituting the base material layer (A) is measured, the lower limit of the amount of components having a molecular weight of 10,000 or less is preferably 1% by mass, and more preferably 1.5% by mass. %.

另一方面，GPC累計曲線下之分子量1萬以下的成分的量的上限較佳係5質量%，更佳係4質量%，又更佳係3.5質量%，尤佳係3重量%。 On the other hand, the upper limit of the amount of components having a molecular weight of 10,000 or less under the GPC cumulative curve is preferably 5 mass%, more preferably 4 mass%, still more preferably 3.5 mass%, and even more preferably 3 weight%.

此時的聚丙烯樹脂的熔體流動速率(MFR；230℃、2.16kgf)較佳係6.2g/10分鐘至10.0g/10分鐘。 The melt flow rate (MFR; 230 ° C, 2.16 kgf) of the polypropylene resin at this time is preferably 6.2 g / 10 minutes to 10.0 g / 10 minutes.

聚丙烯樹脂的MFR的下限更佳係6.5g/10分鐘，又更佳係7g/10分鐘，尤佳係7.5g/10分鐘。聚丙烯樹脂的MFR的上限更佳係9g/10分鐘，又更佳係8.5g/10分鐘，尤佳係8.2g/10分鐘。 The lower limit of the MFR of the polypropylene resin is more preferably 6.5 g / 10 minutes, more preferably 7 g / 10 minutes, and even more preferably 7.5 g / 10 minutes. The upper limit of the MFR of the polypropylene resin is more preferably 9 g / 10 minutes, more preferably 8.5 g / 10 minutes, and even more preferably 8.2 g / 10 minutes.

若熔體流動速率(MFR；230℃、2.16kgf)為6.2g/10分鐘以上，則高溫下之熱收縮率可變得更小。然後，由於延伸所產生的膜的結晶化的程度變強，故膜的剛性變高，尤其是寬度(TD)方向的拉伸彈性模數(楊氏模數)變高。此外，若熔體流動速率(MFR；230℃、2.16kgf)為9.0g/10分鐘以下則容易進行製膜而不破裂。 If the melt flow rate (MFR; 230 ° C, 2.16 kgf) is 6.2 g / 10 minutes or more, the thermal shrinkage at a high temperature can be made smaller. Then, since the degree of crystallization of the film produced by stretching becomes stronger, the rigidity of the film becomes higher, and in particular, the tensile elastic modulus (Young's modulus) in the width (TD) direction becomes high. In addition, if the melt flow rate (MFR; 230 ° C, 2.16 kgf) is 9.0 g / 10 minutes or less, it is easy to form a film without cracking.

另外，聚丙烯樹脂的分子量分布係可藉由如下方式調整：將不同分子量的成分多段階地以一系列的設備聚合；將不同分子量的成分以離線(off-line)以捏合機摻合；摻合具有不同性能的催化劑而聚合；使用可實現期望的分子量分布的催化劑。 In addition, the molecular weight distribution of polypropylene resin can be adjusted by: polymerizing components of different molecular weights in a series of steps in a series of equipment; blending components of different molecular weights off-line with a kneader; blending Polymerize catalysts with different properties; use catalysts that achieve the desired molecular weight distribution.

本發明所使用之聚丙烯樹脂，係使用齊格勒-納他催化劑或二茂金屬催化劑等的公知的催化劑，藉由使原料的丙烯進行聚合所獲得。其中，為了消除異構結合而使用齊格勒-納他催化劑，較佳係使用立體規則性高的可聚合的催化劑。 The polypropylene resin used in the present invention is obtained by polymerizing propylene, which is a known catalyst, such as a Ziegler-Natta catalyst or a metallocene catalyst. Among them, a Ziegler-Natta catalyst is used to eliminate heterogeneous bonding, and a polymerizable catalyst having high stereoregularity is preferably used.

作為丙烯的聚合方法而言，可採用公知的方法即可，可列舉例如：在己烷、庚烷、甲苯、二甲苯等的惰性溶劑中進行聚合的方法；液狀的單體中進行聚合的方法；於氣體的單體添加催化劑，以氣相狀態進行聚合的方法；或是將這些組合而進行聚合的方法等。 The polymerization method of propylene may be a known method, and examples thereof include a method of polymerization in an inert solvent such as hexane, heptane, toluene, xylene, and the like; Method; a method of adding a catalyst to a monomer of a gas to perform polymerization in a gas phase state; or a method of combining these to perform polymerization.

聚丙烯樹脂亦可含有添加劑或其它的樹脂。作為添加劑而言，可列舉例如：抗氧化劑、紫外線吸收劑、成核劑、黏著劑、防霧劑、阻燃劑、無機或是有機的充填劑等。作為其它的樹脂而言，可列舉本發明所使用之聚丙烯樹脂以外的聚丙烯樹脂、丙烯與乙烯以及/或是碳數4以上的α-烯烴的共聚物之無規共 聚物、或各種彈性體等。這些可使用多段的反應器進行逐次聚合、或是與聚丙烯樹脂以亨舍爾攪拌器進行摻合、或是事先使用熔融捏合機將製作之母粒以成為預定的濃度的方式以聚丙烯進行稀釋、或是預先將總量經熔融混練而使用亦可。 The polypropylene resin may also contain additives or other resins. Examples of the additives include antioxidants, ultraviolet absorbers, nucleating agents, adhesives, antifog agents, flame retardants, inorganic or organic fillers, and the like. Examples of other resins include random copolymers of polypropylene resins other than the polypropylene resins used in the present invention, copolymers of propylene with ethylene, and / or α-olefins having 4 or more carbon atoms. Polymers, or various elastomers. These can be carried out by using a multi-stage reactor for sequential polymerization, or blended with a polypropylene resin using a Henschel mixer, or by using a melt kneader to prepare the master batches in a predetermined concentration in polypropylene. It may be diluted, or the total amount may be melt-kneaded before use.

(熱封層(B)) (Heat Sealing Layer (B))

此外，本發明之中，用於熱封層(B)的樹脂較佳係熔點為150℃以下的低熔點的丙烯無規共聚物，或是分散有含有共聚單體的彈性體成分之丙烯嵌段共聚物，此外，可單獨使用這些共聚物或是混合使用。作為共聚單體而言，較佳係由乙烯、丁烯、戊烯、己烯、辛烯或是癸烯等的碳數為3至10的α-烯烴所選擇之1種以上。 In addition, in the present invention, the resin used for the heat-seal layer (B) is preferably a low-melting propylene random copolymer having a melting point of 150 ° C. or lower, or a propylene insert in which an elastomer component containing a comonomer is dispersed. The segment copolymers may be used alone or in combination. As the comonomer, one or more kinds selected from α-olefins having 3 to 10 carbon atoms such as ethylene, butene, pentene, hexene, octene, or decene are preferred.

再者，形成熱封層(B)的丙烯無規共聚物的熔點較佳係60℃至150℃。藉此可賦予延伸聚丙烯系樹脂積層膜充分的熱封強度。若形成熱封層(B)之丙烯無規共聚物的熔點小於60℃則缺乏熱封部的耐熱性，若超過150℃則無法期待提高熱封強度。此外，丙烯嵌段共聚物中所包含之彈性體成分的熔點亦較佳係150℃以下。 The melting point of the propylene random copolymer forming the heat-sealing layer (B) is preferably 60 ° C to 150 ° C. Thereby, sufficient heat-sealing strength can be imparted to the stretched polypropylene-based resin laminated film. If the melting point of the propylene random copolymer forming the heat-sealing layer (B) is less than 60 ° C, the heat resistance of the heat-sealed portion is insufficient, and if it exceeds 150 ° C, the heat-sealing strength cannot be expected to increase. The melting point of the elastomer component contained in the propylene block copolymer is also preferably 150 ° C or lower.

此外，可例示MFR係0.1g/10min至100g/10min，較佳係0.5g/10min至20g/10min，又更佳係1.0g/10min至10g/10min的範圍。 In addition, MFR is exemplified by a range of 0.1 g / 10min to 100g / 10min, preferably 0.5g / 10min to 20g / 10min, and more preferably 1.0g / 10min to 10g / 10min.

熱封層(B)所使用之聚丙烯樹脂係使用齊格勒-納他催化劑或二茂金屬催化劑等的公知的催化劑，使得成為原料的丙烯進行聚合所獲得。其中為了消除異構結合而使用齊格勒-納他催化 劑，且較佳係使用立體規則性高的可聚合的催化劑。 The polypropylene resin used for the heat-seal layer (B) is obtained by polymerizing propylene as a raw material using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. In which Ziegler-Natta catalysis is used to eliminate heterogeneous binding It is preferred to use a polymerizable catalyst having high stereoregularity.

作為丙烯的聚合方法而言，以公知的方法亦可，可列舉如下方法：在己烷、庚烷、甲苯、二甲苯等的惰性溶劑中進行聚合的方法；在液狀的丙烯或乙烯中進行聚合的方法；於氣體的丙烯或乙烯中添加催化劑，以氣相狀態進行聚合的方法；或是將這些組合而進行聚合的方法等。 As a method for polymerizing propylene, a known method may be used, and examples thereof include a method of polymerizing in an inert solvent such as hexane, heptane, toluene, and xylene; and a method of polymerizing propylene or ethylene in a liquid state. A method of polymerization; a method of adding a catalyst to gaseous propylene or ethylene to perform polymerization in a gas phase state; or a method of combining these to perform polymerization.

高分子量成分、低分子量成分可分別聚合之後進行混合，亦可在多段階的反應器以一系列的設備進行製造。尤其使用具有多段階的反應器的設備，在最初將高分子量成分聚合之後在該聚合物存在下將低分子量成分進行聚合之方法較佳。 The high-molecular-weight component and the low-molecular-weight component can be polymerized and mixed separately, or they can be produced by a series of equipment in a multi-stage reactor. In particular, using an apparatus having a multi-stage reactor, a method of polymerizing a low-molecular-weight component in the presence of the polymer after polymerizing a high-molecular-weight component initially is preferred.

(聚丙烯膜的製造方法) (Manufacturing method of polypropylene film)

本發明的聚丙烯系積層膜而言係長度方向(MD方向)或是橫向方向(TD方向)的一軸延伸膜亦可，但較佳係雙軸延伸膜。 The polypropylene-based laminated film of the present invention may be a uniaxially stretched film in a longitudinal direction (MD direction) or a transverse direction (TD direction), but is preferably a biaxially stretched film.

雙軸延伸的情況可為逐次雙軸延伸亦可為同時雙軸延伸。 The case of biaxial extension may be sequential biaxial extension or simultaneous biaxial extension.

藉由作成延伸膜，可以獲得在以往的聚丙烯系積層膜無法預料的即使在150℃之熱收縮率亦低的膜。 By forming the stretched film, it is possible to obtain a film having a low thermal shrinkage rate which is unexpected even in a conventional polypropylene-based laminated film even at 150 ° C.

以下說明最佳例之縱向延伸-横向延伸的逐次雙軸延伸的膜的製造方法。 Hereinafter, a method for producing a film that is sequentially stretched biaxially and stretched in the longitudinal direction and the transverse direction in the best example will be described.

首先，藉由其中一方的擠出機熔融擠出基材層(A)，藉由另一方的擠出機熔融擠出熱封層(B)，於T字模內以成為聚丙烯系樹脂層(A)與熱封層(B)的方式積層，於冷卻輥(CR；Cooling roller)經冷卻固化以獲得未延伸片材。作為熔融擠出條件而言，樹脂溫度以成為200℃至280℃的方式從T字模擠出為片材狀，以10℃至100℃的溫度的冷卻輥進行冷卻固化。隨後，以120℃至 165℃的延伸輥將膜在長度(MD)方向延伸3倍至7倍，然後在寬度(TD)方向以155℃至175℃的溫度進行6倍至12倍延伸，較佳係158℃至170℃的溫度進行6倍至12倍延伸。 First, the base material layer (A) is melt-extruded by one extruder, and the heat-seal layer (B) is melt-extruded by the other extruder to form a polypropylene resin layer in a T-die ( A) It is laminated with the heat-sealing layer (B), and is cooled and solidified on a cooling roller (CR) to obtain an unstretched sheet. In terms of melt extrusion conditions, the resin temperature is extruded from a T-die into a sheet shape so as to become 200 ° C to 280 ° C, and is cooled and solidified by a cooling roll at a temperature of 10 ° C to 100 ° C. Subsequently, at 120 ° C to The stretching roller at 165 ° C stretches the film 3 to 7 times in the length (MD) direction, and then stretches 6 to 12 times in the width (TD) direction at a temperature of 155 ° C to 175 ° C, preferably 158 ° C to 170. The temperature at 6 ° C is extended from 6 to 12 times.

然後，以165℃至175℃的氛圍溫度容許1%至15%的鬆弛一邊施以熱處理，較佳係以166至173℃的氛圍溫度容許1%至15%的鬆弛一邊施以熱處理。 Then, heat treatment is allowed while allowing 1% to 15% relaxation at an ambient temperature of 165 ° C to 175 ° C, and heat treatment is preferably allowed while allowing 1% to 15% relaxation at an ambient temperature of 166 to 173 ° C.

如果需要，可在至少單面施加電暈放電處理之後，藉由以捲繞機捲繞而獲得輥試樣。 If necessary, a roll sample can be obtained by applying a corona discharge treatment on at least one side by winding with a winder.

MD的延伸倍率的下限較佳係3倍，更佳係3.5倍。若小於上述延伸倍率則可能成為膜厚不均。 The lower limit of the MD stretching ratio is preferably 3 times, and more preferably 3.5 times. If it is smaller than the said stretching ratio, it may become uneven | corrugated.

MD的延伸倍率的上限較佳係8倍，更佳係7倍。若超過上述延伸倍率則可能難以繼續進行TD延伸。 The upper limit of the MD stretching ratio is preferably 8 times, and more preferably 7 times. If the stretching ratio is exceeded, it may be difficult to continue TD stretching.

MD的延伸溫度的下限較佳係120℃，更佳係122℃。若小於上述延伸溫度則可能發生機械的負荷變大、或厚度不均變大、或造成膜的表面粗糙。 The lower limit of MD elongation temperature is preferably 120 ° C, and more preferably 122 ° C. If it is less than the said stretching temperature, a mechanical load may increase, thickness unevenness may become large, or the surface of a film may become rough.

MD的延伸溫度的上限較佳係150℃，更佳係145℃，又更佳係135℃，尤佳係130℃。溫度較高雖然有利於降低熱收縮率，但可能附著於輥而無法延伸。 The upper limit of MD elongation temperature is preferably 150 ° C, more preferably 145 ° C, still more preferably 135 ° C, and even more preferably 130 ° C. Although the higher temperature is beneficial for reducing the heat shrinkage rate, it may adhere to the roller and cannot be extended.

TD的延伸倍率的下限較佳係4倍，更佳係5倍，又更佳係6倍。若小於上述延伸倍率則可能厚度不均。 The lower limit of the extension ratio of TD is preferably 4 times, more preferably 5 times, and even more preferably 6 times. If it is smaller than the said draw ratio, thickness may become uneven.

TD延伸倍率的上限較佳係20倍，更佳係17倍，又更佳係15倍。若超過上述延伸倍率則可能熱收縮率變高、或是在延伸時破裂。 The upper limit of the TD extension magnification is preferably 20 times, more preferably 17 times, and even more preferably 15 times. If it exceeds the said stretching ratio, a heat shrinkage rate may become high, or it may break during stretching.

為了TD延伸下之預熱溫度迅速提高膜溫度至延伸溫度附近，較佳係設定高於延伸溫度10℃至15℃。 In order to quickly increase the film temperature to the vicinity of the stretching temperature under the preheating temperature under TD stretching, it is preferable to set the temperature 10 to 15 ° C higher than the stretching temperature.

TD的延伸則以較以往的熱封性聚丙烯積層延伸膜更高溫進行。 The TD is stretched at a higher temperature than the conventional heat-sealable polypropylene laminated stretch film.

TD的延伸溫度的下限較佳係157℃，更佳係158℃。若小於上述延伸溫度則可能無法充分地軟化而破裂或是熱收縮率變高。 The lower limit of the elongation temperature of TD is preferably 157 ° C, and more preferably 158 ° C. If it is less than the said elongation temperature, it may not be softened sufficiently, it may crack | rupture, or a thermal contraction rate may become high.

TD延伸溫度的上限較佳係170℃，更佳係168℃。為了降低熱收縮率雖然溫度高者較佳，但若超過上述溫度則可能有低分子成分熔解、再結晶化而造成表面粗糙或膜白化的情況。 The upper limit of the TD extension temperature is preferably 170 ° C, and more preferably 168 ° C. In order to reduce the thermal shrinkage, it is preferable to use a high temperature, but if it exceeds the above temperature, the low-molecular component may be melted and recrystallized to cause surface roughening or film whitening.

延伸後的膜係被熱固定。熱固定可以較以往的聚丙烯膜更高溫進行。熱固定溫度的下限較佳係165℃，更佳係166℃。若小於上述熱固定溫度則熱收縮率可能變高。此外，為了降低熱收縮率則需要長時間，可能導致生產性差。 The stretched film system is heat-fixed. Heat fixing can be performed at higher temperatures than conventional polypropylene films. The lower limit of the heat fixing temperature is preferably 165 ° C, and more preferably 166 ° C. If it is less than the said heat-fixing temperature, a thermal contraction rate may become high. In addition, it takes a long time to reduce the heat shrinkage rate, which may result in poor productivity.

熱固定溫度的上限較佳係175℃，更佳係173℃。若超過上述熱固定溫度則可能有低分子成分熔解、再結晶化而造成表面粗糙或膜白化的情況。 The upper limit of the heat fixing temperature is preferably 175 ° C, and more preferably 173 ° C. If it exceeds the above-mentioned heat-fixing temperature, the low-molecular component may be melted and recrystallized to cause surface roughening or film whitening.

較佳係於熱固定時鬆弛(鬆緩)。鬆弛的下限較佳係2%，更佳係3%。若小於上述鬆弛的下限則熱收縮率可能變高。 It is preferably loosened (relaxed) during heat fixing. The lower limit of relaxation is preferably 2%, and more preferably 3%. If it is less than the said lower limit of slack, the heat shrinkage rate may become high.

鬆弛的上限較佳係10%，更佳係8%。若超過上述鬆弛的上限則可能厚度不均變大。 The upper limit of relaxation is preferably 10%, and more preferably 8%. When the upper limit of the slack is exceeded, thickness unevenness may increase.

然後，為了降低熱收縮率，可將於上述的步驟所製造之膜暫時捲繞成輥狀之後，離線使其退火。 Then, in order to reduce the thermal shrinkage, the film manufactured in the above steps may be temporarily wound into a roll shape, and then annealed offline.

離線退火溫度的下限較佳係160℃，更佳係162℃，又更佳係163℃。若小於上述離線退火溫度則可能無法獲得退火的功效。 The lower limit of the offline annealing temperature is preferably 160 ° C, more preferably 162 ° C, and even more preferably 163 ° C. If it is lower than the off-line annealing temperature, the effect of annealing may not be obtained.

離線退火溫度的上限較佳係175℃，更佳係174℃，又更佳係173℃。若超過上述離線退火溫度則可能透明性降低或是厚度不均大幅增加。 The upper limit of the offline annealing temperature is preferably 175 ° C, more preferably 174 ° C, and even more preferably 173 ° C. If it exceeds the above-mentioned off-line annealing temperature, transparency may decrease or thickness unevenness may increase significantly.

離線退火時間的下限較佳係0.1分鐘，更佳係0.5分鐘，又更佳係1分鐘。若小於上述離線退火時間則可能無法獲得退火的功效。 The lower limit of the offline annealing time is preferably 0.1 minutes, more preferably 0.5 minutes, and even more preferably 1 minute. If it is shorter than the off-line annealing time, the effect of annealing may not be obtained.

離線退火時間的上限較佳係30分鐘，更佳係25分鐘，又更佳係20分鐘。若超過上述離線退火時間則可能生產性降低。 The upper limit of the offline annealing time is preferably 30 minutes, more preferably 25 minutes, and even more preferably 20 minutes. If the off-line annealing time is exceeded, productivity may be reduced.

膜的厚度可配合各用途而設定，但膜厚度的下限較佳係2μm，更佳係3μm，又更佳係4μm。膜厚度的上限較佳係300μm，更佳係250μm，又更佳係200μm，尤佳係100μm，最佳係50μm。 The thickness of the film can be set according to each application, but the lower limit of the film thickness is preferably 2 μm, more preferably 3 μm, and even more preferably 4 μm. The upper limit of the film thickness is preferably 300 μm, more preferably 250 μm, still more preferably 200 μm, particularly preferably 100 μm, and most preferably 50 μm.

這樣所獲得之聚丙烯系積層膜通常作成寬度2000mm至12000mm、長度1000m至50000m左右的輥而製膜，捲繞成輥狀。 The polypropylene-based laminated film thus obtained is usually formed into a roll having a width of 2000 mm to 12000 mm and a length of about 1000 m to 50,000 m, and is wound into a roll shape.

進而，配合各用途而切割作為寬度300mm至2000mm、長度500m至5000m左右的切割輥。 Furthermore, it cuts as a cutting roll with a width of 300 mm to 2000 mm and a length of about 500 m to 5000 m according to each application.

本發明的聚丙烯系積層膜係具有如上述那樣以往所沒有之 優異之特性。 The polypropylene-based laminated film according to the present invention has a conventionally-unexposed layer as described above. Excellent characteristics.

作為包裝膜使用的情況下，由於高剛性故可薄化，可降低成本、輕量化。 When used as a packaging film, it can be thinned due to its high rigidity, which can reduce cost and weight.

此外，由於耐熱性高，故在塗布或印刷的乾燥時可高溫乾燥，可達成生產的效率化或可以使用以往難以使用的塗布劑或墨水、層疊接著劑等。由於沒有必要使用有機溶劑等的層疊步驟的必要，故由經濟上對地球環境的影響的方面來看亦較佳。 In addition, since it has high heat resistance, it can be dried at high temperature during drying of coating or printing, which can improve production efficiency, and can use coating agents, inks, laminating adhesives, etc., which have been difficult to use in the past. Since a lamination step using an organic solvent or the like is not necessary, it is also preferable from the aspect of economical impact on the global environment.

(膜特性) (Film characteristics)

本發明的聚丙烯系積層膜的MD方向以及TD方向的150℃熱收縮率的下限較佳係0.5%，更佳係1%，又更佳係1.5%，尤佳係2%，最佳係2.5%。若為上述範圍則可能在成本面等實際的製造變得容易，或是厚度不均變小。 The lower limit of the 150 ° C thermal shrinkage of the polypropylene-based laminated film according to the present invention is preferably 0.5%, more preferably 1%, more preferably 1.5%, even more preferably 2%, and the best 2.5%. If it is the said range, actual manufacturing in terms of cost, etc. may become easy, or thickness unevenness may become small.

MD方向的150℃熱收縮率的上限較佳係7%，更佳係6%，又更佳係5%。若為上述範圍則在可能暴露於150℃左右的高溫下的用途變得更容易使用。另外，若150℃熱收縮率要達到2.5%左右，例如可增加低分子量成分、或調整延伸條件、固定條件來達成，但要達到更低熱收縮率較佳係以離線進行退火處理。 The upper limit of the 150 ° C thermal contraction rate in the MD direction is preferably 7%, more preferably 6%, and even more preferably 5%. If it is the said range, it will become easy to use for the use which may be exposed to the high temperature of about 150 degreeC. In addition, if the thermal shrinkage rate at 150 ° C is about 2.5%, it can be achieved by adding low molecular weight components, or adjusting the extension conditions and fixed conditions, but to achieve a lower thermal shrinkage rate, it is better to perform annealing treatment offline.

以往的延伸聚丙烯積層膜中，MD方向的150℃熱收縮率為15%以上，120℃熱收縮率為3%左右。藉由將熱收縮率設為上述的範圍，可獲得耐熱性的優異之聚丙烯系積層膜。 In the conventional stretched polypropylene laminated film, the thermal shrinkage rate at 150 ° C in the MD direction is 15% or more, and the thermal shrinkage rate at 120 ° C is about 3%. By setting the thermal shrinkage to the above range, a polypropylene-based laminated film having excellent heat resistance can be obtained.

TD方向的150℃熱收縮率的上限較佳係8%，更佳係7%，又更佳係7%。若為上述範圍則在可能暴露於150℃左右的高溫下的用途變得更容易使用。另外，若150℃熱收縮率要達到2.5% 左右，例如可增加低分子量成分、或調整延伸條件、固定條件來達成，但要達到更低熱收縮率較佳係以離線進行退火處理。 The upper limit of the 150 ° C thermal shrinkage in the TD direction is preferably 8%, more preferably 7%, and even more preferably 7%. If it is the said range, it will become easy to use for the use which may be exposed to the high temperature of about 150 degreeC. In addition, if the heat shrinkage rate at 150 ° C is 2.5% For example, it can be achieved by adding low-molecular-weight components, or adjusting elongation conditions and fixed conditions. However, to achieve a lower thermal shrinkage ratio, it is preferable to perform annealing treatment offline.

以往的延伸聚丙烯積層膜中，TD方向的150℃熱收縮率為15%以上，120℃熱收縮率為3%左右。藉由將熱收縮率設為上述的範圍，可獲得耐熱性的優異之聚丙烯系積層膜。 In the conventional stretched polypropylene laminated film, the thermal shrinkage rate at 150 ° C in the TD direction is 15% or more, and the thermal shrinkage rate at 120 ° C is about 3%. By setting the thermal shrinkage to the above range, a polypropylene-based laminated film having excellent heat resistance can be obtained.

本發明的聚丙烯系積層膜為雙軸延伸膜的情況下，MD方向的楊氏模數(23℃)的下限較佳係1.8GPa，更佳係1.9GPa，又更佳係2.0GPa，尤佳係2.1GPa，最佳係2.2GPa。 When the polypropylene-based laminated film of the present invention is a biaxially stretched film, the lower limit of the Young's modulus (23 ° C) in the MD direction is preferably 1.8 GPa, more preferably 1.9 GPa, and even more preferably 2.0 GPa, especially The best line is 2.1GPa and the best line is 2.2GPa.

MD方向的楊氏模數的上限較佳係3.7GPa，更佳係3.6GPa，更佳係3.5GPa，尤佳係3.4GPa，最佳係3.3GPa。若為上述範圍則可能在實際的製造變得容易，可優化MD-TD平衡。 The upper limit of the Young's modulus in the MD direction is preferably 3.7 GPa, more preferably 3.6 GPa, more preferably 3.5 GPa, even more preferably 3.4 GPa, and most preferably 3.3 GPa. If it is the said range, it may become easy in actual manufacture, and MD-TD balance may be optimized.

本發明的聚丙烯系積層膜為雙軸延伸膜的情況下，TD方向的楊氏模數(23℃)的下限較佳係4.4GPa，更佳係4.5GPa，又更佳係4.6GPa，尤佳係4.7GPa。 When the polypropylene-based laminated film of the present invention is a biaxially stretched film, the lower limit of the Young's modulus (23 ° C) in the TD direction is preferably 4.4 GPa, more preferably 4.5 GPa, and even more preferably 4.6 GPa, especially The best line is 4.7GPa.

TD方向的楊氏模數的上限較佳係8GPa，更佳係7.5GPa，又更佳係7GPa，尤佳係6.5GPa。若為上述範圍則可能在實際的製造變得容易，可優化MD-TD平衡。 The upper limit of the Young's modulus in the TD direction is preferably 8 GPa, more preferably 7.5 GPa, still more preferably 7 GPa, and even more preferably 6.5 GPa. If it is the said range, it may become easy in actual manufacture, and MD-TD balance may be optimized.

另外，楊氏模數可藉由提高延伸倍率而提高，MD-TD延伸的情況可將MD延伸倍率設定得更低，藉由提高TD延伸倍率而增加TD方向的楊氏模數。 In addition, the Young's modulus can be increased by increasing the stretching ratio. In the case of MD-TD stretching, the MD stretching ratio can be set lower, and the Young's modulus in the TD direction can be increased by increasing the TD stretching ratio.

本發明的聚丙烯系積層膜的面配向係數的下限較佳係0.0125，更佳係0.0126，又更佳係0.0127，尤佳係0.0128。面配向係數的上限，作為實際的值而言，較佳係0.0155，更佳係 0.0150，更佳係0.0148，尤佳係0.0145，更尤佳係0.0140。面配向係數係可藉由延伸倍率的調整而設定於範圍內。若面配向係數為該範圍，則可改善膜的厚度不均。 The lower limit of the surface alignment coefficient of the polypropylene-based laminated film of the present invention is preferably 0.0125, more preferably 0.0126, more preferably 0.0127, and even more preferably 0.0128. The upper limit of the surface alignment coefficient, as a practical value, is preferably 0.0155, more preferably 0.0150, more preferably 0.0148, more preferably 0.0145, more preferably 0.0140. The surface alignment coefficient can be set within a range by adjusting the extension magnification. When the surface alignment coefficient is within this range, the thickness unevenness of the film can be improved.

本發明的聚丙烯系積層膜的熱封強度在140℃較佳係8.0N/15mm以上，更佳係9.0N/15mm以上，更佳係10N/15mm以上。 The heat-sealing strength of the polypropylene-based laminated film of the present invention is 140 ° C., preferably 8.0 N / 15 mm or more, more preferably 9.0 N / 15 mm or more, and more preferably 10 N / 15 mm or more.

此外，本發明的聚丙烯系積層膜的熱封強度在110℃較佳係1.5N/15mm以上，更佳係2.0N/15mm以上，又更佳係2.2N/15mm以上。 In addition, the heat-sealing strength of the polypropylene-based laminated film of the present invention is preferably 110 N or more, 1.5 N / 15 mm or more, more preferably 2.0 N / 15 mm or more, and more preferably 2.2 N / 15 mm or more.

本發明的延伸聚丙烯膜的耐衝撃性(23℃)的下限較佳係0.6J，更佳係0.7J。若為上述範圍的耐衝撃性則作為膜而言有充分的韌性，使用時不會破裂。 The lower limit of the impact resistance (23 ° C) of the stretched polypropylene film of the present invention is preferably 0.6J, and more preferably 0.7J. When the impact resistance is in the above range, the film has sufficient toughness and does not crack during use.

耐衝撃性的上限由實際的方面來看較佳係3J，更佳係2.5J，又更佳係2.2J，尤佳係2J。由於耐衝撃性係在例如低分子量成分多的情況、整體中之分子量低的情況、高分子量成分少的情況或高分子量成分的分子量低的情況下，耐衝撃性有降低的傾向，故可配合用途而調整這些成分設定在範圍內。 From the practical point of view, the upper limit of shock resistance is preferably 3J, more preferably 2.5J, still more preferably 2.2J, and even more preferably 2J. The impact resistance tends to decrease, for example, when there are many low molecular weight components, when the overall molecular weight is low, when there are few high molecular weight components, or when the molecular weight of high molecular weight components is low. Use and adjust these components within the range.

本發明的聚丙烯系積層膜的霧度作為實際的值而言下限較佳係0.1%，更佳係0.2%，更佳係0.3%以上，尤佳係0.4%，最佳係0.5%。 As a practical value, the lower limit of the haze of the polypropylene-based laminated film of the present invention is preferably 0.1%, more preferably 0.2%, more preferably 0.3% or more, particularly preferably 0.4%, and most preferably 0.5%.

霧度的上限較佳係6%，更佳係5%，又更佳係4.5%，尤佳係4%，最佳係3.5%。若為上述範圍的霧度則更容易用於需要透明的用途中。霧度在例如延伸溫度、熱固定溫度過高的情況、 冷卻輥(CR)溫度高而冷卻速度慢的情況、低分子量過多的情況下有變差的傾向，可藉由調節這些而設定在範圍內。 The upper limit of haze is preferably 6%, more preferably 5%, more preferably 4.5%, even more preferably 4%, and the best 3.5%. If the haze is in the above range, it can be more easily used in applications requiring transparency. Haze is e.g. when the elongation temperature, heat-fixing temperature is too high, The temperature of the cooling roll (CR) is high and the cooling rate is slow, and the case of excessively low molecular weight tends to deteriorate, and it can be set within the range by adjusting these.

本發明的聚丙烯系積層膜的厚度均一性的下限較佳係0%，更佳係0.1%，更佳係0.5%，尤佳係1%。 The lower limit of the thickness uniformity of the polypropylene-based laminated film of the present invention is preferably 0%, more preferably 0.1%, more preferably 0.5%, and even more preferably 1%.

厚度均一性的上限較佳係20%，更佳係17%，又更佳係15%，尤佳係12%，最佳係10%。若為上述範圍則在塗布或印刷等的後加工時不易產生缺陷，容易用於需要精密性的用途。 The upper limit of thickness uniformity is preferably 20%, more preferably 17%, still more preferably 15%, particularly preferably 12%, and most preferably 10%. If it is the said range, a defect is hard to generate | occur | produce at the time of post-processing, such as coating and printing, and it is easy to use for the application which requires precision.

[實施例] [Example]

以下基於實施例對本發明進行詳細的說明，但本發明並不限於下述實施例。實施例中之物性的測定方法如下。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples. The measuring method of the physical property in an Example is as follows.

1)熔體流動速率(MFR、g/10分鐘) 1) Melt flow rate (MFR, g / 10 minutes)

依據JIS(Japanese Industrial Standards；日本工業規格)K7210，以溫度230℃測定。 Measured at 230 ° C in accordance with JIS (Japanese Industrial Standards) K7210.

2)分子量以及分子量分布 2) molecular weight and molecular weight distribution

分子量以及分子量分布係使用凝膠滲透層析法(GPC)而依據單分散聚苯乙烯基準所求得。 The molecular weight and molecular weight distribution are obtained by gel permeation chromatography (GPC) based on monodisperse polystyrene standards.

GPC測定所使用之管柱、溶劑如下。 The column and solvent used for GPC measurement are as follows.

溶劑：1,2,4-三氯苯 Solvent: 1,2,4-trichlorobenzene

管柱：TSKgel GMHHR-H(20)HT×3 Column: TSKgel GMH HR -H (20) HT × 3

流量：1.0ml/min Flow: 1.0ml / min

檢測器：RI Detector: RI

測定溫度：140℃ Measurement temperature: 140 ° C

數平均分子量(Mn)、質量平均分子量(Mw)、Z+1平均分子量(Mz+1)係各自透過分子量校正曲線所獲得之GPC曲線的各析出位置的分子量(Mi)的分子數(Ni)而以下列式子來定義。 The number average molecular weight (Mn), mass average molecular weight (Mw), and Z + 1 average molecular weight (Mz + 1) are the number of molecules (Ni) of the molecular weight (Mi) at each precipitation position of the GPC curve obtained through the molecular weight calibration curve It is defined by the following formula.

數平均分子量：Mn=Σ(Ni‧Mi)/ΣNi Number average molecular weight: Mn = Σ (Ni‧Mi) / ΣNi

質量平均分子量：Mw=Σ(Ni‧Mi2)/Σ(Ni‧Mi) Mass average molecular weight: Mw = Σ (Ni‧Mi 2 ) / Σ (Ni‧Mi)

Z+1平均分子量：Mz+1=Σ(Ni‧Mi4)/Σ(Ni‧Mi3) Z + 1 average molecular weight: Mz + 1 = Σ (Ni‧Mi 4 ) / Σ (Ni‧Mi 3 )

分子量分布：Mw/Mn、Mz+1/Mn Molecular weight distribution: Mw / Mn, Mz + 1 / Mn

此外，GPC曲線的峰值位置的分子量設為Mp。 The molecular weight at the peak position of the GPC curve is Mp.

當基線不明確時，係將最接近標準物質的析出峰值的高分子量側的析出峰值的高分子量側的峰尾的最低位置為止的範圍設定為基線。 When the baseline is not clear, the range up to the lowest position of the peak tail on the high molecular weight side of the precipitation peak on the high molecular weight side closest to the precipitation peak of the reference material is set as the baseline.

峰值分離係由所獲得之GPC曲線進行峰值分離為分子量的不同的二個以上的成分。各成分的分子量分布係假定為高斯函數，以成為和通常的聚丙烯的分子量分布相同的方式設為Mw/Mn=4。由所獲得之各成分的曲線計算各平均分子量。 The peak separation is performed by performing peak separation from the obtained GPC curve into two or more components having different molecular weights. The molecular weight distribution of each component is assumed to be a Gaussian function, and it is set to Mw / Mn = 4 so that it may become the molecular weight distribution of normal polypropylene. Each average molecular weight was calculated from the obtained curve of each component.

3)立體規則性 3) Stereo regularity

中五單元組分率([mmmm]%)以及中(meso)平均鏈長的測定係使用13C-NMR進行。中五單元組分率係根據Zambelli等人於Macromolecules，第6卷，925頁(1973)所記載的方法算出，中平均鏈長係根據J.C.Randall所著“Polymer Sequence Distribution”第2章(1977年)(Academic Press,New York)所記載的方法算出。 The measurement of the middle pentad component ratio ([mmmm]%) and the average (meso) chain length were performed using 13C-NMR. The composition rate of the middle five units is calculated according to the method described by Zambelli et al. In Macromolecules, Vol. 6, p. 925 (1973). The average chain length is based on Chapter 2 of "Polymer Sequence Distribution" by JCRandall (1977). ) (Academic Press, New York).

13C-NMR測定係使用BRUKER公司製AVANCE500，將試料200mg以135℃溶解在鄰二氯苯與重苯的8：2的混合液，在110℃進行。 The 13C-NMR measurement was performed using AVANCE500 manufactured by BRUKER, and 200 mg of a sample was dissolved at 135 ° C in a 8: 2 mixed solution of o-dichlorobenzene and heavy benzene at 110 ° C.

4)冷二甲苯可溶部(CXS、質量%) 4) Cold xylene solubles (CXS, mass%)

將聚丙烯試料1g於沸騰二甲苯200ml溶解且放冷後，在20℃的恆溫水槽以1小時再結晶化，將溶解於濾液之質量的相對於原始試料量的比率設為CXS(質量%)。 After dissolving 1 g of polypropylene sample in 200 ml of boiling xylene and letting it cool, it was recrystallized in a constant temperature water bath at 20 ° C for 1 hour, and the ratio of the mass dissolved in the filtrate to the original sample amount was set to CXS (mass%) .

5)熱收縮率(%) 5) Thermal shrinkage (%)

根據JIS Z 1712進行測定。 The measurement was performed in accordance with JIS Z 1712.

(將延伸膜以20mm寬度且200mm的長度在MD、TD方向各自裁切，並懸掛在150℃的熱風爐中加熱5分鐘。測定加熱後的長度相對於原始長度所收縮的長度的比率來求得熱收縮率。) (The stretched film was cut into MD and TD directions with a width of 20 mm and a length of 200 mm, and was hung in a hot air oven at 150 ° C for 5 minutes. The ratio of the length after heating to the length that was shrunk from the original length was determined. Heat shrinkage.)

6)耐衝撃性 6) Shock resistance

使用東洋精機製膜衝擊測試機，於23℃進行測定。 The measurement was performed at 23 ° C using a Toyo Seiki membrane impact tester.

7)楊氏模數(單位：GPa) 7) Young's modulus (unit: GPa)

根據JIS K 7127將MD以及TD方向的楊氏模數於23℃進行測定。 The Young's modulus in the MD and TD directions was measured at 23 ° C in accordance with JIS K 7127.

8)霧度(單位：%) 8) Haze (unit:%)

根據JIS K7105進行測定。 The measurement was performed in accordance with JIS K7105.

9)面配向係數(△P) 9) face alignment coefficient (△ P)

由JIS K7142-1996 5.1(A法)、使用Atago製阿貝折射計進行測定。沿MD、TD方向的折射率各自設為Nx、Ny，厚度方向的折射率設為Nz。面配向係數(△P)係以(Nx+Ny)/2-Nz求 得。 The measurement was performed according to JIS K7142-1996 5.1 (Method A) using an Abbe refractometer manufactured by Atago. The refractive indices in the MD and TD directions are each set to Nx and Ny, and the refractive index in the thickness direction is set to Nz. The surface alignment coefficient (△ P) is obtained by (Nx + Ny) / 2-Nz Got.

若密封層為單面的情況：對與密封層為相反之側的面進行3次測定，作成其平均值。若密封層為兩面的情況：對密封層的面兩側各進行3次測定，作成其平均值。 In the case where the sealing layer is single-sided: The surface on the opposite side to the sealing layer is measured three times to make an average value. In the case where the sealing layer has two surfaces, the measurement is performed three times on each side of the surface of the sealing layer to obtain an average value.

10)熱封強度 10) heat seal strength

在熱封溫度140℃以及110℃、壓力1Kg/cm2、熱封時間1秒的條件下，將積層延伸膜的熱封層(B)面彼此重疊而進行熱板密封，製作10mm寬度的試驗片。測定該試驗片的180度剝離強度，作成熱封強度(N/15mm)。 Under the conditions of heat-sealing temperatures of 140 ° C and 110 ° C, a pressure of 1 Kg / cm 2 and a heat-sealing time of 1 second, the heat-sealing layers (B) of the laminated stretched film were superimposed on each other to perform a hot-plate seal to produce a test with a width of 10 mm. sheet. The 180-degree peel strength of this test piece was measured to obtain a heat seal strength (N / 15 mm).

11)捲邊性 11) Hemming

對於10)的評價所獲得之膜以目視測定積層延伸膜的捲邊的程度。 For the film obtained in the evaluation of 10), the degree of curl of the laminated stretched film was visually measured.

○：無捲邊性 ○: No curling

△：略有捲邊性 △: slightly curled

×：顯著有捲邊性 ×: Significant curling

12)厚度不均 12) Uneven thickness

由經捲繞之膜輥切出長度為1m的正方形的試樣，於MD方向以及TD方向各自10等分而準備100片的測定用試樣。測定用試樣的大約中央部係以接觸式的膜厚度計測定厚度。 A square sample having a length of 1 m was cut out by the wound film roll, and 100 pieces of measurement samples were prepared by dividing each sample into 10 equal parts in the MD direction and the TD direction. Approximately the central portion of the measurement sample is measured with a contact-type film thickness meter.

求出所獲得之100點的數據的平均值，並求得最小值與最大值的差(絕對值)，將最小值與最大值的差的絕對值以平均值除之的值設為膜的厚度不均。 Find the average value of the 100 points of data obtained, and find the difference (absolute value) between the minimum value and the maximum value. Set the absolute value of the difference between the minimum value and the maximum value as the value divided by the average value. Uneven thickness.

13)熱封外觀 13) Heat seal appearance

將所製作之膜與東洋紡股份有限公司製PYLEN膜-CT P1128重疊，使用西部機械股份有限公司(Western Machine Co.,Ltd.)製測試密封劑，於170℃、荷重2Kg維持1秒鐘而進行熱封。藉由目視熱封後的膜的收縮所致之外觀的變化的狀態進行評價。將熱封部的變形量小而不影響使用的範圍設為○、將熱封所致之收縮大且變形量大設為×。 The produced film was superimposed with a PYLEN film-CT P1128 made by Toyobo Co., Ltd., and a test sealant made by Western Machine Co., Ltd. was used, and it was maintained at 170 ° C and a load of 2 Kg for 1 second. Heat sealed. Evaluation was performed by visually observing a change in appearance due to shrinkage of the film after heat-sealing. The range in which the amount of deformation of the heat-sealed portion is small without affecting the use is set to ○, and the amount of shrinkage due to heat-sealing is large and the amount of deformation is set to ×.

(實施例1) (Example 1)

使用2台的熔融擠出機，於第1的擠出機，作為聚丙烯樹脂，如表1所示之聚丙烯同元聚合物PP-1設為基材層(A)，於第2的擠出機，將丙烯-乙烯-丁烯無規共聚物(PP-7：Pr-Et-Bu、密度0.89g/cm3、MFR4.6g/10分鐘、熔點128℃)設為85重量%、丙烯-丁烯無規共聚物(PP-8：Pr-Bu、密度0.89g/cm3、MFR9.0g/10分鐘、熔點130℃)設為15重量%之混合樹脂設為熱封層(B)，於模具內以成為基材層(A)/熱封層(B)的方式，以基材層(A)、熱封層(B)的順序以T字模方式以250℃由T字模熔融共擠出成片材狀之後，以30℃的冷卻輥冷卻固化之後，以125℃在長度方向延伸4.5倍、隨後以夾鉗挾取兩端，導入至熱風爐中，以175℃預熱後，以160℃在橫向方向延伸8.2倍，然後使其鬆弛6.7%後以170℃進行熱處理。之後，對膜的單面進行電暈處理，以捲繞機捲繞。如此所獲得之膜的厚度為20μm，獲得基材層、熱封層的厚度各自依序為18μm、2μm之積層延伸膜。如表1、表2、表3所示，所獲得之積層延伸膜係滿足本發明的要件，熱收縮率低，剛性高，且熱封強度、韌度以及捲邊性亦優異。 Two melt extruders were used. In the first extruder, as the polypropylene resin, the polypropylene homopolymer PP-1 shown in Table 1 was used as the base material layer (A). In an extruder, a propylene-ethylene-butene random copolymer (PP-7: Pr-Et-Bu, density 0.89 g / cm 3 , MFR 4.6 g / 10 minutes, melting point 128 ° C.) was set to 85% by weight, A propylene-butene random copolymer (PP-8: Pr-Bu, density 0.89 g / cm 3 , MFR 9.0 g / 10 minutes, melting point 130 ° C.) was used as a heat-sealable layer with a mixed resin of 15% by weight ), In the mold to be the base material layer (A) / heat seal layer (B), in the order of the base material layer (A), heat seal layer (B) in a T-shaped mold method at 250 ° C melt from the T-shaped mold After being co-extruded into a sheet shape, it was cooled and solidified by a cooling roller at 30 ° C, and then extended 4.5 times in the length direction at 125 ° C. Then, the two ends were picked up with clamps and introduced into a hot air furnace. After preheating at 175 ° C It was stretched by 8.2 times in the transverse direction at 160 ° C, then relaxed by 6.7%, and then heat-treated at 170 ° C. After that, the film was corona-treated on one side and wound with a winder. The thickness of the film thus obtained was 20 μm, and a multilayer stretched film having a thickness of the substrate layer and a heat-seal layer of 18 μm and 2 μm in this order was obtained. As shown in Table 1, Table 2, and Table 3, the obtained laminated stretch film meets the requirements of the present invention, has a low heat shrinkage rate, high rigidity, and is also excellent in heat-sealing strength, toughness, and hemming properties.

(實施例2) (Example 2)

除了將基材層(A)所使用之原料變更為如表1所示之聚丙烯同元聚合物PP-2以外，係與實施例1同樣的方式獲得聚丙烯系積層膜。如表1、表2、表3所示，所獲得之積層延伸膜係滿足本發明的要件，熱收縮率低，剛性高，且熱封強度、韌度以及捲邊性亦優異。 A polypropylene-based laminated film was obtained in the same manner as in Example 1 except that the raw material used for the base material layer (A) was changed to the polypropylene homopolymer PP-2 shown in Table 1. As shown in Table 1, Table 2, and Table 3, the obtained laminated stretch film meets the requirements of the present invention, has a low heat shrinkage rate, high rigidity, and is also excellent in heat-sealing strength, toughness, and hemming properties.

(比較例1) (Comparative example 1)

除了將基材層(A)所使用之原料變更為如表1所示之聚丙烯同元聚合物PP-3以外，係與實施例1同樣的方式獲得聚丙烯系積層膜。如表1、表2、表3所示，所獲得之積層延伸膜雖然熱封強度、韌度以及捲邊性優異，但熱收縮率大。 A polypropylene-based laminated film was obtained in the same manner as in Example 1 except that the raw material used in the substrate layer (A) was changed to the polypropylene homopolymer PP-3 shown in Table 1. As shown in Table 1, Table 2, and Table 3, although the obtained laminated stretched film was excellent in heat-sealing strength, toughness, and curling property, it had a large heat shrinkage rate.

(比較例2) (Comparative example 2)

除了將基材層(A)所使用之原料變更為如表1所示之聚丙烯同元聚合物PP-4以外，係與實施例1同樣的方式欲獲得聚丙烯系積層膜，但在途中膜破損，無法獲得試樣。 A polypropylene-based laminated film was obtained in the same manner as in Example 1 except that the raw material used in the substrate layer (A) was changed to the polypropylene homopolymer PP-4 shown in Table 1. The film was broken and a sample could not be obtained.

(比較例3) (Comparative example 3)

除了將基材層(A)所使用之原料變更為如表1所示之聚丙烯同元聚合物PP-5以外，係與實施例1同樣的方式獲得聚丙烯系積層膜。如表1、表2、表3所示，所獲得之積層延伸膜雖然熱封強度、韌度以及捲邊性優異，但熱收縮率大。 A polypropylene-based laminated film was obtained in the same manner as in Example 1 except that the raw material used for the base material layer (A) was changed to the polypropylene homopolymer PP-5 shown in Table 1. As shown in Table 1, Table 2, and Table 3, although the obtained laminated stretched film was excellent in heat-sealing strength, toughness, and curling property, it had a large heat shrinkage rate.

(比較例4) (Comparative Example 4)

除了將基材層(A)所使用之原料變更為如表1所示之聚丙烯同元聚合物PP-6、寬度方向延伸預熱溫度變更為170℃、寬度方向延伸溫度變更為158℃、熱固定溫度變更為165℃以外，係與實施例1同樣的方式獲得聚丙烯系積層膜。如表1、表2、表 3所示，所獲得之積層延伸膜雖然熱封強度、韌度以及捲邊性優異，但熱收縮率非常大。 In addition to changing the raw materials used in the base material layer (A) to polypropylene homopolymer PP-6 shown in Table 1, the widthwise extension preheating temperature was changed to 170 ° C, the widthwise extension temperature was changed to 158 ° C, A polypropylene-based laminated film was obtained in the same manner as in Example 1 except that the heat-fixing temperature was changed to 165 ° C. As Table 1, Table 2, Table As shown in 3, although the obtained laminated stretched film was excellent in heat-sealing strength, toughness, and curling property, the heat shrinkage rate was very large.

(產業可利用性) (Industrial availability)

本發明的聚丙烯系積層膜用於包裝用途優異，非常適用於進行熱封加工。 The polypropylene-based laminated film of the present invention is excellent in packaging applications and is very suitable for heat-sealing processing.

然後，例如藉由將熱封溫度設定為高，可提高製袋加工之產線速度等，而提高生產性。此外，藉由提高熱封溫度，亦可提高熱封強度。 Then, for example, by setting the heat-sealing temperature to be high, the production line speed of bag-making processing can be increased, and productivity can be improved. In addition, the heat-sealing strength can be increased by increasing the heat-sealing temperature.

Claims (5)

一種聚丙烯系積層膜，係由基材層(A)以及熱封層(B)所構成；前述基材層(A)之構成層之聚丙烯樹脂係滿足下述1)至4)的條件；前述熱封層(B)係由積層於該基材層的單面或是雙面之聚烯烴系樹脂所構成；膜的面配向係數的下限為0.0125：1)中五單元組分率的下限為96%；2)丙烯以外的共聚單體量的上限為0.1mol%；3)質量平均分子量(Mw)/數平均分子量(Mn)為3.0以上5.4以下；4)於230℃、2.16kgf所測定之熔體流動速率(MFR)為6.2g/10min以上9.0g/10min以下。 A polypropylene-based laminated film composed of a base material layer (A) and a heat-sealable layer (B); the polypropylene resin of the constituent layer of the base material layer (A) satisfies the following conditions 1) to 4) The aforementioned heat-sealing layer (B) is composed of a polyolefin resin laminated on one or both sides of the substrate layer; the lower limit of the surface orientation coefficient of the film is 0.0125: 1) The lower limit is 96%; 2) the upper limit of the amount of comonomers other than propylene is 0.1 mol%; 3) the mass average molecular weight (Mw) / number average molecular weight (Mn) is 3.0 or more and 5.4 or less; 4) at 230 ° C, 2.16kgf The measured melt flow rate (MFR) is 6.2 g / 10min or more and 9.0 g / 10min or less. 如請求項1或2所記載之聚丙烯系積層膜，其中膜的縱向方向以及橫向方向的150℃之熱收縮率為8%以下。 The polypropylene-based laminated film according to claim 1 or 2, wherein the film has a thermal shrinkage at a temperature of 150 ° C in the longitudinal direction and the transverse direction of 8% or less. 如請求項1或2所記載之聚丙烯系積層膜，其中機械方向的楊氏模數為2.1GPa以上、橫斷方向的楊氏模數為3.7GPa以上。 The polypropylene-based laminated film according to claim 1 or 2, wherein the Young's modulus in the mechanical direction is 2.1 GPa or more, and the Young's modulus in the transverse direction is 3.7 GPa or more. 如請求項1至3中任一項所記載之聚丙烯系積層膜，其中將熱封層(B)面彼此重疊而以140℃進行1秒鐘熱板密封所獲得之10mm寬度的試驗片的180度剝離強度為8.0N/15mm以上。 The polypropylene-based laminated film according to any one of claims 1 to 3, wherein the 10 mm-wide test piece obtained by overlapping the heat-sealable layers (B) with each other and performing hot-plate sealing at 140 ° C for 1 second The 180-degree peel strength is 8.0 N / 15 mm or more. 如請求項1至4中任一項所記載之聚丙烯系積層膜，其中構成熱封層(B)之聚烯烴系樹脂係丙烯無規共聚物以及/或是丙烯嵌段共聚物。 The polypropylene-based laminated film according to any one of claims 1 to 4, wherein the polyolefin-based resin-based propylene random copolymer and / or the propylene block copolymer constituting the heat-sealable layer (B).
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