WO2023272494A1 - Multilayer film, preparation method therefor, and packaging material comprising same - Google Patents

Multilayer film, preparation method therefor, and packaging material comprising same Download PDF

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Publication number
WO2023272494A1
WO2023272494A1 PCT/CN2021/103162 CN2021103162W WO2023272494A1 WO 2023272494 A1 WO2023272494 A1 WO 2023272494A1 CN 2021103162 W CN2021103162 W CN 2021103162W WO 2023272494 A1 WO2023272494 A1 WO 2023272494A1
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Prior art keywords
layer
multilayer film
film according
weight
ethylene
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PCT/CN2021/103162
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French (fr)
Chinese (zh)
Inventor
李小俊
阮晓凯
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希悦尔（中国）有限公司
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Priority to CN202180092363.0A priority Critical patent/CN116887983A/en
Priority to PCT/CN2021/103162 priority patent/WO2023272494A1/en
Publication of WO2023272494A1 publication Critical patent/WO2023272494A1/en

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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
    • 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

Definitions

  • the invention belongs to the field of packaging materials.
  • the present invention relates to a multilayer film, a method for its preparation and a packaging material comprising the same.
  • the packaging bag described here is a packaging bag formed by heat-sealing the heat-sealable cover of folded or overlapping multi-layer films.
  • the packaging container described here is a container-shaped package in which a substrate (bottom web) and a lid (top web) are heat-sealed. The substrate is formed by stretching a multilayer film by vacuum forming. Adapted to the shape of the contents, the lid material is an unformed film.
  • Pasteurization is usually carried out at a temperature of about 80-95°C.
  • Conventional polyethylene film is crimped after pasteurization. This is caused by a complex combination of internal stress, post crystallization and thermal behavior of the resin. Not only does this curl detract from the pack's cosmetic quality, such as distorting printed information on the pack or other affixed labels, but it can also cause packs to misalign on packaging machines, often damaging packs or prolonging downtime in production .
  • US10363719B2 discloses a longitudinally oriented multilayer cast film comprising at least three layers A, B and C, wherein layer A is an outer layer comprising a heterophasic propylene copolymer and layer B is an outer layer comprising a higher A core layer of tactic polypropylene homopolymer, and layer C is a heat seal layer comprising a propylene based random copolymer or terpolymer, optionally in combination with a heterophasic propylene copolymer, wherein the The machine direction oriented multilayer cast film has (i) a tensile modulus of at least 2600 MPa in the machine direction and at least 1200 MPa in the transverse direction measured according to ISO 527-3 on a 50 ⁇ m film, (ii) A haze value of at most 5.5% measured on the film according to ASTM D1003, (iii) a shrinkage of at most -3.0% in the machine direction measured on a film of 50 ⁇ m after 10 min at 100°
  • US8686323B2 A multi-layer freezable, microwavable package comprising: (a) a polyolefin film comprising an inner heat-sealable layer, at least one core layer adjacent to the heat-sealable layer, and a core layer adjacent to said at least one core layer (b) an outer protective layer bonded to the outer skin layer of the polyolefin film, wherein the polyolefin film bonded to the outer protective layer forms a multilayer freezable, microwavable film that can be exposed to about 0°C To a temperature of about -20°C without cracking, and temperature resistant at about 150°C.
  • This patent does not address the problem of curling after retort sterilization.
  • An object of the present invention is to provide a packaging material which can withstand high temperatures during microwave heating and which does not curl after pasteurization.
  • the present invention provides a multilayer film, characterized in that, comprising:
  • HDPE high density polyethylene
  • An outer skin layer comprising polypropylene (PP) and ethylene-alpha-olefin elastomer.
  • the present invention provides a method for preparing a multilayer film according to the first aspect of the invention, characterized in that it comprises the following steps:
  • the invention provides a packaging material, characterized in that it comprises the multilayer film according to the first aspect.
  • the multilayer film according to the present invention can withstand the high temperature during microwave heating, and after pasteurization at 95° C. for 10 minutes, the entire multilayer film is still smooth, and its temperature resistance can reach above 120° C.
  • the multilayer film according to the invention can be used as a bottom web in a HFFS (horizontal form-fill-seal) process.
  • Figure 1 shows a schematic diagram of the structure of a multilayer film according to one embodiment of the present invention.
  • Fig. 2 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
  • Fig. 3 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
  • Fig. 4 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
  • Fig. 5 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
  • Fig. 6 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
  • Fig. 7 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
  • Fig. 8 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
  • Fig. 9 shows a photo of the pouch package of the invention example 1 after retort sterilization.
  • Fig. 10 shows a photo of the pouch package of Comparative Example 1 after retort sterilization.
  • the present invention provides a multilayer film, characterized in that, comprising:
  • HDPE high density polyethylene
  • An outer skin layer comprising polypropylene (PP) and ethylene-alpha-olefin elastomer.
  • the multilayer film further comprises a reinforcing layer disposed between the heat-sealing layer and the outer skin layer.
  • the reinforcing layer can increase the strength of the multilayer film.
  • the multilayer film further comprises a barrier layer disposed between the heat seal layer and the outer skin layer.
  • the barrier layer can increase the barrier properties of the multilayer film.
  • the multilayer film includes a reinforcement layer and a barrier layer disposed between the heat seal layer and the outer skin layer.
  • Adhesive layers may be provided between adjacent layers, depending on the bonding properties between the materials selected for each layer.
  • a tie layer is disposed between two or more adjacent layers.
  • the multilayer film includes the layers listed in one of (i)-(v) in order:
  • Figure 1 shows a multilayer film according to one embodiment of the present invention comprising: a heat seal layer and an outer skin layer.
  • Figure 2 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a reinforcement layer and an outer skin layer.
  • Figure 3 shows a multilayer film according to another embodiment of the present invention comprising, in order: a heat seal layer, a barrier layer and an outer skin layer.
  • Figure 4 shows a multilayer film according to another embodiment of the present invention comprising in order: a heat seal layer, a reinforcement layer, a barrier layer and an outer skin layer.
  • Figure 5 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a barrier layer, a reinforcement layer and an outer skin layer.
  • Figure 6 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a tie layer, a reinforcement layer, a tie layer, a barrier layer, a tie layer and an outer skin layer.
  • Figure 7 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a tie layer, a barrier layer, a tie layer, a reinforcement layer, a tie layer and an outer skin layer.
  • Figure 8 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a tie layer, a reinforcement layer, a barrier layer, a reinforcement layer, a tie layer and an outer skin layer.
  • the multilayer film of the present invention has an overall thickness in the range of 50-250 microns.
  • the heat seal layer of the multilayer film comprises high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • the content of high-density polyethylene in the heat-sealing layer is at least 70% by weight relative to the total weight of the heat-sealing layer.
  • the heat seal layer may also comprise medium density polyethylene (MDPE).
  • MDPE medium density polyethylene
  • the heat seal layer contains only high density polyethylene (HDPE) and medium density polyethylene (MDPE).
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • the content of high-density polyethylene (HDPE) is 70%-95% by weight, preferably 80%-90% by weight, relative to the total weight of the heat-sealing layer.
  • the content of medium density polyethylene (MDPE) is 5%-30% by weight, preferably 15%-25% by weight, relative to the total weight of the heat-sealing layer.
  • MDPE medium density polyethylene
  • high density polyethylene refers to a copolymer of ethylene and a small amount of ⁇ -olefin selected from the group consisting of propylene, 1-butene and hexene.
  • said high density polyethylene has a density in the range of 0.940-0.965 g/cc.
  • the high density polyethylene has a melting point in the range of 130°C-140°C, preferably in the range of 131°C-136°C.
  • the high density polyethylene is metallocene catalyzed high density polyethylene.
  • HDPE high-density polyethylene
  • Medium density polyethylenes may be those commonly used in the art, being copolymers of ethylene and alpha-olefins.
  • the melting point of the medium density polyethylene is in the range of 120°C-130°C.
  • the content of units derived from ethylene is 8 mol% to 35 mol%, relative to the total number of moles of units derived from ethylene and ⁇ -olefin.
  • the alpha-olefin is selected from butene, octene and hexene.
  • the medium density polyethylene is an ethylene-hexene copolymer.
  • MDPE medium density polyethylene
  • Novapol the product supplied by the company SWRM under the trade name Novapol, which has a melting point of 128°C.
  • the thickness of the heat-sealing layer accounts for 35-45% of the total thickness of the multilayer film.
  • a multilayer film comprising the heat-sealing layer can resist heating without melting or deforming.
  • the multilayer film includes a reinforcement layer.
  • the reinforcing layer may be formed using materials generally used in the art to form a reinforcing layer in a multilayer film for food packaging.
  • said reinforcing layer comprises polyamide.
  • said reinforcing layer comprises polyamide only.
  • the polyamides may be those commonly used in the art.
  • the polyamide can be selected from homopolyamide or copolyamide, such as PA6, PA66, PA6/66, PA6/6T.
  • the thickness of the reinforcing layer accounts for 10-20% of the total thickness of the multilayer film.
  • the multilayer film comprises a barrier layer.
  • the reinforcement layer may be formed using materials commonly used in the art to form barrier layers in multilayer films for food packaging.
  • the barrier layer comprises ethylene vinyl alcohol copolymer.
  • the barrier layer comprises only ethylene-vinyl alcohol copolymer.
  • the ethylene-vinyl alcohol may be those commonly used in the art.
  • the content of units derived from ethylene is 27 mol%-44 mol%, relative to the total number of moles of units derived from ethylene and vinyl alcohol.
  • the thickness of the barrier layer accounts for 5-10% of the total thickness of the multilayer film.
  • the multilayer film includes a tie layer.
  • the reinforcement layer may be formed using materials generally used in the art to form an adhesive layer in a multilayer film for food packaging.
  • the tie layer comprises a maleic anhydride graft of polyethylene.
  • the barrier layer comprises only polyethylene maleic anhydride grafts.
  • the maleic anhydride grafted polyethylene may be those commonly used in the art.
  • the content of units derived from maleic anhydride is 0.5-2 mol%, relative to the total number of moles of units derived from ethylene and maleic anhydride.
  • maleic anhydride grafts of polyethylene mention may be made of the products sold under the trade name ADMER TM by the company MITSUI.
  • the thickness of each adhesive layer accounts for 5-10% of the total thickness of the multilayer film.
  • the outer skin layer of the multilayer film comprises polypropylene (PP) and ethylene-alpha-olefin elastomer.
  • said outer skin contains only polypropylene (PP) and said ethylene-alpha-olefin elastomer.
  • the content of polypropylene (PP) is 70%-95% by weight relative to the total weight of the outer layer.
  • the content of the ethylene- ⁇ -olefin elastomer is 5% by weight to 30% by weight, relative to the total weight of the outer layer.
  • the polypropylene has a melt flow index (MFI) of 10-50 g/10 min, measured at 230° C. with a weight of 2.16 Kg.
  • MFI melt flow index
  • polypropylene As a commercial example of polypropylene, mention may be made of the product offered by the company Basell under the trade name Moplen with an MFI of 31 g/10 min.
  • the melting point of the ethylene- ⁇ -olefin elastomer is in the range of 60°C to 70°C.
  • the ethylene- ⁇ -olefin elastomer is an ethylene-propylene-octene copolymer.
  • the content of units derived from ethylene is 8 mol%-35 mol%, relative to the total number of moles of units derived from ethylene, propylene and octene.
  • the thickness of the outer layer accounts for 25-35% of the total thickness of the multilayer film.
  • Multilayer films comprising the outer skin do not curl after pasteurization.
  • slip agents and/or antiblocking agents may be added to the heat seal layer and the skin layer and its adjacent layers.
  • antioxidants and additives can be added to either layer.
  • the multilayer film according to the present invention can be used as bottom web in HFFS (Horizontal Form-Fill-Seal) process, and can be used for packaging sausage/ham and other foods that require microwave heating.
  • HFFS Horizontal Form-Fill-Seal
  • the multilayer films of the present invention can be prepared using any suitable method, including but not limited to casting.
  • the present invention provides a method for preparing a multilayer film according to the first aspect of the invention, characterized in that it comprises the following steps:
  • the molten polymer is extruded through a slit die onto a cooling roll, so that the polymer is cooled and solidified into a multilayer film.
  • the polymers of each respective individual layer are first compressed and melted in an extruder. The melt is then forced through a slot die (flat film die) and the extruded film is removed from one or more chill rolls, during which time it is cooled and solidified.
  • the temperature of each section in the extruder may be in the range of 150-250°C.
  • the temperature of each section in the extruder may be in the range of 200-270°C.
  • the temperature of each section in the extruder may be in the range of 200-250°C.
  • the temperature of each section in the extruder may be in the range of 150-230°C.
  • the temperature of each section in the extruder may be in the range of 180-250°C.
  • the temperature of the slot die can be in the range of 200-250°C.
  • the temperature of the chill roll may be in the range of 10-25°C.
  • the multilayer film according to the invention can be used as a bottom web in a HFFS (horizontal form-fill-seal) thermoforming process.
  • HFFS horizontal form-fill-seal
  • the present invention provides a packaging material, characterized in that it comprises the multilayer film according to the first aspect.
  • the multilayer film is a bottom web and the packaging material further includes a top web.
  • the top web may be those commonly used in the art for food or pharmaceutical packaging.
  • the packaging material is in the form of a bag or bag.
  • the packaging material can be used for packaging foods or medicines that need to be heated by microwaves, such as sausages and hams.
  • HDPE High Density Polyethylene, melting point 134°C, sold under the tradename Lumicene MPE by the company Total.
  • MDPE Ethylene-hexene copolymer, melting point 128° C., sold under the trade name Novapol by the company SWRM.
  • Binder resin maleic anhydride graft of polyethylene sold under the trade name Admer TM by the company Mitsui.
  • Nylon PA66/PA6, under the trade name of BASF Sales.
  • EVOH Ethylene-vinyl alcohol copolymer sold under the trade name Soarnol by the company Nippon Goshei.
  • Polypropylene has a melt flow index of 31 g/10 min, sold under the trade name Moplen by the company Basell.
  • Elastomer Ethylene-propylene-octene copolymer, melting point 63°C, sold under the trade name Affinity by the company Dow.
  • M-PE Ethylene-hexene copolymer, melting point 116° C., sold under the trade name EXACT TM by the company Exxson.
  • a multi-layer film with a structure as shown in Figure 8 is prepared by a multi-layer co-extrusion casting process, that is, the multi-layer film sequentially includes a heat-sealing layer, an adhesive layer, a reinforcing layer, a barrier layer, a reinforcing layer, an adhesive layer and outer layer.
  • the types and weights of raw materials used in each layer are shown in Table 1.
  • Inventive Example 1 has the same tie layer, reinforcement layer and barrier layer as in each comparative example.
  • HDPE/MDPE refers to a blend of 75% by weight HDPE and 25% by weight MDPE, based on the total weight of the blend.
  • PP/elastomer means a blend of 80% by weight PP and 20% by weight ethylene-propylene-octene copolymer elastomer, based on the total weight of the blend.
  • each layer of the multilayer film is heated and melted in each extruder.
  • the temperature of each zone of the extruder used is as shown in Table 2.
  • the melt from each extruder is delivered to different runners in the distributor.
  • the melt in the flow channel is arranged according to the film layer sequence of the produced seven-layer cast film before entering the die, and then enters the die (the temperature is set at 240 ° C), and then is extruded through the slit die to the cooling roll ( The temperature was set at 15° C.), and stretched to obtain a multilayer film.
  • the total thickness of the multilayer film was 125 microns.
  • the resulting multilayer films were combined as bottom webs with conventional top webs (CPP/BOPA/PE) respectively to form bag-like packages.
  • the pouch packages prepared in Inventive Example 1 and Comparative Example 1 were heated in a microwave oven at a power of 1800 watts for 30 seconds to visually observe the appearance of each multilayer film under microwave heating.
  • Fig. 9 shows a photo of the pouch package of the invention example 1 after retort sterilization.
  • Fig. 10 shows a photo of the pouch package of Comparative Example 1 after retort sterilization.
  • test results show that the multilayer film of the present invention can withstand the high temperature during microwave heating, and after pasteurization at 95° C. for 10 minutes, the whole multilayer film is still smooth.
  • the tolerable temperature of the multilayer film of the present invention can reach above 120°C.
  • test results also show that the multilayer film of the comparative example has the disadvantages of poor flatness and/or low temperature tolerance.

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Abstract

The present invention relates to a multilayer film, a preparation method therefor, and a packaging material comprising same. The multilayer film comprises a heat seal layer comprising a high-density polyethylene (HDPE), and an outer surface layer comprising polypropylene (PP) and an ethylene-α-olefin elastomer. The multilayer film according to the present invention can be subjected to high temperatures during microwave heating, and after 10 minutes of pasteurization at 95°C, the entire multilayer film is still flat.

Description

一种多层膜、其制备方法及包含其的包装材料A kind of multi-layer film, its preparation method and its packaging material 技术领域technical field
本发明属于包装材料领域。具体地，本发明涉及一种多层膜、其制备方法及包含其的包装材料。The invention belongs to the field of packaging materials. In particular, the present invention relates to a multilayer film, a method for its preparation and a packaging material comprising the same.
背景技术Background technique
在包装食品、医药品等的包装袋及包装容器中，为了满足所要求的各种性能，大多使用多层膜。在此所述的包装袋是将折曲或重叠的多层膜的可热封面热封而成的包装袋。另外，在此所述的包装容器是将底材(底部幅材)与盖材(顶部幅材)热封而成的容器状包装，所述底材是将多层膜利用真空成型拉伸成适于内容物的形状而成的，所述盖材是未成型膜。In packaging bags and packaging containers for food and pharmaceuticals, multilayer films are often used in order to satisfy various required performances. The packaging bag described here is a packaging bag formed by heat-sealing the heat-sealable cover of folded or overlapping multi-layer films. In addition, the packaging container described here is a container-shaped package in which a substrate (bottom web) and a lid (top web) are heat-sealed. The substrate is formed by stretching a multilayer film by vacuum forming. Adapted to the shape of the contents, the lid material is an unformed film.
许多用于包装袋和包装容器中的多层膜使用常规聚乙烯形成热封层，然而，常规聚乙烯不能经受微波加热。在加热后，聚乙烯热封层可能熔化。这可能导致包装上产生孔和/褶皱。Many multilayer films used in bags and containers use conventional polyethylene to form the heat seal layer, however, conventional polyethylene cannot withstand microwave heating. After heating, the polyethylene heat seal layer may melt. This can cause holes and/or creases in the packaging.
在一些食物应用(如蒸煮袋)或一些医药应用的领域，需要对包装材料进行灭菌处理，例如巴氏灭菌处理。巴氏灭菌通常在约80-95℃的温度下进行。常规聚乙烯薄膜在巴氏灭菌后卷曲。这是由树脂的内应力、后结晶和热行为的复杂组合引起的。这种卷曲不仅有损于包装的外观质量，例如扭歪了包装上的印刷信息或其它贴上的标签，而且还会使包装在包装机上错排，从而常损坏包装或延长生产中的停机时间。In some food applications (such as retort pouches) or some medical applications, it is necessary to sterilize the packaging materials, such as pasteurization. Pasteurization is usually carried out at a temperature of about 80-95°C. Conventional polyethylene film is crimped after pasteurization. This is caused by a complex combination of internal stress, post crystallization and thermal behavior of the resin. Not only does this curl detract from the pack's cosmetic quality, such as distorting printed information on the pack or other affixed labels, but it can also cause packs to misalign on packaging machines, often damaging packs or prolonging downtime in production .
US10363719B2公开了一种纵向取向的多层流延膜，该多层流延膜包括至少三个层A、B和C，其中层A是包括多相丙烯共聚物的外层，层B是包括高等规度聚丙烯均聚物的芯层，和层C是热封层，该热封层包括基于丙烯的无规共聚物或三元共聚物、任选地与多相丙烯共聚物组合，其中该纵向取向的多层流延膜具有(i)在50μm的膜上根据ISO 527-3所测量的在纵向上为至少2600MPa以及在横向上为至少1200MPa的拉伸模量，(ii)在50μm的膜上根据ASTM D1003所测量的至多5.5％的雾度值，(iii)在50μm的膜上根据实验部分所述的 方法在100℃下10min之后所测量的在纵向上至多-3.0％的收缩率。该专利未关注所述多层膜是否能经受微波加热。US10363719B2 discloses a longitudinally oriented multilayer cast film comprising at least three layers A, B and C, wherein layer A is an outer layer comprising a heterophasic propylene copolymer and layer B is an outer layer comprising a higher A core layer of tactic polypropylene homopolymer, and layer C is a heat seal layer comprising a propylene based random copolymer or terpolymer, optionally in combination with a heterophasic propylene copolymer, wherein the The machine direction oriented multilayer cast film has (i) a tensile modulus of at least 2600 MPa in the machine direction and at least 1200 MPa in the transverse direction measured according to ISO 527-3 on a 50 μm film, (ii) A haze value of at most 5.5% measured on the film according to ASTM D1003, (iii) a shrinkage of at most -3.0% in the machine direction measured on a film of 50 μm after 10 min at 100°C according to the method described in the experimental section . This patent does not address whether the multilayer film can withstand microwave heating.
US8686323B2一种多层可冷冻、可微波包装，包括：(a)聚烯烃薄膜，包括内部可热封层、至少一个与可热封层相邻的芯层和与所述至少一个芯层相邻的外皮层，(b)与聚烯烃薄膜的外皮层粘合的外保护层，其中与外保护层结合的聚烯烃薄膜形成多层可冷冻、可微波化的薄膜，其可暴露于约0℃至约-20℃的温度而不破裂，并且在约150℃下耐温。该专利未关注在蒸煮灭菌后的卷曲问题。US8686323B2 A multi-layer freezable, microwavable package comprising: (a) a polyolefin film comprising an inner heat-sealable layer, at least one core layer adjacent to the heat-sealable layer, and a core layer adjacent to said at least one core layer (b) an outer protective layer bonded to the outer skin layer of the polyolefin film, wherein the polyolefin film bonded to the outer protective layer forms a multilayer freezable, microwavable film that can be exposed to about 0°C To a temperature of about -20°C without cracking, and temperature resistant at about 150°C. This patent does not address the problem of curling after retort sterilization.
因此，希望开发一种包装材料，其能够经受微波加热时的高温并且巴氏灭菌后不卷曲。Therefore, it is desirable to develop a packaging material that can withstand high temperatures during microwave heating and that does not curl after pasteurization.
发明内容Contents of the invention
本发明的一个目的是提供一种包装材料，其能够经受微波加热时的高温并且巴氏灭菌后不卷曲。An object of the present invention is to provide a packaging material which can withstand high temperatures during microwave heating and which does not curl after pasteurization.
根据第一方面，本发明提供一种多层膜，其特征在于，包括：According to a first aspect, the present invention provides a multilayer film, characterized in that, comprising:
热封层，其包含高密度聚乙烯(HDPE)；和a heat seal layer comprising high density polyethylene (HDPE); and
外表层，其包含聚丙烯(PP)与乙烯-α-烯烃弹性体。An outer skin layer comprising polypropylene (PP) and ethylene-alpha-olefin elastomer.
根据第二方面，本发明提供制备根据本发明的第一方面的多层膜的方法，其特征在于，包括以下步骤：According to a second aspect, the present invention provides a method for preparing a multilayer film according to the first aspect of the invention, characterized in that it comprises the following steps:
i)使各层所用的原料在挤出机熔融；和i) melting the raw materials used for each layer in the extruder; and
ii)使各熔体通过狭缝模头挤出、拉伸、冷却并固化形成多层膜。ii) Each melt is extruded through a slot die, stretched, cooled and solidified to form a multilayer film.
根据第三方面，本发明提供一种包装材料，其特征在于，包括根据第一方面的多层膜。According to a third aspect, the invention provides a packaging material, characterized in that it comprises the multilayer film according to the first aspect.
根据本发明的多层膜能够经受微波加热时的高温，并且在95℃巴氏灭菌10分钟后，整个多层膜仍然是平整的，其可耐受温度可达120℃以上。根据本发明的多层膜可在HFFS(水平成型-填充-密封)工艺中用作底部幅材。The multilayer film according to the present invention can withstand the high temperature during microwave heating, and after pasteurization at 95° C. for 10 minutes, the entire multilayer film is still smooth, and its temperature resistance can reach above 120° C. The multilayer film according to the invention can be used as a bottom web in a HFFS (horizontal form-fill-seal) process.
附图说明Description of drawings
在下文中，将结合附图对本发明进行示例说明，在附图中，相同的数字表示相同的结构层，其中：Hereinafter, the present invention will be illustrated with reference to the accompanying drawings, in which the same numerals represent the same structural layers, wherein:
图1显示了根据本发明的一个实施方式的多层膜的结构示意图。Figure 1 shows a schematic diagram of the structure of a multilayer film according to one embodiment of the present invention.
图2显示了根据本发明的另一个实施方式的多层膜的结构示意图。Fig. 2 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
图3显示了根据本发明的另一个实施方式的多层膜的结构示意图。Fig. 3 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
图4显示了根据本发明的另一个实施方式的多层膜的结构示意图。Fig. 4 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
图5显示了根据本发明的另一个实施方式的多层膜的结构示意图。Fig. 5 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
图6显示了根据本发明的另一个实施方式的多层膜的结构示意图。Fig. 6 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
图7显示了根据本发明的另一个实施方式的多层膜的结构示意图。Fig. 7 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
图8显示了根据本发明的另一个实施方式的多层膜的结构示意图。Fig. 8 shows a schematic diagram of the structure of a multilayer film according to another embodiment of the present invention.
图9显示了发明实施例1的袋状包装在蒸煮灭菌后的照片。Fig. 9 shows a photo of the pouch package of the invention example 1 after retort sterilization.
图10显示了对比实施例1的袋状包装在蒸煮灭菌后的照片。Fig. 10 shows a photo of the pouch package of Comparative Example 1 after retort sterilization.
具体实施方式detailed description
在下文中，将更详细地描述本发明的各方面以及更进一步的目的、特征和优点。然而，应当理解的是，本发明可以不同的形式实现，而不应局限于本文中描述的具体实施方式。Hereinafter, aspects of the present invention as well as further objects, features and advantages will be described in more detail. It should be understood, however, that the invention may be embodied in different forms and should not be limited to the specific embodiments described herein.
根据第一方面，本发明提供一种多层膜，其特征在于，包括：According to a first aspect, the present invention provides a multilayer film, characterized in that, comprising:
热封层，其包含高密度聚乙烯(HDPE)；和a heat seal layer comprising high density polyethylene (HDPE); and
外表层，其包含聚丙烯(PP)与乙烯-α-烯烃弹性体。An outer skin layer comprising polypropylene (PP) and ethylene-alpha-olefin elastomer.
优选地，所述多层膜还包括设置于热封层与外表层之间的增强层。所述增强层可以提高所述多层膜的强度。Preferably, the multilayer film further comprises a reinforcing layer disposed between the heat-sealing layer and the outer skin layer. The reinforcing layer can increase the strength of the multilayer film.
优选地，所述多层膜还包括设置于热封层与外表层之间的阻隔层。所述阻隔层可以提高所述多层膜的阻隔性。Preferably, the multilayer film further comprises a barrier layer disposed between the heat seal layer and the outer skin layer. The barrier layer can increase the barrier properties of the multilayer film.
更优选地，所述多层膜包括设置于热封层与外表层之间的增强层与阻隔层。More preferably, the multilayer film includes a reinforcement layer and a barrier layer disposed between the heat seal layer and the outer skin layer.
根据各层所选的材料之间的粘结性，可以在相邻层之间设置粘结层。Adhesive layers may be provided between adjacent layers, depending on the bonding properties between the materials selected for each layer.
在一些实施方案中，在两个或更多个相邻层之间设置粘结层。In some embodiments, a tie layer is disposed between two or more adjacent layers.
在一些实施方案中，所述多层膜依次包括(i)-(v)之一所列出的层：In some embodiments, the multilayer film includes the layers listed in one of (i)-(v) in order:
(i)：热封层、增强层与外表层；(i): heat seal layer, reinforcement layer and outer layer;
(ii)：热封层、阻隔层与外表层；(ii): heat seal layer, barrier layer and outer layer;
(iii)：热封层、粘结层、增强层、粘结层与外表层；(iii): heat seal layer, adhesive layer, reinforcement layer, adhesive layer and outer skin;
(iv)：热封层、粘结层、阻隔层、粘结层与外表层；(iv): heat seal layer, adhesive layer, barrier layer, adhesive layer and outer skin;
(v)：热封层、增强层、阻隔层与外表层；(v): heat seal layer, reinforcement layer, barrier layer and outer skin layer;
(vi)：热封层、阻隔层、增强层与外表层；(vi): heat seal layer, barrier layer, reinforcement layer and outer layer;
(vii)：热封层、粘结层、增强层、粘结层、阻隔层、粘结层与外表层；(vii): Heat seal layer, adhesive layer, reinforcement layer, adhesive layer, barrier layer, adhesive layer and outer skin;
(viii)：热封层、粘结层、阻隔层、粘结层、增强层、粘结层与外表层；(viii): heat seal layer, adhesive layer, barrier layer, adhesive layer, reinforcement layer, adhesive layer and outer skin;
(ix)：热封层、粘结层、增强层、阻隔层、增强层、粘结层与外表层。(ix): heat seal layer, adhesive layer, reinforcement layer, barrier layer, reinforcement layer, adhesive layer and outer skin layer.
下面参考图1-8，列出根据本发明的一些实施例的多层膜作为示例。Referring now to Figures 1-8, multilayer films according to some embodiments of the present invention are listed as examples.
图1显示了根据本发明的一个实施方案的多层膜，其包括：热封层和外表层。Figure 1 shows a multilayer film according to one embodiment of the present invention comprising: a heat seal layer and an outer skin layer.
图2显示了根据本发明的另一个实施方案的多层膜，其依次包括：热封层、增强层与外表层。Figure 2 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a reinforcement layer and an outer skin layer.
图3显示了根据本发明的另一个实施方案的多层膜，其依次包括：热封层、阻隔层与外表层。Figure 3 shows a multilayer film according to another embodiment of the present invention comprising, in order: a heat seal layer, a barrier layer and an outer skin layer.
图4显示了根据本发明的另一个实施方案的多层膜，其依次包括：热封层、增强层、阻隔层与外表层。Figure 4 shows a multilayer film according to another embodiment of the present invention comprising in order: a heat seal layer, a reinforcement layer, a barrier layer and an outer skin layer.
图5显示了根据本发明的另一个实施方案的多层膜，其依次包括：热封层、阻隔层、增强层与外表层。Figure 5 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a barrier layer, a reinforcement layer and an outer skin layer.
图6显示了根据本发明的另一个实施方案的多层膜，其依次包括：热封层、粘结层、增强层、粘结层、阻隔层、粘结层与外表层。Figure 6 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a tie layer, a reinforcement layer, a tie layer, a barrier layer, a tie layer and an outer skin layer.
图7显示了根据本发明的另一个实施方案的多层膜，其依次包括：热封层、粘结层、阻隔层、粘结层、增强层、粘结层与外表层。Figure 7 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a tie layer, a barrier layer, a tie layer, a reinforcement layer, a tie layer and an outer skin layer.
图8显示了根据本发明的另一个实施方案的多层膜，其依次包括：热封层、粘结层、增强层、阻隔层、增强层、粘结层与外表层。Figure 8 shows a multilayer film according to another embodiment of the present invention, comprising in order: a heat seal layer, a tie layer, a reinforcement layer, a barrier layer, a reinforcement layer, a tie layer and an outer skin layer.
优选地，本发明的多层膜的总厚度在50-250微米范围内。Preferably, the multilayer film of the present invention has an overall thickness in the range of 50-250 microns.
热封层heat seal layer
所述多层膜的热封层包含高密度聚乙烯(HDPE)。The heat seal layer of the multilayer film comprises high density polyethylene (HDPE).
高密度聚乙烯在所述热封层中的含量为至少70重量％，相对于所述热封层的总重量计。The content of high-density polyethylene in the heat-sealing layer is at least 70% by weight relative to the total weight of the heat-sealing layer.
所述热封层还可以包含中密度聚乙烯(MDPE)。The heat seal layer may also comprise medium density polyethylene (MDPE).
优选地，所述热封层仅含有高密度聚乙烯(HDPE)和中密度聚乙烯(MDPE)。Preferably, the heat seal layer contains only high density polyethylene (HDPE) and medium density polyethylene (MDPE).
优选地，在所述热封层中，高密度聚乙烯(HDPE)的含量为70重量％-95重量％，优选80重量％-90重量％，相对于所述热封层的总重量计。Preferably, in the heat-sealing layer, the content of high-density polyethylene (HDPE) is 70%-95% by weight, preferably 80%-90% by weight, relative to the total weight of the heat-sealing layer.
优选地，在所述热封层中，中密度聚乙烯(MDPE)的含量为5重量％-30重量％，优选15重量％-25重量％，相对于所述热封层的总重量计。Preferably, in the heat-sealing layer, the content of medium density polyethylene (MDPE) is 5%-30% by weight, preferably 15%-25% by weight, relative to the total weight of the heat-sealing layer.
在本申请中高密度聚乙烯(HDPE)是指乙烯与少量α-烯烃的共聚物，所述α-烯烃选自选自丙烯、1-丁烯和己烯。In this application high density polyethylene (HDPE) refers to a copolymer of ethylene and a small amount of α-olefin selected from the group consisting of propylene, 1-butene and hexene.
优选地，所述高密度聚乙烯(HDPE)的密度在0.940-0.965g/cc范围内。Preferably, said high density polyethylene (HDPE) has a density in the range of 0.940-0.965 g/cc.
优选地，所述高密度聚乙烯(HDPE)的熔点在130℃-140℃范围内，优选在131℃-136℃范围内。Preferably, the high density polyethylene (HDPE) has a melting point in the range of 130°C-140°C, preferably in the range of 131°C-136°C.
优选地，所述高密度聚乙烯(HDPE)为茂金属催化的高密度聚乙烯。Preferably, the high density polyethylene (HDPE) is metallocene catalyzed high density polyethylene.
本领域技术人员能够根据加工要求选择具有合适熔体流动指数的高密度聚乙烯共聚物。Those skilled in the art can select a high-density polyethylene copolymer with a suitable melt flow index according to processing requirements.
作为所述高密度聚乙烯(HDPE)的商品实例，可以提及由Total公司以商品名Lumicene MPE提供的产品，熔点为134℃。As a commercial example of said high-density polyethylene (HDPE), mention may be made of the product offered by the company Total under the trade name Lumicene MPE, melting point 134°C.
中密度聚乙烯可以为本领域中常用的那些，是乙烯与α-烯烃的共聚物。Medium density polyethylenes may be those commonly used in the art, being copolymers of ethylene and alpha-olefins.
优选地，所述中密度聚乙烯的熔点在120℃-130℃范围内。Preferably, the melting point of the medium density polyethylene is in the range of 120°C-130°C.
优选地，在所述中密度聚乙烯中，衍生自乙烯的单元的含量为8摩尔％-35摩尔％，相对于衍生自乙烯与α-烯烃的单元的总摩尔数计。Preferably, in the medium density polyethylene, the content of units derived from ethylene is 8 mol% to 35 mol%, relative to the total number of moles of units derived from ethylene and α-olefin.
优选地，所述α-烯烃选自选自丁烯、辛烯和己烯。Preferably, the alpha-olefin is selected from butene, octene and hexene.
优选地，所述中密度聚乙烯(MDPE)为乙烯-己烯共聚物。Preferably, the medium density polyethylene (MDPE) is an ethylene-hexene copolymer.
作为中密度聚乙烯(MDPE)的商品实例，可以提及由SWRM公司以商品名Novapol提供的产品，其熔点为128℃。As a commercial example of medium density polyethylene (MDPE), mention may be made of the product supplied by the company SWRM under the trade name Novapol, which has a melting point of 128°C.
本领域技术人员可以根据需要选择热封层的厚度。Those skilled in the art can select the thickness of the heat-sealing layer according to needs.
优选地，所述热封层的厚度占多层膜总厚度的35-45％。Preferably, the thickness of the heat-sealing layer accounts for 35-45% of the total thickness of the multilayer film.
包含所述热封层的多层膜能抵抗加热而不熔化或变形。A multilayer film comprising the heat-sealing layer can resist heating without melting or deforming.
增强层enhancement layer
优选地，所述多层膜包括增强层。Preferably, the multilayer film includes a reinforcement layer.
可以采用本领域中通常用于形成食品包装用多层膜中的增强层的材料来形成所述增强层。The reinforcing layer may be formed using materials generally used in the art to form a reinforcing layer in a multilayer film for food packaging.
优选地，所述增强层包含聚酰胺。Preferably, said reinforcing layer comprises polyamide.
优选地，所述增强层仅包含聚酰胺。Preferably, said reinforcing layer comprises polyamide only.
所述聚酰胺可以为本领域中常用的那些。The polyamides may be those commonly used in the art.
所述聚酰胺可选自均聚聚酰胺或共聚聚酰胺，例如PA6、PA66、PA6/66、PA6/6T。The polyamide can be selected from homopolyamide or copolyamide, such as PA6, PA66, PA6/66, PA6/6T.
作为均聚聚酰胺或共聚聚酰胺的商品实例，可以提及由BASF公司以商品名
Figure PCTCN2021103162-appb-000001
销售的产品。 As commercial examples of homopolyamides or copolyamides, mention may be made by the company BASF under the trade name
Figure PCTCN2021103162-appb-000001
Products on sale.
本领域技术人员可以根据需要选择增强层的厚度。Those skilled in the art can select the thickness of the reinforcement layer according to needs.
优选地，所述增强层的厚度占多层膜总厚度的10-20％。Preferably, the thickness of the reinforcing layer accounts for 10-20% of the total thickness of the multilayer film.
阻隔层barrier layer
优选地，所述多层膜包括阻隔层。Preferably, the multilayer film comprises a barrier layer.
可以采用本领域中通常用于形成食品包装用多层膜中的阻隔层的材料来形成所述增强层。The reinforcement layer may be formed using materials commonly used in the art to form barrier layers in multilayer films for food packaging.
优选地，所述阻隔层包含乙烯-乙烯醇共聚物。Preferably, the barrier layer comprises ethylene vinyl alcohol copolymer.
优选地，所述阻隔层仅包含乙烯-乙烯醇共聚物。Preferably, the barrier layer comprises only ethylene-vinyl alcohol copolymer.
所述乙烯-乙烯醇可以为本领域中常用的那些。The ethylene-vinyl alcohol may be those commonly used in the art.
优选地，在所述乙烯-乙烯醇共聚物中，衍生自乙烯的单元的含量为27摩尔％-44摩尔％，相对于衍生自乙烯与乙烯醇的单元的总摩尔数计。Preferably, in the ethylene-vinyl alcohol copolymer, the content of units derived from ethylene is 27 mol%-44 mol%, relative to the total number of moles of units derived from ethylene and vinyl alcohol.
作为乙烯-乙烯醇共聚物的商品实例，可以提及由Nippon Goshei公司以商品名
Figure PCTCN2021103162-appb-000002
销售的产品。 As commercial examples of ethylene-vinyl alcohol copolymers, mention may be made of Nippon Goshei under the trade name
Figure PCTCN2021103162-appb-000002
Products on sale.
本领域技术人员可以根据需要选择阻隔层的厚度。Those skilled in the art can select the thickness of the barrier layer according to needs.
优选地，所述阻隔层的厚度占多层膜总厚度的5-10％。Preferably, the thickness of the barrier layer accounts for 5-10% of the total thickness of the multilayer film.
粘结层Adhesive layer
任选地，所述多层膜包括粘结层。Optionally, the multilayer film includes a tie layer.
可以采用本领域中通常用于形成食品包装用多层膜中的粘结层的材料来形成所述增强层。The reinforcement layer may be formed using materials generally used in the art to form an adhesive layer in a multilayer film for food packaging.
优选地，所述粘结层包含聚乙烯的马来酸酐接枝物。Preferably, the tie layer comprises a maleic anhydride graft of polyethylene.
优选地，所述阻隔层仅包含聚乙烯的马来酸酐接枝物。Preferably, the barrier layer comprises only polyethylene maleic anhydride grafts.
所述聚乙烯的马来酸酐接枝物可以为本领域中常用的那些。The maleic anhydride grafted polyethylene may be those commonly used in the art.
优选地，在所述聚乙烯的马来酸酐接枝物中，衍生自马来酸酐的单元的含量为0.5-2摩尔％，相对于衍生自乙烯与马来酸酐的单元的总摩尔数计。Preferably, in the maleic anhydride graft of polyethylene, the content of units derived from maleic anhydride is 0.5-2 mol%, relative to the total number of moles of units derived from ethylene and maleic anhydride.
作为聚乙烯的马来酸酐接枝物的商品实例，可以提及由MITSUI公司以商品名ADMER TM销售的产品。 As commercial examples of maleic anhydride grafts of polyethylene, mention may be made of the products sold under the trade name ADMER ™ by the company MITSUI.
本领域技术人员可以根据需要选择粘结层的厚度。Those skilled in the art can select the thickness of the adhesive layer according to needs.
优选地，每层所述粘结层的厚度占多层膜总厚度的5-10％。Preferably, the thickness of each adhesive layer accounts for 5-10% of the total thickness of the multilayer film.
外表层outer layer
所述多层膜的外表层包含聚丙烯(PP)与乙烯-α-烯烃弹性体。The outer skin layer of the multilayer film comprises polypropylene (PP) and ethylene-alpha-olefin elastomer.
优选地，所述外表层仅含有聚丙烯(PP)和所述乙烯-α-烯烃弹性体。Preferably, said outer skin contains only polypropylene (PP) and said ethylene-alpha-olefin elastomer.
优选地，在所述外表层中，聚丙烯(PP)的含量为70重量％-95重量％，相对于所述外表层的总重量计。Preferably, in the outer layer, the content of polypropylene (PP) is 70%-95% by weight relative to the total weight of the outer layer.
优选地，在所述外表层中，所述乙烯-α-烯烃弹性体的含量为5重量％-30重量％，相对于所述外表层的总重量计。Preferably, in the outer layer, the content of the ethylene-α-olefin elastomer is 5% by weight to 30% by weight, relative to the total weight of the outer layer.
优选地，所述聚丙烯的熔体流动指数(MFI)为10-50g/10min，在230℃下采用2.16Kg砝码测定。Preferably, the polypropylene has a melt flow index (MFI) of 10-50 g/10 min, measured at 230° C. with a weight of 2.16 Kg.
作为聚丙烯的商品实例，可以提及由Basell公司以商品名Moplen提供的产品，其MFI为31g/10min。As a commercial example of polypropylene, mention may be made of the product offered by the company Basell under the trade name Moplen with an MFI of 31 g/10 min.
优选地，所述乙烯-α-烯烃弹性体的熔点在60℃-70℃范围内。Preferably, the melting point of the ethylene-α-olefin elastomer is in the range of 60°C to 70°C.
优选地，所述乙烯-α-烯烃弹性体为乙烯-丙烯-辛烯共聚物。Preferably, the ethylene-α-olefin elastomer is an ethylene-propylene-octene copolymer.
优选地，在所述乙烯-丙烯-辛烯共聚物中，衍生自乙烯的单元的含量为8摩尔％-35摩尔％，相对于衍生自乙烯、丙烯与辛烯的单元的总摩尔数计。Preferably, in the ethylene-propylene-octene copolymer, the content of units derived from ethylene is 8 mol%-35 mol%, relative to the total number of moles of units derived from ethylene, propylene and octene.
作为乙烯-丙烯-辛烯共聚物的商品实例，可以提及由Dow公司以商品名Affinity提供的产品，其熔点为63℃。As commercial examples of ethylene-propylene-octene copolymers, mention may be made of the product offered by the company Dow under the trade name Affinity, which has a melting point of 63°C.
本领域技术人员可以根据需要选择外表层的厚度。Those skilled in the art can select the thickness of the outer layer according to needs.
优选地，所述外表层的厚度占多层膜总厚度的25-35％。Preferably, the thickness of the outer layer accounts for 25-35% of the total thickness of the multilayer film.
所述外表层由于含有具有较低熔点的弹性体，从而降低了成型过程中的内应力。包含此外表层的多层膜在巴氏灭菌后不发生卷曲。Since the outer layer contains the elastomer with a lower melting point, the internal stress during the molding process is reduced. Multilayer films comprising the outer skin do not curl after pasteurization.
在以上描述的各层中，还可以另外添加一些功能性助剂。In each layer described above, some functional additives can also be added.
例如，可以在热封层和表层及其相邻层中添加爽滑剂和/或开口剂。For example, slip agents and/or antiblocking agents may be added to the heat seal layer and the skin layer and its adjacent layers.
例如，可以在任一层中添加抗氧剂和助剂。For example, antioxidants and additives can be added to either layer.
根据本发明的多层膜可在HFFS(水平成型-填充-密封)工艺中用作底部幅材，可用于包装香肠/火腿等需要微波加热的食品。The multilayer film according to the present invention can be used as bottom web in HFFS (Horizontal Form-Fill-Seal) process, and can be used for packaging sausage/ham and other foods that require microwave heating.
本发明的多层膜可以使用任何合适的方法制备来制备，包括但不限于流延法。The multilayer films of the present invention can be prepared using any suitable method, including but not limited to casting.
根据第二方面，本发明提供制备根据本发明的第一方面的多层膜的方法，其特征在于，包括以下步骤：According to a second aspect, the present invention provides a method for preparing a multilayer film according to the first aspect of the invention, characterized in that it comprises the following steps:
i)使各层所用的原料在挤出机熔融；和i) melting the raw materials used for each layer in the extruder; and
ii)使各熔体在排序后通过狭缝模头挤出、拉伸、冷却并固化形成多层膜。ii) Extrude each melt through a slot die after sorting, draw, cool and solidify to form a multilayer film.
具体地，使熔融的聚合物通过狭缝模头挤出到冷却辊上，以使聚合物冷却固化成多层膜。典型地，每个相应的单独层的聚合物在挤出机中首先被压缩和熔化。熔体然后被强制通过狭缝模头(平膜模头)，并且从一个或更多个冷却辊上取出所挤出的膜，在此期间其被冷却和固化。Specifically, the molten polymer is extruded through a slit die onto a cooling roll, so that the polymer is cooled and solidified into a multilayer film. Typically, the polymers of each respective individual layer are first compressed and melted in an extruder. The melt is then forced through a slot die (flat film die) and the extruded film is removed from one or more chill rolls, during which time it is cooled and solidified.
本领域技术人员可以根据选择的聚合物确定挤出机中各段的温度以及狭缝模头与冷却辊的温度。Those skilled in the art can determine the temperature of each section in the extruder and the temperature of the slot die and cooling roll according to the selected polymer.
例如，对于热封层原料，所述挤出机中各段的温度可以在150-250℃范围内。For example, for heat-sealing layer raw materials, the temperature of each section in the extruder may be in the range of 150-250°C.
对于增强层原料，所述挤出机中各段的温度可以在200-270℃范围内。For the reinforcement layer raw material, the temperature of each section in the extruder may be in the range of 200-270°C.
对于阻隔层原料，所述挤出机中各段的温度可以在200-250℃范围内。For barrier layer raw materials, the temperature of each section in the extruder may be in the range of 200-250°C.
对于粘结层原料，所述挤出机中各段的温度可以在150-230℃范围内。For the tie layer raw material, the temperature of each section in the extruder may be in the range of 150-230°C.
对于外表层原料，所述挤出机中各段的温度可以在180-250℃范围内。For the raw material of the outer skin, the temperature of each section in the extruder may be in the range of 180-250°C.
狭缝模头的温度可以在200-250℃范围内。The temperature of the slot die can be in the range of 200-250°C.
冷却辊的温度可以在10-25℃范围内。The temperature of the chill roll may be in the range of 10-25°C.
根据本发明的多层膜可在HFFS(水平成型-填充-密封)热成型工艺中用作底部幅材。The multilayer film according to the invention can be used as a bottom web in a HFFS (horizontal form-fill-seal) thermoforming process.
因此，根据第三方面，本发明提供一种包装材料，其特征在于，包括根据第一方面的多层膜作。Therefore, according to a third aspect, the present invention provides a packaging material, characterized in that it comprises the multilayer film according to the first aspect.
在一些实施方案中，所述多层膜为底部幅材，所述包装材料还包括顶部幅材。In some embodiments, the multilayer film is a bottom web and the packaging material further includes a top web.
所述顶部幅材可为本领域通常用于食品或药物包装的那些。The top web may be those commonly used in the art for food or pharmaceutical packaging.
所述包装材料呈包或袋的形式。The packaging material is in the form of a bag or bag.
所述包装材料可用于包装诸如香肠、火腿等需要经过微波加热的食品或者药物。The packaging material can be used for packaging foods or medicines that need to be heated by microwaves, such as sausages and hams.
本申请中所述的“包含”和“包括”涵盖还包含或包括未明确提及的其它要素的情形以及由所提及的要素组成的情形。The words "comprising" and "including" described in the present application encompass the case of also including or including other elements not explicitly mentioned and the case of consisting of the mentioned elements.
除非另外限定，本文所使用的所有技术和科学术语具有本发明所属领域技术人员通常理解的相同意义。当本说明书中术语的定义与本发明所属领域技术人员通常理解的意义有矛盾时，以本文中所述的定义为准。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. When the definitions of terms in this specification conflict with the meanings generally understood by those skilled in the art to which the present invention belongs, the definitions stated herein shall prevail.
除非另有说明，否则在说明书和权利要求书中使用的表达成分的量、反应条件等的所有数值被理解为在被术语“约”修饰。因此，除非有相反指示，否则在这里阐述的数值参数是能够根据需要获得的所需性能来变化的近似值。Unless otherwise indicated, all numbers expressing amounts of ingredients, reaction conditions, etc. used in the specification and claims are understood to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary as required to obtain the desired properties.
实施例Example
以下将结合实施例对本发明的构思及产生的技术效果作进一步说明，以使本领域技术人员能够充分地了解本发明的目的、特征和效果。应该理解一些实施例仅为示意性的，不构成对本发明范围的限定。The concept and technical effects of the present invention will be further described below in conjunction with the embodiments, so that those skilled in the art can fully understand the purpose, features and effects of the present invention. It should be understood that some embodiments are only illustrative and not intended to limit the scope of the present invention.
所用原料：Raw materials used:
HDPE：高密度聚乙烯，熔点为134℃，由Total公司以商品名Lumicene MPE销售。HDPE: High Density Polyethylene, melting point 134°C, sold under the tradename Lumicene MPE by the company Total.
MDPE：乙烯-己烯共聚物，熔点为128℃，由SWRM公司以商品名Novapol销售。MDPE: Ethylene-hexene copolymer, melting point 128° C., sold under the trade name Novapol by the company SWRM.
粘结树脂：聚乙烯的马来酸酐接枝物，由Mitsui公司以商品名Admer TM销售。 Binder resin: maleic anhydride graft of polyethylene sold under the trade name Admer ™ by the company Mitsui.
尼龙：PA66/PA6，由BASF公司以商品名
Figure PCTCN2021103162-appb-000003
销售。 Nylon: PA66/PA6, under the trade name of BASF
Figure PCTCN2021103162-appb-000003
Sales.
EVOH：乙烯-乙烯醇共聚物，由Nippon Goshei公司以商品名Soarnol销售。EVOH: Ethylene-vinyl alcohol copolymer sold under the trade name Soarnol by the company Nippon Goshei.
聚丙烯：其熔体流动指数为31g/10min，由Basell公司以商品名Moplen销售。Polypropylene: has a melt flow index of 31 g/10 min, sold under the trade name Moplen by the company Basell.
弹性体：乙烯-丙烯-辛烯共聚物，熔点为63℃，由Dow公司以商品名Affinity销售。Elastomer: Ethylene-propylene-octene copolymer, melting point 63°C, sold under the trade name Affinity by the company Dow.
M-PE：乙烯-己烯共聚物，熔点为116℃，由Exxson公司以商品名EXACT TM销售。 M-PE: Ethylene-hexene copolymer, melting point 116° C., sold under the trade name EXACT ™ by the company Exxson.
发明实施例1和对比实施例1-4Invention Example 1 and Comparative Examples 1-4
采用多层共挤出流延工艺制备具有如图8所示结构的多层膜，即该多层膜依次包括热封层、粘结层、增强层、阻隔层、增强层、粘结层与外表层。其中各层所用原料的种类与重量如表1中所示。发明实施例1与各对比实施例中的粘结层、增强层和阻隔层相同。在表1中所示，HDPE/MDPE表示75重量％HDPE与25重量％MDPE的共混物，以该共混物的总重量为基准。并且在表1中所示，PP/弹性体表示80重量％PP与20重量％乙烯-丙烯-辛烯共聚物弹性体的共混物，以该共混物的总重量为基准。A multi-layer film with a structure as shown in Figure 8 is prepared by a multi-layer co-extrusion casting process, that is, the multi-layer film sequentially includes a heat-sealing layer, an adhesive layer, a reinforcing layer, a barrier layer, a reinforcing layer, an adhesive layer and outer layer. The types and weights of raw materials used in each layer are shown in Table 1. Inventive Example 1 has the same tie layer, reinforcement layer and barrier layer as in each comparative example. As indicated in Table 1, HDPE/MDPE refers to a blend of 75% by weight HDPE and 25% by weight MDPE, based on the total weight of the blend. And as shown in Table 1, PP/elastomer means a blend of 80% by weight PP and 20% by weight ethylene-propylene-octene copolymer elastomer, based on the total weight of the blend.
表1Table 1
Figure PCTCN2021103162-appb-000004
Figure PCTCN2021103162-appb-000004
*：相对整个多层膜的重量计。*: Relative to the weight of the entire multilayer film.
具体地，首先将根据多层膜的各层所需材料在各挤出机中加热熔融。在各实施例中，所用挤出机的各区温度如表2中所示。Specifically, firstly, materials required for each layer of the multilayer film are heated and melted in each extruder. In each example, the temperature of each zone of the extruder used is as shown in Table 2.
表2Table 2
Figure PCTCN2021103162-appb-000005
Figure PCTCN2021103162-appb-000005
将来自各挤出机中的熔体输送至分配器内的不同流道。流道内的熔体在进入模头前根据所生产的七层流延膜的膜层顺序排列，然后进入模头(温度设定在240℃)，然后通过狭缝模口挤出到冷却辊(温度设定在15℃)上，拉伸得到多层膜。多层膜的总厚度为125微米。The melt from each extruder is delivered to different runners in the distributor. The melt in the flow channel is arranged according to the film layer sequence of the produced seven-layer cast film before entering the die, and then enters the die (the temperature is set at 240 ° C), and then is extruded through the slit die to the cooling roll ( The temperature was set at 15° C.), and stretched to obtain a multilayer film. The total thickness of the multilayer film was 125 microns.
将所得多层膜分别作为底部幅材与常用的顶部幅材(CPP/BOPA/PE)结合形成袋状包装。The resulting multilayer films were combined as bottom webs with conventional top webs (CPP/BOPA/PE) respectively to form bag-like packages.
耐微波加热性Resistance to Microwave Heating
将发明实施例1和对比实施例1中制备的袋状包装在微波炉中1800瓦的功率下加热30秒目测观察各多层膜在微波加热的外观。The pouch packages prepared in Inventive Example 1 and Comparative Example 1 were heated in a microwave oven at a power of 1800 watts for 30 seconds to visually observe the appearance of each multilayer film under microwave heating.
观察到发明实施例1中制备的袋状包装在微波加热前后没有明显变化，而对比实施例1中制备的袋状包装在微波加热后由于聚合物部分熔融产生白点。It was observed that the pouch package prepared in Inventive Example 1 had no significant change before and after microwave heating, while the pouch package prepared in Comparative Example 1 produced white spots due to partial melting of the polymer after microwave heating.
蒸煮灭菌后平整性Flatness after cooking and sterilization
将发明实施例1和对比实施例1-4中制备的袋状包装在95℃下蒸煮灭菌10分钟，目测观察各袋装包装在蒸煮灭菌后的平整性。观察结果列于表3中。The pouch packages prepared in Invention Example 1 and Comparative Examples 1-4 were retorted and sterilized at 95° C. for 10 minutes, and the flatness of each pouch package after retort sterilization was visually observed. The observations are listed in Table 3.
图9显示了发明实施例1的袋状包装在蒸煮灭菌后的照片。Fig. 9 shows a photo of the pouch package of the invention example 1 after retort sterilization.
图10显示了对比实施例1的袋状包装在蒸煮灭菌后的照片。Fig. 10 shows a photo of the pouch package of Comparative Example 1 after retort sterilization.
观察到发明实施例1的袋状包装在蒸煮灭菌后非常平整，而对比实施例1的袋状包装在蒸煮灭菌后严重地向上卷曲。It was observed that the bag-like package of Inventive Example 1 was very flat after retort sterilization, while the bag-like package of Comparative Example 1 was severely curled upward after retort sterilization.
可耐受温度Tolerable temperature
将各实施例中的多层膜以热封层对热封层对折叠放，其上放置2Kg负载，在设置为指定温度的烘箱内放置1天，取出，参照QB/T2358-1998测量其热封强度。以热封强度>10N的起始温度作为其可耐受温度。测试结果列于表3中。Fold the multilayer film in each embodiment with the heat-seal layer to the heat-seal layer, place a 2Kg load on it, place it in an oven set at a specified temperature for 1 day, take it out, and measure its heat with reference to QB/T2358-1998 seal strength. The initial temperature of the heat seal strength > 10N is taken as its tolerable temperature. The test results are listed in Table 3.
表3table 3
Figure PCTCN2021103162-appb-000006
Figure PCTCN2021103162-appb-000006
测试结果表明：本发明的多层膜能够经受微波加热时的高温，并且在95℃巴氏灭菌10分钟后，整个多层膜仍然是平整的。此外，本发明的多层膜的可耐受温度可达120℃以上。The test results show that the multilayer film of the present invention can withstand the high temperature during microwave heating, and after pasteurization at 95° C. for 10 minutes, the whole multilayer film is still smooth. In addition, the tolerable temperature of the multilayer film of the present invention can reach above 120°C.
测试结果还表明：对比实施例的多层膜存在平整性差和/或可耐受温度低的缺点。The test results also show that the multilayer film of the comparative example has the disadvantages of poor flatness and/or low temperature tolerance.
虽然已经展现和讨论了本发明的一些方面，但是本领域内的技术人员应该意识到，可以在不背离本发明原理和精神的条件下对上述方面进行改变，因此本发明的范围将由权利要求以及等同的内容所限定。Although some aspects of the present invention have been shown and discussed, those skilled in the art should appreciate that the above-mentioned aspects can be changed without departing from the principle and spirit of the present invention, so the scope of the present invention will be determined by the claims and equivalent content.

Claims (25)

  1. 一种多层膜，其特征在于，包括：A multilayer film, characterized in that, comprising:
    热封层，其包含高密度聚乙烯(HDPE)；和a heat seal layer comprising high density polyethylene (HDPE); and
    外表层，其包含聚丙烯(PP)与乙烯-α-烯烃弹性体。An outer skin layer comprising polypropylene (PP) and ethylene-alpha-olefin elastomer.
  2. 根据权利要求1所述的多层膜，其特征在于，其依次包括(i)-(v)之一所列出的层：The multilayer film according to claim 1, characterized in that it comprises successively the layers listed in one of (i)-(v):
    (i)：热封层、增强层与外表层；(i): heat seal layer, reinforcement layer and outer layer;
    (ii)：热封层、阻隔层与外表层；(ii): heat seal layer, barrier layer and outer layer;
    (iii)：热封层、粘结层、增强层、粘结层与外表层；(iii): heat seal layer, adhesive layer, reinforcement layer, adhesive layer and outer skin;
    (iv)：热封层、粘结层、阻隔层、粘结层与外表层；(iv): heat seal layer, adhesive layer, barrier layer, adhesive layer and outer skin;
    (v)：热封层、增强层、阻隔层与外表层；(v): heat seal layer, reinforcement layer, barrier layer and outer skin layer;
    (vi)：热封层、阻隔层、增强层与外表层；(vi): heat seal layer, barrier layer, reinforcement layer and outer layer;
    (vii)：热封层、粘结层、增强层、粘结层、阻隔层、粘结层与外表层；(vii): Heat seal layer, adhesive layer, reinforcement layer, adhesive layer, barrier layer, adhesive layer and outer skin;
    (viii)：热封层、粘结层、阻隔层、粘结层、增强层、粘结层与外表层；(viii): heat seal layer, adhesive layer, barrier layer, adhesive layer, reinforcement layer, adhesive layer and outer skin;
    (ix)：热封层、粘结层、增强层、阻隔层、增强层、粘结层与外表层。(ix): heat seal layer, adhesive layer, reinforcement layer, barrier layer, reinforcement layer, adhesive layer and outer skin layer.
  3. 根据权利要求1或2所述的多层膜，其特征在于，所述多层膜的总厚度在50-250微米范围内。The multilayer film according to claim 1 or 2, characterized in that the total thickness of the multilayer film is in the range of 50-250 microns.
  4. 根据权利要求3所述的多层膜，其特征在于，所述增强层包含聚酰胺。The multilayer film of claim 3, wherein the reinforcing layer comprises polyamide.
  5. 根据权利要求2至4中任一项所述的多层膜，其特征在于，所述增强层的厚度占多层膜总厚度的10-20％。The multilayer film according to any one of claims 2 to 4, characterized in that, the thickness of the reinforcing layer accounts for 10-20% of the total thickness of the multilayer film.
  6. 根据权利要求2至5中任一项所述的多层膜，其特征在于，所述阻隔层包含乙烯-乙烯醇共聚物。A multilayer film according to any one of claims 2 to 5, wherein the barrier layer comprises ethylene vinyl alcohol copolymer.
  7. 根据权利要求2至6中任一项所述的多层膜，其特征在于，所述阻隔层的厚度占多层膜总厚度的5-10％。The multilayer film according to any one of claims 2 to 6, characterized in that the thickness of the barrier layer accounts for 5-10% of the total thickness of the multilayer film.
  8. 根据权利要求2至7中任一项所述的多层膜，其特征在于，所述粘结层包含聚乙烯的马来酸酐接枝物。A multilayer film according to any one of claims 2 to 7, wherein the tie layer comprises a maleic anhydride graft of polyethylene.
  9. 根据权利要求2至8中任一项所述的多层膜，其特征在于，每层所述粘结层的厚度占多层膜总厚度的5-10％。The multilayer film according to any one of claims 2 to 8, characterized in that the thickness of each adhesive layer accounts for 5-10% of the total thickness of the multilayer film.
  10. 根据权利要求1至9中任一项所述的多层膜，其特征在于，高密度聚乙烯在所述热封层中的含量为至少70重量％，相对于所述热封层的总重量计。The multilayer film according to any one of claims 1 to 9, characterized in that the content of high-density polyethylene in the heat-sealing layer is at least 70% by weight, relative to the total weight of the heat-sealing layer count.
  11. 根据权利要求1至10中任一项所述的多层膜，其特征在于，在所述热封层中，高密度聚乙烯(HDPE)的含量为70重量％-95重量％，优选80重量％-90重量％，相对于所述热封层的总重量计。The multilayer film according to any one of claims 1 to 10, characterized in that, in the heat-sealing layer, the content of high-density polyethylene (HDPE) is 70% by weight-95% by weight, preferably 80% by weight %-90% by weight, relative to the total weight of the heat-sealing layer.
  12. 根据权利要求1至11中任一项所述的多层膜，其特征在于，所述热封层还包含中密度聚乙烯，其为乙烯-α-烯烃共聚物(MDPE)，其含量为5重量％-30重量％，优选15重量％-25重量％，相对于所述热封层的总重量计。The multilayer film according to any one of claims 1 to 11, wherein the heat-sealing layer further comprises medium density polyethylene, which is ethylene-alpha-olefin copolymer (MDPE), and its content is 5 % by weight - 30% by weight, preferably 15% by weight - 25% by weight, relative to the total weight of the heat-sealing layer.
  13. 根据权利要求1至12中任一项所述的多层膜，其特征在于，所述高密度聚乙烯(HDPE)的熔点在130℃-140℃范围内。The multilayer film according to any one of claims 1 to 12, characterized in that the high density polyethylene (HDPE) has a melting point in the range of 130°C to 140°C.
  14. 根据权利要求12所述的多层膜，其特征在于，所述中密度聚乙烯的熔点在120℃-130℃范围内。The multilayer film of claim 12, wherein the medium density polyethylene has a melting point in the range of 120°C to 130°C.
  15. 根据权利要求12所述的多层膜，其特征在于，在所述中密度聚乙烯中，衍生自乙烯的单元的含量8摩尔％-35摩尔％，相对于衍生自乙烯与α-烯烃的单元的总摩尔数计。The multilayer film according to claim 12, characterized in that, in the medium density polyethylene, the content of units derived from ethylene is 8 mol% to 35 mol%, relative to the units derived from ethylene and α-olefin in total moles.
  16. 根据权利要求12所述的多层膜，其特征在于，所述中密度聚乙烯中的α-烯烃选自选自丁烯、辛烯和己烯。The multilayer film according to claim 12, characterized in that the alpha-olefin in the medium density polyethylene is selected from the group consisting of butene, octene and hexene.
  17. 根据权利要求1至15中任一项所述的多层膜，其特征在于，所述热封层的厚度占多层膜总厚度的35-45％。The multilayer film according to any one of claims 1 to 15, characterized in that the thickness of the heat-sealing layer accounts for 35-45% of the total thickness of the multilayer film.
  18. 根据权利要求1至17中任一项所述的多层膜，其特征在于，所述外表层仅含有聚丙烯(PP)和所述弹性体。A multilayer film according to any one of claims 1 to 17, characterized in that said outer skin layer comprises only polypropylene (PP) and said elastomer.
  19. 根据权利要求1至18中任一项所述的多层膜，其特征在于，在所述外表层中，聚丙烯(PP)的含量为70重量％-95重量％，相对于所述外表层的总重量计。The multilayer film according to any one of claims 1 to 18, characterized in that, in the outer layer, the content of polypropylene (PP) is 70% by weight to 95% by weight, relative to the outer layer of total weight.
  20. 根据权利要求1至19中任一项所述的多层膜，其特征在于，在所述外表层中，所述乙烯-α-烯烃弹性体的含量为5重量％-30重量％，相对于所述外表层的总重量计。The multilayer film according to any one of claims 1 to 19, characterized in that, in the outer layer, the content of the ethylene-α-olefin elastomer is 5% by weight to 30% by weight, relative to The total weight of the outer layer.
  21. 根据权利要求1至20中任一项所述的多层膜，其特征在于，所述乙烯-α-烯烃弹性体的熔点在60℃-70℃范围内。The multilayer film according to any one of claims 1 to 20, characterized in that the ethylene-α-olefin elastomer has a melting point in the range of 60°C to 70°C.
  22. 根据权利要求1至22中任一项所述的多层膜，其特征在于，所述弹性体为乙烯-丙烯-辛烯共聚物，其中衍生自乙烯的单元的含量为8摩尔％-35摩尔％，相对于衍生自乙烯、丙烯与辛烯的单元的总摩尔数计。The multilayer film according to any one of claims 1 to 22, characterized in that the elastomer is an ethylene-propylene-octene copolymer, wherein the content of units derived from ethylene is from 8 mol % to 35 mol % relative to the total number of moles of units derived from ethylene, propylene and octene.
  23. 根据权利要求1至22中任一项所述的多层膜，其特征在于，所述外表层的厚度占多层膜总厚度的25-35％。The multilayer film according to any one of claims 1 to 22, characterized in that, the thickness of the outer layer accounts for 25-35% of the total thickness of the multilayer film.
  24. 制备根据权利要求1-23中任一项所述的多层膜的方法，其特征在于，包括以下步骤：The method for preparing the multilayer film according to any one of claims 1-23, is characterized in that, comprises the following steps:
    i)使各层所用的原料在挤出机熔融；和i) melting the raw materials used for each layer in the extruder; and
    ii)使各熔体通过狭缝模头挤出、拉伸、冷却并固化形成多层膜。ii) Each melt is extruded through a slot die, stretched, cooled and solidified to form a multilayer film.
  25. 一种包装材料，其特征在于，包括根据权利要求1-23中任一项所述的多层膜作为底部幅材。A packaging material characterized in that it comprises a multilayer film according to any one of claims 1-23 as a bottom web.
PCT/CN2021/103162 2021-06-29 2021-06-29 Multilayer film, preparation method therefor, and packaging material comprising same WO2023272494A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009124805A1 (en) * 2008-04-10 2009-10-15 Mahle International Gmbh Coupling unit
CN102555379A (en) * 2011-12-16 2012-07-11 江阴升辉包装材料有限公司 Highly obstructed multilayer coextrusion thermal shrink film
CN109895486A (en) * 2017-12-08 2019-06-18 希悦尔（中国）有限公司 A kind of plural layers
CN110001167A (en) * 2019-03-28 2019-07-12 江阴市格瑞包装材料有限公司 A kind of low temperature resistant frozen-pack film and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009124805A1 (en) * 2008-04-10 2009-10-15 Mahle International Gmbh Coupling unit
CN102555379A (en) * 2011-12-16 2012-07-11 江阴升辉包装材料有限公司 Highly obstructed multilayer coextrusion thermal shrink film
CN109895486A (en) * 2017-12-08 2019-06-18 希悦尔（中国）有限公司 A kind of plural layers
CN110001167A (en) * 2019-03-28 2019-07-12 江阴市格瑞包装材料有限公司 A kind of low temperature resistant frozen-pack film and preparation method thereof

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