CN1278851C - 可剥离的密封薄膜 - Google Patents
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Abstract
本发明涉及一种可热封的共挤出多层包装薄膜，它可以在各种基底上剥离，所述基底包括聚乙烯、聚丙烯、聚酯、聚氯乙烯、聚酰胺、聚丙烯腈和纸，该薄膜包括至少一个得自预混前体配方的可剥离层，所述预混前体配方含有：50-80%重量的乙烯均聚物和/或共聚物、15-25%重量的苯乙烯均聚物或/和共聚物、5-20%重量的热塑性弹性苯乙烯-丁二烯-苯乙烯嵌段共聚物，特征在于，由所述预混前体制备的所述可剥离的密封薄膜中的剥离力是通过向最后挤出步骤中的所述前体内加入5-25，并优选10-20%重量的均匀支化的LLDPE和/或聚丁烯-1改进的。
Description
技术领域
本发明涉及一种可多层热封的共挤出薄膜，用较低的剥离力它就产生一可剥离且夯实明显的密封接头，特别是涉及包括所述薄膜的包装。本发明还公开了一种所述可剥离的密封薄膜的制备方法。
背景技术
最近几十年来，已开发了剥离/密封组合的各种包装薄膜。就高质量剥离薄膜应用而言，这些质量标准极具选择性，并且断开力应大大低于该剥离薄膜和支撑该薄膜的基底的内部粘合力，以避免分层。而且该剥离强度必须可以在大的热封温度窗口下操作，特别是对密封速度是重要因素的全自动包装线而言。
文献EP0024270于1980年描述了一种可热封的包装单层薄膜，它可以对各种包装薄膜产生一种可剥离的密封。该文献公开了一种组合物，它包括乙烯聚合物、聚苯乙烯、和以苯乙烯-丁二烯-苯乙烯或苯乙烯-丁二烯-苯乙烯为主的热塑性弹性体，它们以单层薄膜热封在各种基底上，这些基底包括聚乙烯、聚丙烯、聚酯、聚氯乙烯、聚酰胺、聚丙烯腈和纸。
这类包装剥离薄膜不再满足现代共挤出多层薄膜的要求，这些多层薄膜需要包括如下的性能：氧阻隔性或无撕破且可剥离的薄膜/纸组合、夯实明显、大的粘合剥离-密封窗口、辐射或环氧乙烷的可灭菌性和热粘接性。
具体地说，就药用而言，要求该剥离薄膜夯实明显，在包装打开期间必需发生不能粘合的机理，并且没有齿状、纤维撕破或边缘起毛。这意味着该剥离痕迹应光滑并且没有任何肉眼可见的破坏。而且，该薄膜在包括聚酯、聚氯乙烯和聚酰胺的各种基底上可剥离。
为了满足这些标准，必需在挤出混合步骤中将该剥离混合组合物中的不相容的不同聚合物高度分散并均质。导致高度分散的高水平的剪切例如可以通过在双螺杆挤出机中在预混段将这些组分混合来达到。
然而工业离线混合操作的问题主要是经济上的，并且实际混合机械的高输出速度(每小时几吨)需要大的容积。
这一步骤的大规模操作不可避免地限制了例如各种具体的特制剥离产品的较小规模所需的灵活性。因此本发明的挑战是发现该问题的一个解决方法，该方法不需要昂贵的在线混合设备的投资。
EP-A-0 0240 270公开了一种包装薄膜，它适宜层压在载体上用于必需按照US-A-6,080,456杀菌的物品的包装。这两个文献都没有公开将一均匀支化的LLDPE和/或聚丁烯-1用于本发明的最后挤出步骤以如下面描述中呈现的微调剥离力。
发明内容
发明目的
本发明旨在提供一种特制的可剥离的密封薄膜的制备方法，通过改进最后挤出步骤中预混配方，最终具有改进的热粘接性，并且所述薄膜尤其用于极具选择性标准的高质量包装应用。
发明概述
本发明涉及一种可热封的共挤出多层包装薄膜，它可在各种基底上剥离，所述基底包括聚乙烯、聚丙烯、聚酯、聚氯乙烯、聚酰胺、聚丙烯腈和纸，该薄膜包括至少一个得自预混前体配方的可剥离层，所述前体配方含有50-80％重量的乙烯均聚物和/或共聚物、15-25％重量的苯乙烯均聚物或/和共聚物、5-20％重量的热塑性弹性苯乙烯-丁二烯-苯乙烯嵌段共聚物，特征在于，由所述预混前体制备的所述可剥离的密封薄膜中的剥离力是通过向最后挤出步骤中的所述前体内加入5-25，并优选10-20％重量的均匀支化的LLDPE改进的。
本发明的一个关键方面是相对于可剥离层中的聚合物总重量，所述预混前体配方占70-90％重量。在可剥离层中所述薄膜的总重量含有高达4％重量的选自氟弹性体的加工添加剂。
本发明的另一关键方面是所述共挤出多层薄膜中的剥离层用于多层复合物剥离时可以位于该多层复合物的表面或内部并且该剥离层的厚度在该多层薄膜的总厚度中最大占15％。
本发明的包含HDPE作为乙烯聚合物的共挤出的可剥离多层密封薄膜用于可杀菌包装应用的用途。
本发明的可热封的共挤出多层包装薄膜的包装。
本发明的另一方面公开了一种可热封且可剥离的共挤出多层包装薄膜的制备方法，特征在于第一步，在高剪切和分散的挤出设备中将可剥离层的前体配方预混，所述可剥离层的前体配方含有：50-80％重量的乙烯均聚物和/或共聚物；15-25％重量的苯乙烯均聚物或/和共聚物；5-20％重量的热塑性弹性苯乙烯-丁二烯-苯乙烯嵌段共聚物；然后在第二步将所述预混前体配方通过一单螺杆挤出设备挤出，同时加入均匀支化的LLDPE以改进该包装薄膜的剥离力和热粘接性。
尤其出人意料和预料不到的是，在第二次挤出步骤中可以将高于25％重量的LLDPE分散到单螺杆设备中的前体配方中。这证实了与所述前体配方的优选相容性。
本发明的再一方面是在加工期间通过施加外部的捏合力和温度来从光学上提高所述薄膜的表面积。
本发明获得的薄膜可用于相对纸剥离，并且可用于可杀菌且夯实明显的包装应用。
附图说明
图1代表相对横坐标上的密封温度的50μm共挤出配方(A)和含有10％均匀支化的LLDPE的配方(B)和含有10％PB1的配方(C)的剥离密封曲线的图。密封：相对其自身的未处理的剥离面。
图2代表相对横坐标上的密封温度的50μm共挤出配方(A)、含有10％均匀支化的LLDPE的配方(B)和含有10％PB1的配方(C)的剥离密封曲线的图。密封：相对作为剥离层载体的300μmPVC的电晕处理过的剥离面。
图3代表50μm共挤出配方(A)和含有10％均匀支化的LLDPE的配方(B)热粘接曲线。
图4代表加入均匀支化的LLDPE(B)和PB-1(C)对50μm共挤出前体配方的剥离力的影响。在140℃下密封：相对其自身的未处理的剥离面。
发明详述
本发明的思想是开发一种可以大容积混合的标准预混配方并将其用作最终可剥离的密封薄膜的前体。
在最终薄膜挤出时，通过加入该预混配方中没有的其它组分，可以将该特定配方快速调向特定消费者的要求。以这种方式，可以在最终薄膜挤出步骤期间调整预混前体配方的剥离力和热粘接性，并且不会改变必须预挤出的混合物的组成。
更具体地说，在薄膜挤出时通过将均匀支化的LLDPE直接混合到预混前体配方中，可以使该剥离密封薄膜具有较低和较高的剥离力以及较高的热粘接性，不会失去必要的剥离-密封性能如夯实明显、粘合破碎、光滑的剥离痕迹、没有齿状以及包括聚酯、聚氯乙烯、聚酰胺、聚丙烯腈和纸的各种基底上的纤维撕破和可剥离性。
具体实施方式
本发明优选实施方式的描述
按照下面所述的条件挤出各种配方并进行测定。常规薄膜单螺杆挤出设备不能均匀分散配方A中所述的前体。因此该步骤必需用例如双螺杆挤出设备的混合挤出设备中进行。预料不到的是，在第二个单螺杆挤出步骤中可以将LLDPE和PB-1均质。
配方A
该配方是预混前体配方的一个实例：
62％的聚乙烯(LDPE)
20％的聚苯乙烯(PS)
13％的苯乙烯-丁二烯-苯乙烯(SBS)
2.5％的氟弹性体基或聚合物基母料
2.5％的抗氧化剂基母料
前体配方原料的实例
LDPE
Escorene LD150BW(Exxon Mobil，ρ＝0.923，MI＝0.923)、Lacqtène(Atofina，ρ＝0.923，MI＝0.3)、Novex LD5307AA(BP Chemicals，ρ＝0.921，MI＝0.7)。
PS
Lacqrene 1240(Atofina，MI＝2)，Lacqrene 1320(MI＝3.5)。
SBS
Finaprene 411(Atofina，MI＜0.5，丁二烯/苯乙烯69/31)、Finaprene 417(Atofina，MI＝1.7，丁二烯/苯乙烯71/29)。
氟弹性体基或聚合物基母料
Ampacet 10562-A(PE-载体)
Schulman AMF 705(PE-载体)
抗氧化剂基母料
Ampacet 10886(PE-载体)
Schulman A0 25(PE-载体)
在第二步将该配方加入到一单螺杆薄膜共挤出设备中。以下配方(B和C)仅涉及共挤出的多层复合物的可剥离层。
配方B
这是朝着增加剥离力和较好热粘接性的改进。
制品B＝制品A+5-25％重量的均匀支化的LLDPE。这种LLDPE的实例是：Exact 0203(Dex Plastomers，ρ＝0.902，MI＝3.0)、Exceed 2518 CB(ExxonMobil，ρ＝0.918，MI＝2.5)、Evolue SP2020(Mitsui，ρ＝0.916，MI＝1.5)、mPact D143(Phillips Petroleum(ρ＝0.916，MI＝1.3)
配方C
这是朝着降低剥离力的改进。制品C＝制品A+5-25％聚丁烯-1。这种聚丁烯-1的实例是：
PB8340(Basell，ρ＝0.908，MI＝4.0)、PB8310(Basell，P＝0.895，MI＝3.0)、Tafmer BL3110(Mitsui，ρ＝0.910，MI＝1.0)、Tafmer BL4000(Mitsui，ρ＝0.915，MI＝1.8)。
在这些挤出薄膜上观察到的试验剥离力取决于测定条件，因此必需在相同试验条件下将它们彼此比较。这是为什么配方A、B和C呈现在相同图上的理由。
试验的密封条件
用括普(Kopp)密封仪进行密封曲线、相对剥离以及相对300μm PVC的剥离。将上颌加热，而含有硬度为邵氏A60的橡胶的下颌在室温下。在2bar压力下用1秒钟的停留时间进行密封。以90°剥离角测定剥离力。在剥离密封试验之前，该50μm薄膜相对19μmOPET层压以避免弹性影响，这样获得比现实更好的结果。
热粘接性测定
用DTC热粘接性测定仪测定热粘接性。将50μm薄膜相对19μmOPET层压并在5bar压力下密封0.5秒钟。密封0.1秒钟之后将该受热颌打开。
在该挤出步骤期间通过施加不同的捏合力或温度可以对该可剥离薄膜的光学质量进行改进。
Claims (13)
1、一种可热封的共挤出多层包装薄膜，它可以在各种基底上剥离，所述基底包括聚乙烯、聚丙烯、聚酯、聚氯乙烯、聚酰胺、聚丙烯腈和纸，该薄膜包括至少一个得自预混前体配方的可剥离层，所述预混前体配方含有：
-50-80％重量的乙烯均聚物和/或共聚物
-15-25％重量的苯乙烯均聚物或/和共聚物
-5-20％重量的热塑性弹性苯乙烯-丁二烯-苯乙烯嵌段共聚物
特征在于，为了改进所述可剥离密封薄膜中的剥离力，所述可剥离层还包括5-25％重量的均匀支化的LLDPE。
2、如权利要求1的包装薄膜，特征在于，所述可剥离层中的均匀支化的LLDPE的含量为10-20％重量。
3、如权利要求1的包装薄膜，特征在于，相对于可剥离层中的聚合物总重量，所述预混前体配方的量为70-90％重量。
4、如权利要求1-3中任一项的包装薄膜，特征在于，在可剥离层中所述薄膜含有4％重量的选自氟弹性体的加工添加剂。
5、如权利要求1的包装薄膜，特征在于，所述共挤出多层薄膜中的剥离层位于该多层复合物的表面或内部。
6、如权利要求4的包装薄膜，特征在于，所述共挤出多层薄膜中的剥离层的厚度在该多层薄膜的总厚度中最大占15％。
7、如权利要求4的包装薄膜，特征在于，所述共挤出多层薄膜中的剥离层的厚度在该多层薄膜的总厚度中占10％。
8、一种可热封且可剥离的共挤出多层包装薄膜的制备方法，特征在于，第一步，在高剪切和分散的挤出设备中将如权利要求1中所述的可剥离层的前体配方预混，然后在第二步将所述预混前体配方通过一单螺杆挤出设备挤出，同时加入均匀支化的LLDPE以改进该包装薄膜的剥离力和热粘接性。
9、如权利要求8的方法，特征在于，在加工期间通过施加外部的捏合力和温度来光学地改进所述薄膜的表面积。
10、如权利要求1的共挤出的可剥离多层密封薄膜用于相对纸的剥离的用途。
11、如权利要求1的包含HDPE作为乙烯聚合物的共挤出的可剥离多层密封薄膜用于可杀菌包装应用的用途。
12、如权利要求1的共挤出的可剥离多层密封薄膜用于夯实明显的包装应用的用途。
13、包含如权利要求1-7中的任一项的薄膜的包装。
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| EP01870249.8 | 2001-11-20 |
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| US8398306B2 (en) | 2005-11-07 | 2013-03-19 | Kraft Foods Global Brands Llc | Flexible package with internal, resealable closure feature |
| US20070259029A1 (en) * | 2006-05-08 | 2007-11-08 | Mcentire Edward Enns | Water-dispersible patch containing an active agent for dermal delivery |
| US20070258935A1 (en) * | 2006-05-08 | 2007-11-08 | Mcentire Edward Enns | Water dispersible films for delivery of active agents to the epidermis |
| US20080057090A1 (en) * | 2006-09-01 | 2008-03-06 | Mcentire Edward Enns | Wrinkle masking film composition for skin |
| US7879942B2 (en) * | 2006-10-05 | 2011-02-01 | Eastman Chemical Company | Switchable adhesive article for attachment to skin and method of using the same |
| US7871696B2 (en) | 2006-11-21 | 2011-01-18 | Kraft Foods Global Brands Llc | Peelable composite thermoplastic sealants in packaging films |
| US7871697B2 (en) | 2006-11-21 | 2011-01-18 | Kraft Foods Global Brands Llc | Peelable composite thermoplastic sealants in packaging films |
| US9232808B2 (en) | 2007-06-29 | 2016-01-12 | Kraft Foods Group Brands Llc | Processed cheese without emulsifying salts |
| US7681732B2 (en) | 2008-01-11 | 2010-03-23 | Cryovac, Inc. | Laminated lidstock |
| EP2085213B1 (en) * | 2008-01-30 | 2010-08-18 | Amcor Flexibles Transpac | Tamper-evident push-through packaging |
| NZ591354A (en) | 2010-02-26 | 2012-09-28 | Kraft Foods Global Brands Llc | A low-tack, UV-cured pressure sensitive acrylic ester based adhesive for reclosable packaging |
| AU2011220771A1 (en) | 2010-02-26 | 2012-09-06 | Intercontinental Great Brands Llc | Reclosable package using low tack adhesive |
| CN102381514A (zh) * | 2010-09-06 | 2012-03-21 | 苏州海顺包装材料有限公司 | 一种食品、药品用封盖膜 |
| US9533472B2 (en) | 2011-01-03 | 2017-01-03 | Intercontinental Great Brands Llc | Peelable sealant containing thermoplastic composite blends for packaging applications |
| EP2540492A1 (en) | 2011-06-30 | 2013-01-02 | Amcor Flexibles Transpac N.V. | Peelable film |
| US20130095335A1 (en) | 2011-10-17 | 2013-04-18 | Becton, Dickinson And Company | Film Composition for Controlled Peelable Seal Film |
| WO2013170199A1 (en) * | 2012-05-10 | 2013-11-14 | Berry Plastics Corporation | Peelable film for packaging |
| EP2669086A1 (en) * | 2012-05-28 | 2013-12-04 | Dow Global Technologies LLC | Cast silage film with enhanced cling properties |
| US20140065397A1 (en) | 2012-08-28 | 2014-03-06 | 3M Innovative Properties Company | Coextruded polymer film configured for successive irreversible delamination |
| US11319131B2 (en) | 2012-11-15 | 2022-05-03 | Bemis Company, Inc. | Sterilization pouch |
| ES2688287T3 (es) | 2012-12-19 | 2018-10-31 | Amcor Flexibles Kreuzlingen Ag | Envase flowpack |
| BR112015030324A2 (pt) | 2013-06-06 | 2017-07-25 | 3M Innovative Properties Co | filme, combinação e método |
| EP3112150A1 (en) | 2015-06-30 | 2017-01-04 | Dow Global Technologies LLC | Methods of preparing a peelable seal layer |
| GB201516575D0 (en) * | 2015-09-18 | 2015-11-04 | Johnson Matthey Plc | Food Packaging |
| US10351305B2 (en) | 2015-11-23 | 2019-07-16 | Amcor Flexibles, Inc. | Package seal having a fibrous breathable material |
| EP3544804A1 (en) | 2016-11-24 | 2019-10-02 | Amcor Flexibles Transpac BVBA | Peelable seal layer |
| DE102016125669B4 (de) | 2016-12-23 | 2021-07-15 | Mondi Ag | Aufreißverpackung |
| CN111844666B (zh) * | 2020-06-29 | 2022-07-05 | 四川东方绝缘材料股份有限公司 | 一种液晶聚合物薄膜和tpx阻胶膜的同步制备方法 |
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| DK169553B1 (da) * | 1979-08-08 | 1994-11-28 | Ucb Sa | Varmforseglelig emballeringsfilm, fremgangsmåde til dens fremstilling samt emballager deraf |
| TW232671B (zh) * | 1990-01-16 | 1994-10-21 | Idemitsu Petrochemical Co | |
| AU2690095A (en) * | 1994-06-06 | 1996-01-04 | W.R. Grace & Co.-Conn. | Laminates for form-fill-seal packaging |
| DE4428291A1 (de) * | 1994-08-10 | 1996-02-15 | Borries Horst Von | Verpackung für zu sterilisierende Artikel |
| CN1110514C (zh) * | 1996-05-06 | 2003-06-04 | 蒙特尔技术有限公司 | 可控剥离强度可热封膜的聚烯烃组合物 |
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| JP2005509564A (ja) | 2005-04-14 |
| CA2461786C (en) | 2011-08-09 |
| PT1453671E (pt) | 2006-08-31 |
| BR0213675A (pt) | 2004-10-26 |
| CY1105031T1 (el) | 2010-03-03 |
| EP1453671B1 (en) | 2006-04-12 |
| WO2003043816A1 (en) | 2003-05-30 |
| KR100931599B1 (ko) | 2009-12-14 |
| TWI291971B (en) | 2008-01-01 |
| US20050008802A1 (en) | 2005-01-13 |
| SI1453671T1 (sl) | 2006-08-31 |
| MY128707A (en) | 2007-02-28 |
| PL369926A1 (en) | 2005-05-02 |
| EP1312470A1 (en) | 2003-05-21 |
| DK1453671T3 (da) | 2006-07-31 |
| PL206828B1 (pl) | 2010-09-30 |
| US7354635B2 (en) | 2008-04-08 |
| DE60210664D1 (de) | 2006-05-24 |
| CA2461786A1 (en) | 2003-05-30 |
| ATE322979T1 (de) | 2006-04-15 |
| BR0213675B1 (pt) | 2013-01-08 |
| KR20040054785A (ko) | 2004-06-25 |
| DE60210664T2 (de) | 2006-11-16 |
| TW200407364A (en) | 2004-05-16 |
| EP1453671A1 (en) | 2004-09-08 |
| BR0213675B8 (pt) | 2013-02-19 |
| JP4030503B2 (ja) | 2008-01-09 |
| AU2002342854A1 (en) | 2003-06-10 |
| ES2260485T3 (es) | 2006-11-01 |
| CN1571727A (zh) | 2005-01-26 |
| ZA200403511B (en) | 2005-08-31 |
| HK1069149A1 (en) | 2005-05-13 |
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