CN1172795C - 热收缩性多层薄膜 - Google Patents
热收缩性多层薄膜 Download PDFInfo
- Publication number
- CN1172795C CN1172795C CNB998054100A CN99805410A CN1172795C CN 1172795 C CN1172795 C CN 1172795C CN B998054100 A CNB998054100 A CN B998054100A CN 99805410 A CN99805410 A CN 99805410A CN 1172795 C CN1172795 C CN 1172795C
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- China
- Prior art keywords
- film
- heat
- resin
- layers
- shrinkable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Abstract
提供了一种以聚酯作表面的热收缩性多层薄膜,其具有良好的可印刷性和对各种自动包装工艺具有良好的适应性。该薄膜防止过大的热收缩应力出现,同时确保必要程度的热收缩性。该多层薄膜包括至少三层,即包含聚酯树脂的外表面层(a)、包含聚酰胺树脂的中间层(b)和包含可密封树脂的内表面层(c)。该薄膜在50℃下在纵向和横向均具有至多3MPa的热收缩应力,以及在90℃下的热水收缩率至少为20%。该薄膜通过双轴吹胀法在较高的拉伸比(7,9,8-3c)下适当生产,然后用蒸汽或温水在较低的温度(10,12,13,11-3e)下热处理。
Description
[技术领域]
本发明涉及一种适于用作热收缩性包装材料的热收缩性多层薄膜,包括含聚酯树脂的外表面层、含聚酰胺树脂的中间层和可密封树脂层,以及生产该热收缩性多层薄膜的方法。
[背景技术]
迄今为止,人们已经借助制袋机广泛制造热收缩性树脂薄膜的包装材料,如袋或囊(pouch),并用内容物填充包装材料或借助自动包装机对包装材料进行流体包装(flow packaging)、托盘包装(traypackaging)或紧缩包装(skin packaging),主要是用于包装火腿、香肠和其它食物。
此类热收缩性树脂薄膜在许多情况下通常以热收缩性多层薄膜形式提供,该多层薄膜包括各种形式或结构的不同树脂的层合体,所述不同树脂包括密封性、可挤出性和拉伸性优异的聚烯烃树脂(下文有时缩写为“PO”),力学性能、拉伸性和阻气性优异的聚酰胺树脂(缩写为“PA”),阻气性特别优异的偏二氯乙烯树脂(缩写为“VdCl”)或乙烯-乙烯醇共聚物树脂(缩写为“EVOH”),热密封性和粘合性优异的乙烯-乙酸乙烯酯共聚物树脂(缩写为“EVA”)或在一定意义上包括离聚物树脂的改性聚烯烃树脂(缩写为“M-PO”)等。层合体形式或结构的代表性例子可包括:PO/PA/PO,EVA/PA/EVA,PO/PA/EVA(例如如日本专利申请公开(JP-A)51-92882、JP-A55-130743、JP-A8-23035所公开),还有PA/EVA/VdCl/EVA/PA(例如如JP-A62-273849所公开),其中在各层合体结构中各层由外表面层向内表面层编号。
当该类具有PO/PA/PO,EVA/PA/EVA或PO/PA/EVA等代表性层合体结构的热收缩性多层薄膜借助包括在代表性自动包装模式中的熔接棒进行热密封时,构成内表面层的PO或EVA层具有良好的密封性,但PO或EVA的外表面层也易于因热熔融而与熔接棒粘合,因而难以增加热密封速度,相应地难以增加自动包装速度。此外,具有这种层合体结构的薄膜也通常易于具有不足的透明度。此外,具有PO外表面层的薄膜易于具有不足的可印刷性。大多数这类困难在具有PA/EVA/VdCl/EVA/PA层合体结构的热收缩性多层薄膜中没有遇到,但这种薄膜的缺点在于其薄膜性能易于随环境条件的变化而改变,因为PA表面层的吸湿性很高。
为了解决常规热收缩性多层薄膜的层合体结构所具有的多数问题,我们的研究和开发小组提出了一种热收缩性多层薄膜,其包括迄今为止尚未用于通过与聚酰胺树脂共挤出和拉伸形成层合薄膜的较薄聚酯树脂(下文有时代表性地缩写为“PET”)外表面层以及聚酰胺树脂中间层,通过使PET外表面层的拉伸性和PA中间层的拉伸性一致而实现(JP-A4-99621,对应于US-A5336549和EP-A476836)。其中公开的热收缩性多层薄膜的层合结构的代表性例子包括:PET/PA/PO,PET/M-PO/PA/M-PO/PO和PET/M-PO/PA/EVOH/M-PO/PO。在该热收缩性多层薄膜中,PET外表面层比作为典型的可密封树脂的PO具有明显要大的耐热性和明显更好的可印刷性且比PA具有更好的防湿稳定性。此外,由于PET外表面层与PA中间层的共拉伸性已经一致,所得薄膜在双轴拉伸之后具有较好的尺寸稳定性,而不需施加引起热收缩性降低的热处理,从而提供作为热收缩性包装材料具有优异性能的热收缩性多层薄膜。
但是我们通过进一步研究发现,上述以PET作为表面的热收缩性多层薄膜因其固有的热收缩性而在用于自动包装时产生几个问题。这些问题例如如下。(a)在其中将加工过的肉类制品放置在发泡塑料托盘上并用热收缩性薄膜包装,然后使薄膜热收缩以提供薄膜紧密贴合于内容物的包装产品的托盘包装情况下,包装产品中的托盘发生变形。(b)在其中以三侧密封的形式用热收缩性薄膜包装皮杂饼,然后热收缩以提供包装产品的皮杂饼包装情况下,皮杂饼弯曲而降低商业价值。(c)当其中含有内容物的深拉容器或托盘用作为盖料的热收缩性薄膜覆盖,然后使薄膜收缩以提供包装产品时,容器或托盘变形。(d)当用热收缩性薄膜包装角形产品(如火腿)并进行煮沸处理(例如在90℃下10分钟)以同时热收缩和消毒时,产品的角圆化而降低商业价值。(e)在包括通过熔接棒热密封在内的自动包装情况下,如果密封速度增加,则在某些情况下发生密封失败。具体而言,在某些情况下因密封间隔减小时的二次密封而发生针孔缺陷。(f)在某些情况下在印刷过程中发生薄膜的不规则收缩,从而使所得印刷薄膜具有印刷偏差或呈非平压状态(non-flat rolled state),因此导致随后的制袋和包装困难。
[发明公开]
因此,本发明的主要目的是提供适合于自动包装的以PET作表面的热收缩性多层薄膜。
为完成上述目的,我们进一步的研究发现已知的以PET作表面的热收缩性多层薄膜所具有的上述问题(a)-(f)大多数归因于其固有的热收缩性,但与热收缩性的程度或幅度相比,更多的是归因于在热收缩过程中在薄膜中出现的过大应力,即过大的热收缩应力。还发现尽管通常对PET(聚酯树脂)薄膜施用热处理或退火作为双轴拉伸之后的后处理以除去热收缩性而提供尺寸稳定性,但与PA层层合的以PET为表面的多层薄膜在合适的条件下双轴拉伸之后可以进行优化的热处理(即能够在较低温度下进行松弛的热处理),以有效地降低热收缩应力,同时保持必要程度的热收缩性,因此解决了在自动包装中遇到的大多数上述问题。还发现为了在低温下在作为优选的双轴拉伸法的吹胀法之后进行发挥均匀松弛效应的这种热处理,特别优选使用蒸汽或具有大热容的温水作为热处理介质。
本发明的热收缩性多层薄膜基于上述发现且更具体地包括至少三层,即包含聚酯树脂的外表面层(a)、包含聚酰胺树脂的中间层(b)和包含可密封树脂的内表面层(c);所述多层薄膜在50℃下在纵向和横向中均具有至多3MPa的热收缩应力且在90℃下的热水收缩率为至少20%。
根据本发明,还提供了一种生产热收缩性多层薄膜的方法,包括以下步骤:
共挤出至少三种熔化的热塑性树脂,形成包含至少三层的管状产品,该至少三层包括含聚酯树脂的外表面层(a)、含聚酰胺树脂的中间层(b)和含可密封树脂的内表面层(c),
用水将管状产品冷却至低于构成层(a)、(b)和(c)的聚酯树脂、聚酰胺树脂和可密封树脂的熔点中最低之一的温度,
将管状产品再加热到最多为构成层(a)、(b)和(c)的聚酯树脂、聚酰胺树脂和可密封树脂的熔点中最低之一的温度,
在将流体引入管状产品中的同时垂直拉伸该管状产品,在垂直方向和圆周方向均以2.5-4倍的拉伸比拉伸该管状产品,从而提供双轴拉伸的管状薄膜,
折叠该管状薄膜,
再次将流体引入折叠的管状薄膜中以形成管状薄膜,
用60-98℃的蒸汽或温水从管状薄膜的外表面层(a)热处理该管状薄膜,和
冷却已热处理的管状薄膜以提供双轴拉伸薄膜,该双轴拉伸薄膜在50℃下的热收缩应力在纵向和横向均为至多3MPa,且在90℃下的热水收缩率为至少20%。
[附图的简要描述]
附图中唯一的图-图1示意说明适合于实施生产本发明热收缩性多层薄膜的方法的实施方案的设备系统。
[本发明的详细描述]
本发明的热收缩性多层薄膜包括至少三层,即包含聚酯树脂的外表面层(a),包含聚酰胺树脂的中间层(b)和包含可密封树脂的内表面层(c)。
构成外表面层(a)的聚酯树脂(PET)可以包含脂族聚酯树脂或芳族聚酯树脂。
更具体地说,构成聚酯树脂的二羧酸的实例可以包括:对苯二甲酸、间苯二甲酸、邻苯二甲酸、5-叔丁基间苯二甲酸、萘二甲酸、二苯基醚二羧酸、环己烷二羧酸、己二酸、草酸、丙二酸、琥珀酸、agelaic酸、癸二酸以及包括不饱和脂肪酸的二聚体在内的二聚酸。这些酸可以单独使用或两种或多种组合使用。构成聚酯树脂的二醇实例可以包括:乙二醇、丙二醇、四亚甲基二醇、新戊二醇、六亚甲基二醇、二甘醇、聚亚烷基二醇、1,4-环己烷二甲醇、1,4-丁二醇和2-烷基-1,3-丙二醇。这些二醇可以单独使用或两种或多种组合使用。
其中优选使用包含芳族二羧酸组分的芳族聚酯树脂,特别优选由作为二羧酸的对苯二甲酸和至多具有10个碳原子的二醇形成的聚酯,如聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯。还优选使用通过用另一二羧酸如间苯二甲酸替换一部分,优选至多30mol%,更优选至多15mol%对苯二甲酸而形成的共聚酯树脂或对苯二甲酸与二醇混合物如乙二醇和1,4-环己烷二醇(如“Kadapack PET#9921”,购自Eastoman Kodak Co.)之间的共聚酯树脂。
聚酯树脂可以优选为特性粘度为约0.6-1.2的树脂。外表面层(a)可以含有至多20wt%的聚酯树脂以外的热塑性树脂,如由热塑性聚氨酯为代表的热塑性弹性体,或用酸如马来酸或其酸酐改性的聚烯烃树脂。
构成中间层(b)的聚酰胺树脂(PA)的例子可以包括:脂族聚酰胺,如尼龙6,尼龙66,尼龙11,尼龙12,尼龙69,尼龙610和尼龙612;以及脂族共聚酰胺,如尼龙6/66,尼龙6/69,尼龙6/610,尼龙66/610和尼龙6/12。其中从模塑性和加工性考虑特别优选尼龙6/66和尼龙6/12。这些脂族(共)聚酰胺可以单独使用或以两种或多种的混合物使用。还可以使用该脂族(共)聚酰胺与少量芳族聚酰胺的共混物。这里,芳族聚酰胺意指二胺与二羧酸之间的缩聚产物,该二胺和二羧酸中至少一种至少部分地含有芳族单元。芳族共聚酰胺是优选的。其例子可以包括:脂族尼龙与包括芳族二胺单元的芳族聚酰胺的共聚物,如尼龙66/610/MXD6(其中“MXD6”代表聚己二酰间苯二甲胺),以及脂族尼龙与包括芳族羧酸单元的芳族聚酰胺的共聚物,如尼龙66/69/6I,尼龙6/6I和尼龙6I/6T(其中“(尼龙)6I”表示聚间苯二甲酰己二胺和“(尼龙)6T”表示聚对苯二甲酰己二胺)。这些聚酰胺树脂可以单独使用或以混合物使用,以提供优选为160-210℃的熔点。中间层(b)可以含有至多约30wt%聚酰胺树脂以外的热塑性树脂,如用酸如马来酸或其酸酐改性的聚烯烃树脂,乙烯-丙烯酸共聚物,乙烯-甲基丙烯酸共聚物,离聚物树脂或(部分)皂化的乙烯-乙酸乙烯酯共聚物。
构成内表面层(c)的可密封树脂可以适当地从热塑性树脂中选择,所述热塑性树脂包括:通过使用单点催化剂或金属茂催化剂(有时缩写为“SSC”)聚合的聚烯烃,包括线形低密度聚乙烯(缩写为“SSC-LLDPE”)和极低密度聚乙烯(缩写为“SSC-VLDPE”);常规类型的乙烯-α-烯烃共聚物,包括以通常被接受的缩写表示的“LLDPE”和“VLDPE”;乙烯-乙酸乙烯酯共聚物(缩写为“EVA”),乙烯-甲基丙烯酸共聚物(缩写为“EMAA”),乙烯-甲基丙烯酸-不饱和脂族羧酸共聚物,低密度聚乙烯,离聚物树脂(缩写为“IO(树脂)”),乙烯-丙烯酸共聚物,乙烯-丙烯酸甲酯共聚物(缩写为“EMA”)和乙烯-丙烯酸丁酯共聚物(缩写为“EBA”)。这类优选的可密封树脂可以称为乙烯共聚物,典型的是主要量(即多于50wt%)的乙烯与少量(即小于50wt%,优选至多30wt%)的可与乙烯共聚的乙烯基单体的共聚物,乙烯基单体选自具有3-8个碳原子的α-烯烃以及不饱和羧酸和至多具有8个碳原子的羧酸的不饱和酯,包括丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯和乙酸乙烯酯,或乙烯共聚物的酸改性产物(优选用至多3wt%不饱和羧酸改性)。还可以使用热塑性树脂,如聚丙烯树脂,聚酯树脂或脂族尼龙。该可密封树脂可以优选具有至多150℃,更优选至多135℃的熔点。还可以使用在不损害所得薄膜或其密封产品的透明性的程度内包括至少一种该可密封树脂的共混物。
在上面所述当中,构成内表面层(c)的该可密封树脂的优选例子可以包括:SSC-LLDPE,SSC-VLDPE,LLDPE,VLDPE,EVA,EMAA,乙烯-甲基丙烯酸-不饱和脂族羧酸共聚物和IO树脂。特别优选的一类SSC类聚烯烃可以包括通过使用几何受限催化剂(DowChemical Company开发的一种金属茂催化剂)得到的那些。几何受限催化剂可以提供乙烯-α-烯烃共聚物,其可以归为每1000个碳原子具有约0.01-约3,优选约0.01-约1,更优选约0.05-约1个长链支化的基本线形聚乙烯树脂。由于长链支化各自具有约6个或更多个选择性引入其分子结构中的碳原子,乙烯-α-烯烃共聚物可以具有优异的物理性能和良好的成型性或加工性,且其例子为可以从Dow ChemicalCompany以商品名“AFFINITY”或“ELITE”购得的那些(包含1-辛烷作为α-烯烃)。
通过使用金属茂催化剂得到的聚乙烯树脂的其他例子可以包括从Exxon Co.以商品名“EXACT”购得的那些。
该金属茂催化的聚烯烃(SSC-聚烯烃)可以优选具有低于3,更优选1.9-2.2的分散因子,其定义为重均分子量(Mw)与数均分子量(Mn)之间的比例(Mw/Mn)。
本发明的热收缩性多层薄膜包括上述包含聚酯树脂的外表面层(a),包含聚酰胺树脂的中间层(b)和包含可密封树脂的内表面层(c)作为其必不可少的组成层,但还可以包括包含聚酰胺树脂的中间层(b)以外的额外中间层,以例如提供具有改进的功能性或加工性的产品多层薄膜。该任选中间层的例子可以包括下述。
阻气中间层(d),特别是氧气阻隔层,包含阻气树脂,其例子可以包括:EVOH;包括芳族二胺单元的芳族聚酰胺,如聚甲基丙烯酸己二酰胺(polymethacrylene adipamide)(尼龙MXD6);和包括芳族羧酸单元的无定形芳族聚酰胺,如聚间苯二甲酰己二胺/对苯二甲酰己二胺(尼龙6I/6T),其为间苯二甲酸、对苯二甲酸和六亚甲基二胺的共聚物。
另一类型的优选中间层可以包括乙烯和至少一种在其分子中含有氧原子的单体的共聚物。其具体例子可以包括:EVA,EMAA,乙烯-甲基丙烯酸-不饱和脂族羧酸共聚物,EMA,EAA,EBA和IO树脂。
此外,密度低于0.900g/cm3的金属茂催化的聚烯烃层具有良好的拉伸取向特性且可以优选插入作为任选的中间层以提供具有大热收缩率的多层薄膜。
可以根据需要插入一层或多层粘合树脂层作为任选的中间层,例如在上述各层之间不能确保足够的粘合性的情况下。该粘合树脂可以选自构成上述任选中间层的那些。用于上述目的的粘合树脂的其他优选例子可以包括:EVA,EEA,EAA,酸改性的聚烯烃(包括烯烃均聚物或共聚物与不饱和羧酸如马来酸和富马酸、这些酸的酸酐、酯类或金属盐之间的反应产物,如酸改性的VLDPE,酸改性的LLDPE和酸改性的EVA)。特别合适的是使用用酸如马来酸或其酸酐改性的聚烯烃树脂。
在任一个或多个上述层中,可以加入添加剂,如润滑剂或抗静电剂。
润滑剂的例子可以包括:烃类润滑剂,脂肪酸润滑剂,脂肪酸酰胺润滑剂,酯类润滑剂和金属皂。润滑剂可以是液体或固体。烃类润滑剂的具体例子可以包括:液体石蜡,天然石蜡,聚乙烯蜡和微晶蜡。脂肪酸润滑剂可以包括硬脂酸和月桂酸。脂肪酸酰胺润滑剂可以包括硬脂酸酰胺,棕榈酸酰胺,N-油基-棕榈酸酰胺,芥酸酰胺,花生酸酰胺,油酸酰胺,亚甲基双硬脂酰胺和亚乙基双硬脂酰胺。酯类润滑剂可以包括硬脂酸丁酯,硬化蓖麻油,乙二醇单硬脂酸酯和硬脂酸单甘油酯。金属皂可以衍生自具有12-30个碳原子的脂肪酸且可以包括硬脂酸锌和硬脂酸钙作为代表性例子。其中优选脂肪酸酰胺润滑剂和钙金属皂,因为其与热塑性树脂,特别是聚烯烃树脂具有良好的相容性。润滑剂的具体优选例子可以包括山萮酸酰胺,油酸酰胺和芥酸酰胺。这些润滑剂的加入形式优选为母料。含有例如5-20wt%的润滑剂的该母料的加入量优选足以在所涉及的树脂层中提供浓度为0.05-2wt%的润滑剂。
抗静电剂可以优选为表面活性剂,其可以是阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂及其混合物中的任一种。抗静电剂的加入比例优选为加入它的树脂层的0.05-2wt%,更优选0.1-1wt%。
在上述层结构中,还可以加入无机润滑剂(抗粘剂)或防雾剂。
无机润滑剂可以包括待加入成膜树脂中以防止薄膜相互粘连的已知无机填料,如滑石、硅藻土、硅石、沸石、碳酸钙和硅铝酸盐。优选球形填料。其中优选硅石和硅铝酸盐,因为它们具有良好的分散性。该无机润滑剂以母料的形式加入。
防雾剂的加入是为了防止含太多水分的内容物(如“肉”)的可观察性在托盘包装等情况下因水滴粘于包装薄膜的内表面而变差且可以使用已知的防雾剂。该防雾剂可以捏合到薄膜材料中或施用于表面上。防雾剂通常加入内表面层,但可以加入外表面层以在沿其折皱部分(pinch portion)将管状薄膜切成单一薄膜且随后绕辊卷绕时转移到内表面层上。
热收缩性多层薄膜优选可以通过层合上述各层,然后拉伸成总厚度为3-120μm,特别是10-90μm的多层薄膜的最终形式而形成。更具体地说,如在托盘包装、皮杂饼包装、成盖(lid-forming)等中在干加热下进行收缩的薄膜优选可以具有至多50μm的较小厚度,且如在沸腾或热水收缩中在湿加热下收缩的薄膜优选可以具有至少35μm的较大厚度。
更具体地说,优选包含聚酯树脂的外表面层(a)的厚度为0.5-10μm,特别是1-5μm,包含聚酰胺树脂的中间层(b)的厚度为3-50μm,特别是5-30μm,且包含可密封树脂的内表面层(c)的厚度为8-80μm,优选10-60μm。为了提供具有适当一致的双轴拉伸性的多层薄膜,优选层(a)的厚度小于层(b)的厚度,更具体地说为层(b)厚度的3-70%,特别是6-50%。
任选叠置的阻气层(d)可以具有例如1-30μm,优选2-15μm的厚度。低于1μm时,改进氧气阻隔性的作用可能很小,而高于30μm时,各层的挤出以及多层薄膜的拉伸和加工变得困难。
可以设置多层粘合树脂层,各自具有合适地为0.5-5μm的厚度。
热收缩性多层薄膜可以通过首先通过多个挤出机共挤出形成尚未拉伸的薄膜、然后由已知方法如拉幅机法双轴拉伸薄膜而形成。拉伸比在纵向和横向均可以优选为2.5-4倍。如此形成的热收缩性多层薄膜还可以根据已知的层合方法与另一树脂层层合。
热收缩性多层薄膜可以优选根据本发明的方法通过吹胀形成。其优选实施方案参照附图中的唯一图-图1描述。
相应于层合树脂种类的数目提供多个挤出机1(仅显示一个),并将来自各挤出机的各树脂通过环形口模2共挤出,形成管状产品(型坯)3,其包括至少三层,即包含聚酯树脂的外表面层(a)、包含聚酰胺树脂的中间层(b)和包含可密封树脂的内表面层(c)。然后将型坯3垂直下拉到水浴4中并由夹紧辊5卷绕,同时冷却到低于构成各树脂层的主要树脂(即聚酯树脂、聚酰胺树脂和可密封树脂)的熔点中最低之一的温度,优选冷却到40℃或更低。如此卷取的薄膜3a在根据需要任选引入开孔助剂(opening aid)如大豆油于其中的同时引入温度例如为80-95℃的温水浴6中,该温水浴6的温度至多为构成各层的主要树脂的熔点中最低者,并将如此温热的管状薄膜3b上拉,形成管状薄膜3c的膜泡,在夹紧辊对7和8之间引入流体空气,从而在用来自冷却空气环9的10-20℃冷空气冷却薄膜3C的同时在垂直或加工方向(MD)和横向或侧向(TD)各自以优选2.5-4倍,更优选2.8-4倍的拉伸比同时双轴拉伸管状薄膜3C。将由此双轴拉伸的薄膜3d折叠一次或平折,然后下拉,再次形成管状薄膜的膜泡3e,在夹紧辊对10和11之间引入流体空气。将管状薄膜的膜泡3e固定在热处理管12中,在其中将来自吹入口13的蒸汽吹向(或将来自喷射口的温水喷射于)管状薄膜3e,以在60-98℃、优选60-80℃下将双轴拉伸后的管状薄膜3e热处理约1-20秒钟,优选约1.5-10秒钟,从而使管状薄膜在垂直方向(MD)和横向(TD)各自松弛2-25%,优选5-15%。热处理后的管状薄膜3e对应于本发明的热收缩性多层薄膜且绕卷绕辊14卷绕。
如此得到的本发明热收缩性多层薄膜在50℃下在加工方向(MD)和横向(TD)各自具有至多为3MPa,优选至多2.5MPa的降低热收缩率,同时在至少一个方向,优选在MD和TD方向上各自保留足够程度的90℃热水收缩率,至少为20%,优选至少为25%,进一步优选为至少30%,从而具有良好的自动包装性能。
在90℃下热水收缩率至少为20%,优选至少25%,特别优选至少30%的薄膜可以紧密贴合几乎所有类型的内容物,提供包装漂亮的产品。这类程度的热水收缩率对应于在120℃下的干热收缩率为至少15%,特别是20%或更高,从而在包括干热收缩包装步骤的自动包装方法中具有漂亮地包装内容物的作用。
此外,由于适度降低的热收缩应力至多为3MPa,优选2.5MPa或更低,本发明的热收缩性多层薄膜对包装机具有优异的适应性或匹配性且具有优异的热密封性,可以有效地防止内容物和容器如托盘和深拉容器的变形,从而允许高速生产具有极好外观的自动包装产品。进一步地说,在包装的实际热收缩温度下的最大热收缩应力优选应至多为4MPa,更优选至多3.5MPa。
为了实现这种低热收缩应力,同时保持足够高的热水收缩率,特别优选的是在MD/TD各方向上确保2.5-4倍、特别是2.8-4倍的较高拉伸比,然后用蒸汽或具有大热容的温水在60-98℃、特别是60-80℃下进行低温热处理。在较低的拉伸比下,难于确保热处理后具有必要程度的热收缩率,且产品薄膜具有大的局部厚度波动,因而易于呈现与自动包装机的充分匹配。另一方面,当在双轴拉伸后的热处理中使用具有小热容的介质如加热空气或使用较低温度的加热空气或采用低于60℃的较低温度时,难于得到充分降低热收缩应力的目标效果。
在本发明的上述热收缩性多层薄膜生产方法中,多层薄膜在拉伸之前或之后可以暴露于光化辐射。通过暴露于光化辐射,产品多层薄膜可以具有改进的耐热性和机械强度。由于其交联作用适中,暴露于光化辐射可以提供改进的拉伸薄膜成型性和改进的耐热性。在本发明中,可以使用已知的光化辐射如α射线、β射线、电子射线、γ射线或X射线。为了提供足够程度的交联作用,优选电子射线和γ射线,且鉴于处理的容易性和生产目标多层薄膜的高加工能力,特别优选电子射线。
上述暴露于光化辐射的条件可以根据其目的如所要求的交联程度适当设定。例如,优选在150-500kV范围的加速电压下进行电子射线暴光,以提供10-200kGy(千戈瑞)的吸收剂量或在0.05-3kGy/小时的放射剂量率下进行γ-射线暴光,以提供10-200kGy的吸收剂量。
通过暴露于光化辐射,如电子射线,还可以提供内表面层(c)的改进肉类粘合性,即与加工的肉类制品如火腿和香肠的粘合性,从而防止在薄膜和内容物之间产生滞留汁,改进包装产品的外观并保持内容物的质量。
为了相似的目的,还可以将内表面层(c)暴露于电晕放电。电晕放电处理可以通过使用装有包括高频振荡器和高压转换器的高频电源的电晕放电器而进行,将薄膜施用于聚硅氧烷涂敷的处理辊上并通过在放电电极和处理辊之间施用电压至多为18kV且频率为5-120kHz的交流波形,优选正弦波的至多4kW AC电能将薄膜暴露于电晕放电,从而得到至多36达因/cm2,更优选至多34达因/cm2的降低表面张力的处理薄膜表面。
[实施例]
下文中将基于实施例和对比例更具体地描述本发明。然而,应该注意的是本发明的范围并不受这些实施例的限制。其中所述的某些物理性能基于根据下列方法测定的值。
<物理性能测量方法>
1.热水收缩率
将其上于加工方向(MD)和垂直于加工方向的横向(TD)各自以10cm的间距划有标记的样品薄膜在调至90℃的热水中浸渍10秒钟,然后从中取出,接着立即在室温下在水中骤冷。然后测量各标记之间的间距并将距离的降低表示为原始距离10cm的百分数。将来自各产品薄膜的五个样品薄膜进行上述测量并在MD和TD各方向上显示降低百分数的平均值。
2.干热收缩率
将3mm厚的瓦楞板放置在导轨上并将Geer烘箱(“MOG-600型”,购自K.K.Robert)放置在其上并加热到预定的温度。将样品薄膜放入该烘箱中,在样品上在MD和TD方向上各自以10cm的间距划上标记。此时,在放入样品薄膜后立即关闭烘箱门,以使门开启时间限制为3分钟以内。门关闭之后,将样品薄膜在Geer烘箱中放置30秒钟,然后取出,自然冷却。然后测量样品薄膜上各标记之间的距离并将距离的降低以原始距离10cm的百分数表示。将来自各产品薄膜的五个样品薄膜进行上述测量并在MD和TD各方向上显示降低百分数的平均值。
3.热收缩应力
从产品多层薄膜中切出在其MD和TD方向分别具有150mm长度和15mm宽度的样品薄膜条,并将其以100mm的夹具跨距固定在通用试验机(“5565型”,购自Instron Co.)上,该试验机放置在保持23℃的恒温容器(“3119系列”,购自Instron Co.)中,然后在恒温容器中以2℃/分钟的速率升温。在下列实施例和对比例中,示出了随温度升高而变化且在升温过程中于40℃和50℃下测定的热收缩应力。
<薄膜生产实施例>
下面描述用于生产热收缩性多层薄膜的实施例和对比例。用于下列生产实施例中的树脂与其缩写一起示于表1中。
实施例1
使用具有如图1粗略所示的结构的设备,分别通过多个挤出机1(仅示出一个)挤出各种树脂并将熔化的树脂引入环形口模2中以下述顺序将各层熔融粘合而共挤出从外层到内层具有PET(2)/M-PE(1.5)/NY-1(7)/EVOH(5)/M-PE(1.5)/VL-2(24)的层状结构的管状层合产品(型坯),各层的厚度比如括号中所示。用水浴4将从模头2挤出的熔融型坯3骤冷至10-18℃以形成扁平的管状产品3a。然后将该扁平的管状产品3a通过92℃的温水浴6并成型为膜泡状的管状薄膜3c,然后通过吹胀法将其在MD方向以3.1倍且在TD方向以3.2倍的拉伸比双轴拉伸,同时用来自空气环9的15-20℃的冷却空气冷却。然后将双轴拉伸的薄膜3d导入2米长的热处理管12中以形成膜泡状的管状薄膜3e,然后用由蒸汽吹入口13吹出的70℃蒸汽将其热处理2秒钟,同时使其在MD方向松弛5%且在TD方向松弛5%,从而得到双轴拉伸的薄膜(热收缩性多层薄膜)3f。如此得到的双轴拉伸薄膜具有362mm的平折宽度和41μm的厚度。
如此得到的双轴拉伸薄膜与在其它实施例和对比例中得到的双轴拉伸薄膜的层合体结构和薄膜生产(双轴拉伸)条件等示于表2中。
实施例2-21和对比例1-12
以与实施例1相似的方式制备各种双轴拉伸的薄膜,不同的是如表2所示分别改变层结构和薄膜生产(双轴拉伸)条件并如表3所示分别改变松弛和热处理条件。
在上面各实施例和对比例中得到的各双轴拉伸的薄膜进行上述物理性能的测量和下述性能评价试验。结果示于下述表3-7中。
<性能评价试验>
1.煮沸试验
将以上述方式得到的样品管状薄膜在两个方向上,即在MD和TD方向上热密封,并切开一个折皱部分,得到长350mm(薄膜的TD方向)和宽150mm(薄膜的MD方向)的袋。将作为内容物的长方体形状的火腿插入袋中并以15%的富余百分数(room percentage)(即薄膜袋的周长为内容物的115%)在其中真空密封,然后在90℃的热水浴中进行10分钟的热消毒。然后根据下列标准评价包装产品的外观。
A:热消毒后火腿的形状基本没有变化,且薄膜紧密贴合在火腿上。在煮沸之后未观察到薄膜袋的破裂。
B:热消毒后火腿的各角发生一定程度的变形,从而降低其商业价值。
C1:热消毒后火腿的各角因发生圆形变形而消失,因而降低其商业价值。
C2:由于收缩不足而不能达到充分的紧密贴合,且在包装薄膜上出现一些褶皱。
2.可印刷性
通过使用胶印机(购自SMB Co.)在下列条件下在样品薄膜的一个表面(在外表面侧上)上进行印刷:
油墨:RESINO INK WHITE(10kg),含15%硬化剂。
橡胶板:将两块橡胶板以190mm的间距连于直径为380mm的圆筒上。
加热器温度:操作台(at station)为21℃,电桥(at bridge)为50℃。
运转速度:70m/min
根据下列标准进行评价:
A:基本未观察到印刷后的收缩(<3%),且未观察到印刷偏差。通过印刷机后的薄膜可卷成平滑的筒且能随后用于制袋而不出现问题。
B:印刷后的收缩≥3%且≤5%,但未观察到印刷偏差。印刷后的薄膜可卷成基本平滑的筒且能随后用于制袋。
C:印刷后的收缩大于5%,且发生印刷偏差而在薄膜中产生褶皱。将印刷后的薄膜卷成筒,其不是平滑的,因而在随后的制袋中引起困难。
3.紧缩包装性能
将各样品薄膜与作为基础薄膜的市售多层薄膜(“FA-1”,购自Kureha Kagaku K.K.)一起用作紧缩包装的盖膜(lid film)。将纸板放置在基础薄膜上并将腊肉的平切片材放置在其上以用在130℃下加热的样品薄膜通过紧缩包装机进行紧缩包装。
A:形成包装产品的薄膜基本上没有褶皱,且甚至在不存在腊肉切片的边界部分未观察到翘曲。
B:形成包装产品的薄膜基本上没有褶皱,但不存在腊肉切片的边界部分朝盖膜侧轻微翘曲,翘曲部分的高度距放置包装产品的水平基线小于1cm。
C1:形成包装产品的薄膜基本上没有褶皱,但不存在腊肉切片的边界部分朝盖膜侧明显翘曲,从而得到较差的包装产品外观。边界部分的翘曲高度距放置包装产品的水平基线超过1cm。
C2:形成包装产品的薄膜发生褶皱,从而得到成问题的包装产品外观,严重损害其商业价值。
4.流体包装性能
通过使用水平流体包装机(“NW406”,购自Ohmori Kikai K.K.)评价流体包装性能。将样品薄膜以通过在生产实施例中得到的管状薄膜的双侧尺寸上割掉边缘部分形成的380mm宽薄膜提供。将样品薄膜在中心密封温度为180℃、上封口上部温度为100℃和上封口下部温度为140℃的条件下进行流体包装袋的制备,得到宽170mm和长300mm的流体包装袋。在流体包装袋中插入周长为300mm且长度为200mm的圆柱形火腿并真空包装,然后在90℃的热水中煮沸10分钟。
A:熔接棒与叠置薄膜的待密封部分对齐,并在30m/min的薄膜速度下稳定地进行制袋,同时沿密封部分几乎不产生收缩。
B:在熔接棒的位置和叠置薄膜的待密封部分之间发生偏差。结果使得稳定的制袋由于沿密封部分发生收缩而不能在30m/min的薄膜速度下进行,但在10m/sec的薄膜速度下可以制袋。
5.托盘包装性能
通过切割切除生产实施例中得到的产品管状薄膜的折皱部分,形成450mm宽的平膜。将各自盛有生肉的聚苯乙烯制成的托盘通过使用流体包装机(“Delta 2000”,购自Dapack Co.)在35击(shot)/分钟的速率下进行气体替换(gas-substitution)包装,同时吹入80%(体积)二氧化碳和20%(体积)氧气的混合物作为替换气体。在相对于该托盘的富裕比(room rate)为20%下进行包装。然后将包装体引入收缩管道(购自Meurer Co.),以在其中收缩,同时吹入170℃的空气6秒钟。
A:在通过收缩管道后未观察到托盘变形,因而得到具有漂亮外观的包装产品。
B:在通过收缩管道后观察到一些托盘变形。
C1:在通过收缩管道后观察到显著的托盘变形,因而得到外观成问题的包装产品。
C2:由于收缩不足,薄膜不能与托盘贴合,因而得到外观成问题的包装产品。
6.皮杂饼包装性能
将在生产实施例中得到的产品管状薄膜沿折皱线切开,形成750mm宽的平膜。将平膜用于通过使用流体包装机(“Delta 2000”,购自Dapack Co.)以35击/分钟的速率气体替换包装直径为300mm且高度为10mm且放置于聚苯乙烯泡沫盘上的未煮熟的皮杂饼,同时吹入碳酸盐气体。所得包装袋的尺寸为长380mm,宽360mm。将包装袋通过收缩管道(购自Meurer Co.)以在其中收缩,同时吹入200℃的空气。
A:包装的皮杂饼通过收缩管道后未出现翘曲,因而具有良好的外观。
B:包装的皮杂饼通过收缩管道后出现翘曲,因而严重损害其商业价值。
7.成盖(Lidding)性能(作为托盘盖料的适应性)
将在生产实施例中得到的产品管状薄膜沿折皱线切开,形成840mm宽的平膜。将平膜用作覆盖各自具有从内侧到外侧为聚乙烯(20μm)/粘合树脂/EVOH(皂化乙烯-乙酸乙烯酯共聚物)(7μm)/粘合树脂/聚苯乙烯泡沫(300μm)的层状结构且尺寸为225mm(长度)×155mm(宽度)×40mm(高度)的托盘的盖膜,从而通过在密封温度为110℃且速率为20击/分钟的条件下使用预制托盘机(“INPACKNEMA 4”,购自Ross Co.)使该平膜在其内侧表面用各托盘的聚乙烯上(内)侧表面覆盖。根据下列标准评价由此得到的已包装托盘。
A:在包装后放置一天的产品中,没有观察到盖膜的松脱或托盘的变形,包装体具有漂亮的外观。
C:在包装后放置一天的产品中,没有观察到薄膜的松脱,但托盘发生变形而降低其商业价值。
表1:组分树脂和添加剂
缩写 | 树脂/添加剂* | 制造商(商标名) | 结晶熔点(℃) | 备注** |
Ny-1 | 尼龙6/66共聚物 | Mistubishi Engineering Plastic K.K.(NOVAMID 2340A1) | 195 | ηrel=4.5 |
Ny-2 | 尼龙6/66共聚物 | Ube Kosan K.K.(UBE NYLON 5034B) | 193 | ηrel=4.4 |
Ny-3 | 尼龙6/12共聚物 | Toray K.K.(AMILAN CM 6541X3) | 133 | ηrel=2.7 |
Ny-4 | 尼龙66/610/MXD 6共聚物 | EMS K.K.(MULTIPOLYAMID BM18SBH) | 181 | - |
PET | 对苯二甲酸乙二醇酯共聚酯*1 | Kanebo K.K.(BELBET IFG-8L) | 228 | ηint=0.80 |
PET-2 | 对苯二甲酸乙二醇酯共聚酯*2 | Eastman Kodak Co.(KODAPAK PET9921) | 234 | ηint=0.80 |
EVOH | 皂化乙烯-乙酸乙烯酯共聚物 | Kurary K.K.(EVAL EPG156B) | 160 | MFR=6.5g/10min. |
VL-1 | 乙烯-丁烯-1共聚物(d=0.905g/cm3) | Sumitomo Kagaku K.K.(SMIKASEN CN2011) | 107 | MFR=4.0g/10min. |
VL-2 | 乙烯-己烯共聚物(d=0.908g/cm3) | Sumitomo Kagaku K.K.(SMIKASEN CS3009) | 119 | MFR=3.0g/10min. |
VL-3 | 乙烯-辛烯共聚物(d=0.902g/cm3) | DSM(TEAMEX 1000F) | 124 | MFR=3.0g/10min. |
SVL-1 | 乙烯-辛烯共聚物*3(d=0.910g/cm3) | Dow Chemical Co.(AFFINITY PL1845) | 106 | MFR=3.5g/10min. |
SVL-2 | 乙烯-辛烯共聚物*3(d=0.895g/cm3) | Dow Chemical Co.(AFFINITY PF1140) | 94 | MFR=1.6g/10min. |
表1(续)
SLL | 乙烯-辛烯共聚物*3(d=0.916g/cm3) | Dow Chemical Co.(ELITE5400) | 122 | MFR=1.2g/10min. |
M-PE | 改性的极低密度聚乙烯*4 | Mitsui Kagaku K.K.(ADMER SF730) | - | MFR=2.7g/10min. |
TPU | 热塑性聚氨酯*5 | Kuraray K.K.(KURAMILON U1195E) | - | - |
LUB-1 | 润滑剂母料*6 | Nippon Pigment K.K.(NIPPISUN COLOUR MB60) | - | - |
LUB-2 | 润滑剂母料*7 | Sumitomo Kagaku K.K.(SMIASEN A-26) | - | MFR=2.0g/10min. |
AF | 防雾添加剂*8 | Riken Vitamin K.K.(KP-410) | - | - |
*1:酸为12mol%间苯二甲酸与88mol%对苯二甲酸的混合物。
*2:对苯二甲酸与乙二醇和1,4-环己烷二甲醇的二醇之间的共聚酯。
*3:在金属茂催化剂存在下聚合。
*4:用不饱和羧酸改性。
*5:氮含量=4.1%,d(密度)=1.21g/cm3。
*6:聚对苯二甲酸乙二醇酯(基础树脂),含2.5wt%二氧化硅。
*7:聚乙烯(基础树脂),含4%硅铝酸盐和2%elucic酸酰胺。
*8:线性极低密度聚乙烯(基础树脂),含8wt%月桂酸二甘油酯/高级醇环氧乙烷醚(4.5/3.5)混合物。
**:ηrel=相对粘度(JIS-K6810),ηint=特性粘度,MFR=熔体流动速率
表2:薄膜结构和成膜条件
实施例和对比例 | 层合层(厚度) | 总厚度(μm) | 成膜条件 | 薄膜平折宽度(mm) | |||||||
第一层(μm) | 第二层(μm) | 第三层(μm) | 第四层(μm) | 第五层(μm) | 第六层(μm) | 加热温度(℃) | 拉伸比 | ||||
MD | TD | ||||||||||
实施例1-3对比例1 | PET+LUB-1*1(2) | M-PE(1.5) | Ny-1(7) | EVOH(5) | M-PE(1.5) | VL-2+LUB-2*3(24) | 41 | 92 | 3.1 | 3.2 | 362 |
实施例4-11对比例2-3 | PET+LUB-1*2(1.5) | M-PE(1.5) | Ny-1(8) | EVOH(5) | M-PE(1.5) | VL-1+LUB-2*3(19) | 36.5 | 92 | 2.9 | 3.1 | 362 |
实施例12-15对比例4-5 | PET+LUB-1*1(1) | M-PE(1) | Ny-1(5) | EVOH(3) | M-PE(1) | VL-2+AF*4(13) | 24 | 92 | 2.9 | 3.1 | 515 |
实施例16 | PET+LUB-1*1(1.5) | M-PE(1) | Ny-1(7) | EVOH(4) | M-PE(1) | VL-2+AF*4(16) | 30.5 | 92 | 2.9 | 3.1 | 515 |
实施例17对比例6 | PET+LUB-1*1(1.5) | M-PE(1.5) | Ny-1+Ny-3(50%+50%)(8) | EVOH(5) | M-PE(1.5) | VL-1+LUB-2*3(19) | 36.5 | 92 | 3.0 | 2.9 | 515 |
实施例18对比例7 | PET+LUB-1*1(2) | M-PE(1.5) | Ny-1+Ny-4(70%+30%)(7) | EVOH(5) | M-PE(1.5) | VL-2+LUB-2*3(22) | 39 | 87 | 3.0 | 3.4 | 515 |
实施例19对比例8 | PET+LUB-1*1(3) | M-PE(2) | Ny-1(15) | M-PE(2) | VL-1+LUB-2*3(42) | - | 64 | 92 | 2.9 | 3.1 | 362 |
表2(续)
实施例20 | PET+LUB-1*1(4) | M-PE(2) | Ny-1(25) | M-PE(2) | SLL(25) | -- | 58 | 92 | 2.9 | 3.1 | 362 |
实施例21 | PET+LUB-1*1(4) | M-PE(1.5) | Ny-1(20) | EVOH(3) | M-PE(1.5) | SLL(50) | 80 | 92 | 2.6 | 2.9 | 412 |
实施例22 | PET-2(2) | M-PE(1.5) | Ny-2(8) | EVOH(5) | M-PE(1.5) | VL-3+LUB-2*3(21) | 39 | 92 | 3.1 | 3.2 | 335 |
对比例9-11 | PET+LUB-1*1(4) | M-PE(3) | Ny-1(17) | M-PE(1.5) | VL-1+LUB-2*3(27) | - | 54 | 92 | 2.3 | 2.5 | 515 |
对比例11-12 | PET+LUB-1*1(4) | M-PE(2) | Ny-1(12) | EVOH(6) | M-PE(2) | VL-1+LUB-2*3(19) | 45 | 92 | 2.3 | 2.5 | 515 |
*1:PET∶LUB-1=98∶2(wt.)
*2:PET∶TPU∶LUB-1=88∶10∶2(wt.)
*3:VL-1∶LUB-2=97∶3(wt.),VL-2∶LUB-2=97∶3(wt.),VL-3∶LUB-2=97∶3(wt.)
*4:VL-2∶AF=90∶10(wt.)
表3:热处理条件和性能评价(1)
实施例1 | 实施例2 | 实施例3 | 对比例1 | 实施例4 | 实施例5 | 实施例6 | |
处理温度(℃) | 70 | 80 | 70 | N.T.* | 70 | 70 | 70 |
松弛率(%)MD/TD | 5/5 | 5/5 | 10/10 | - | 5/5 | 5/10 | 10/10 |
热收缩应 40℃力(MPa) 50℃ | 1.2/0.32.3/2.0 | 0.5/0.21.8/0.7 | 0.3/0.30.9/1.1 | 2.6/3.33.3/3.1 | 2.1/1.42.7/2.6 | 1.0/0.21.8/1.1 | 1.0/0.61.5/1.5 |
热水收缩率(%)MD/TD 90℃ | 32/35 | 27/32 | 27/33 | 33/36 | 28/33 | 28/32 | 27/31 |
干热收缩率120℃(%)MD/TD 160℃ | 20/2225/27 | 17/1920/22 | 16/1820/22 | 22/2428/30 | 21/2325/26 | 20/2124/23 | 17/1821/22 |
流体包装 | A | A | A | B | A | A | A |
煮沸试验 | A | A | A | C1 | A | A | A |
可印刷性 | A | A | A | C | A | A | A |
紧缩包装 | A | A | A | C1 | A | A | A |
*N.T.=未处理
表4:热处理条件和性能评价(2)
实施例7 | 实施例8 | 实施例9 | 实施例10 | 实施例11 | 对比例2 | 对比例3 | |
处理温度(℃) | 70 | 70 | 60 | 80 | 90 | N.T.* | 70 |
松弛率(%)MD/TD | 10/15 | 15/15 | 5/10 | 5/10 | 5/10 | - | 0/0 |
热收缩应 40℃力(MPa) 50℃ | 0.6/0.11.2/0.7 | 0.8/0.31.1/1.1 | 1.4/1.12.1/2.2 | 0.7/0.22.0/0.5 | 0.7/0.32.2/0.7 | 2.7/3.93.2/4.7 | 2.5/3.03.1/4.7 |
热水收缩率(%)MD/TD 90℃ | 27/31 | 25/32 | 30/33 | 27/33 | 25/26 | 31/36 | 30/34 |
干热收缩率120℃(%)MD/TD 160℃ | -/--/- | -/--/- | -/--/- | -/--/- | -/--/- | 23/2428/29 | 22/2226/27 |
流体包装 | A | A | A | A | A | B | B |
煮沸试验 | A | A | A | A | A | C1 | B |
可印刷性 | A | A | A | A | A | C | B |
紧缩包装 | - | - | - | - | - | C1 | B |
*N.T.=未处理
表5:热处理条件和性能评价(3)
实施例12 | 实施例13 | 实施例14 | 实施例15 | 实施例16 | 对比例4 | 对比例5 | |
处理温度(℃) | 70 | 70 | 65 | 60 | 70 | N.T.* | 60 |
松弛率(%)MD/TD | 5/5 | 10/10 | 5/5 | 5/10 | 10/10 | - | 5/5 |
热收缩应 40℃力(MPa) 50℃ | 1.2/1.52.0/2.6 | 1.1/0.61.8/1.3 | 1.3/0.62.5/1.8 | 1.9/1.32.4/1.9 | 0.6/0.21.3/0.7 | 3.0/4.43.4/5.0 | 2.9/2.53.4/3.2 |
热水收缩率(%)MD/TD 90℃ | 31/34 | 28/31 | 37/36 | 33/33 | 28/32 | 32/35 | 33/35 |
干热收缩率120℃(%)MD/TD 160℃ | 22/2526/29 | 17/2021/23 | 20/2325/28 | 23/2226/26 | 14/1920/23 | 24/2730/33 | 22/2526/29 |
流体包装 | A | A | A | A | A | B | A |
托盘包装 | A | A | A | A | A | C1 | B |
可印刷性 | A | A | A | B | A | C | B |
紧缩包装 | A | A | A | - | - | - | - |
成盖 | A | A | A | A | A | C | C |
皮杂饼包装 | A | A | A | A | A | C | C |
*N.T.=未处理
表6:热处理条件和性能评价(4)
实施例17 | 对比例6 | 实施例18 | 对比例7 | 实施例19 | 对比例8 | 实施例20 | |
处理温度(℃) | 70 | N.T.* | 70 | N.T.* | 70 | N.T.* | 70 |
松弛率(%)MD/TD | 5/5 | - | 5/5 | - | 5/15 | - | 5/15 |
热收缩应40℃力(MPa) 50℃ | 1.4/0.42.7/1.6 | 2.3/2.23.3/3.1 | 1.5/0.92.7/2.0 | 3.1/3.03.4/3.5 | 0.2/0.20.6/0.5 | 1.7/2.73.1/3.9 | 0.8/0.20.7/1.2 |
热水收缩率(%)MD/TD 90℃ | 36/39 | 39/42 | 39/40 | 42/43 | 26/22 | 29/32 | 24/26 |
流体包装 | A | B | A | B | - | - | - |
煮沸试验 | A | B | A | B | A | B | A |
托盘包装 | A | B | A | B | - | - | - |
可印刷性 | A | C | A | C | A | C | A |
*N.T.=未处理
表7:热处理条件和性能评价(5)
实施例21 | 实施例22 | 对比例9 | 对比例10 | 对比例11 | 对比例12 | |
处理温度(℃) | 70 | 70 | 70 | N.T.* | 70 | N.T.* |
松弛率(%)MD/TD | 10/10 | 5/5 | 10/10 | - | 10/10 | - |
热收缩应40℃力(MPa) 50℃ | 0.1/0.20.3/0.5 | 1.4/1.32.1/2.6 | 0.1/0.20.4/0.5 | 1.4/2.52.6/3.4 | 0.1/0.20.4/0.6 | 0.8/2.03.2/3.8 |
热水收缩率(%)MD/TD 90℃ | 22/25 | 28/34 | 18/19 | 25/28 | 17/18 | 24/26 |
煮沸试验 | A | A | C2 | A | C2 | A |
托盘包装 | - | - | C2 | - | C2 | - |
可印刷性 | A | A | A | C | A | C |
紧缩包装 | - | - | C2 | - | C2 | - |
*N.T.=未处理
[工业应用性]
如上所述,本发明提供了一种热收缩性多层薄膜,其防止了过大的热收缩应力的出现,同时确保必要程度的热收缩率,因而对各种自动包装工艺具有优异的适应性且具有良好的印刷性。
Claims (27)
1.一种热收缩性多层薄膜,包含至少三层,该至少三层包括含聚酯树脂的外表面层(a)、含聚酰胺树脂的中间层(b)和含可密封树脂的内表面层(c);所述多层薄膜在50℃下在纵向和横向的热收缩应力均为至多3MPa且在90℃下的热水收缩率为至少20%。
2.根据权利要求1的热收缩性多层薄膜,其中外表面层(a)的厚度小于中间层(c)。
3.根据权利要求1的热收缩性多层薄膜,在外表面层(a)和内表面层(c)之间还包括含阻气性树脂的中间层(d)。
4.根据权利要求1的热收缩性多层薄膜,其中外表面层(a)的聚酯树脂包括对苯二甲酸与至多具有10个碳原子的二醇之间的聚酯。
5.根据权利要求1的热收缩性多层薄膜,其中外表面层(a)的聚酯树脂包括乙二醇与包含主要量的对苯二甲酸和少量间苯二甲酸的二羧酸混合物之间的共聚酯。
6.根据权利要求1的热收缩性多层薄膜,其中外表面层(a)的聚酯树脂包括对苯二甲酸与包含主要量的乙二醇和少量1,4-环己烷二甲醇的二醇混合物之间的共聚酯。
7.根据权利要求1的热收缩性多层薄膜,其中中间层(b)的聚酰胺树脂包括脂族共聚酰胺。
8.根据权利要求1的热收缩性多层薄膜,其中内表面层(c)的可密封树脂包括乙烯共聚物或乙烯共聚物的酸改性产品。
9.根据权利要求8的热收缩性多层薄膜,其中乙烯共聚物包括主要量的乙烯与少量乙烯基单体的共聚物,所述乙烯基单体选自α-烯烃、不饱和羧酸和羧酸的不饱和酯。
10.根据权利要求1的热收缩性多层薄膜,其中可密封树脂包括选自如下的树脂:金属茂催化的线性低密度聚乙烯、金属茂催化的极低密度聚乙烯、线性低密度聚乙烯、线性极低密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸-不饱和羧酸共聚物和离聚物树脂。
11.根据权利要求3的热收缩性多层薄膜,其中阻气性树脂包括皂化的乙烯-乙酸乙烯酯共聚物。
12.根据权利要求1的热收缩性多层薄膜,还在外表面层(a)和内表面层(c)之间包括含有乙烯与含氧乙烯基单体的共聚物的中间层。
13.根据权利要求1的热收缩性多层薄膜,还在120℃下显示至少15%的干热收缩率。
14.根据权利要求1的热收缩性多层薄膜,还在外表面层(a)上具有印刷图案。
15.一种生产热收缩性多层薄膜的方法,包括如下步骤:共挤出至少三种熔化的热塑性树脂,形成包含至少三层的管状产品,该至少三层包括含聚酯树脂的外表面层(a)、含聚酰胺树脂的中间层(b)和含可密封树脂的内表面层(c),用水将管状产品冷却至低于构成层(a)、(b)和(c)的聚酯树脂、聚酰胺树脂和可密封树脂的熔点中最低之一的温度,将管状产品再加热到最多为构成层(a)、(b)和(c)的聚酯树脂、聚酰胺树脂和可密封树脂的熔点中最低之一的温度,在将流体引入管状产品中的同时垂直拉伸该管状产品,在垂直方向和圆周方向均以2.5-4倍的拉伸比拉伸该管状产品,从而提供双轴拉伸的管状薄膜,折叠该管状薄膜,再次将流体引入折叠的管状薄膜中以形成管状薄膜,用60-98℃的蒸汽或温水从管状薄膜的外表面层(a)热处理该管状薄膜,和冷却已热处理的管状薄膜以提供双轴拉伸薄膜,该双轴拉伸薄膜在50℃下的热收缩应力在纵向和横向均为至多3MPa,且在90℃下的热水收缩率为至少20%。
16.一种吹塑塑料容器,包含根据权利要求1-14中任一项的多层薄膜,呈吹塑管状形式。
17.一种包装产品,包含根据权利要求1-14中任一项的多层薄膜和被热收缩状态的多层薄膜包装的内容物。
18.根据权利要求17的包装产品,在外表面层(a)上具有印刷图案。
19.根据权利要求17的包装产品,其中所述多层薄膜已经用热水进行热收缩。
20.根据权利要求17的包装产品,其中所述多层薄膜已经用热气进行热收缩。
21.根据权利要求17的包装产品,其中内容物已经通过将放置在基础薄膜上的内容物用所述多层薄膜覆盖并将该多层薄膜与该基础薄膜在其中不存在内容物的该多层薄膜和基础薄膜的边缘部分热密封而进行紧缩包装。
22.根据权利要求17的包装产品,其中内容物已经通过将该内容物插入由所述多层薄膜形成的流体包装材料中并将该多层薄膜的边缘部分相互热密封而进行流体包装。
23.根据权利要求17的包装产品,其中内容物已经通过用所述多层薄膜将放置在托盘上的内容物包装并使多层薄膜热收缩而进行托盘包装。
24.根据权利要求17的包装产品,其中内容物已经通过将内容物放置在具有其中不存在内容物的周边边缘部分的树脂托盘上、用所述多层薄膜覆盖内容物和将多层薄膜与树脂托盘的边缘部分热密封而进行托盘包装。
25.根据权利要求17的包装产品,其中内容物包括食物。
26.根据权利要求25的包装产品,其中食物包括肉类。
27.根据权利要求25的包装产品,其中食物包括比萨饼。
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JP12975898A JP4495264B2 (ja) | 1998-04-24 | 1998-04-24 | 熱収縮性多層フィルム |
JP129758/1998 | 1998-04-24 |
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US (1) | US6699549B1 (zh) |
EP (1) | EP1084035B2 (zh) |
JP (1) | JP4495264B2 (zh) |
CN (1) | CN1172795C (zh) |
AT (1) | ATE299435T1 (zh) |
AU (1) | AU749877B2 (zh) |
BR (1) | BR9909881B1 (zh) |
DE (1) | DE69926125T3 (zh) |
DK (1) | DK1084035T3 (zh) |
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WO (1) | WO1999055528A1 (zh) |
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GB2617889B (en) | 2022-02-15 | 2024-08-14 | Flexopack Sa | Heat shrinkable film |
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CN115489057B (zh) * | 2022-11-07 | 2024-06-18 | 南通环球塑料工程有限公司 | 一种用于制备热收缩薄膜的吹胀拉伸装置 |
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US4188443A (en) | 1978-08-30 | 1980-02-12 | W. R. Grace & Co. | Multi-layer polyester/polyolefin shrink film |
JPS5924628A (ja) * | 1982-07-31 | 1984-02-08 | Dainippon Printing Co Ltd | 化粧シ−トの製造法 |
JP2714441B2 (ja) | 1989-06-12 | 1998-02-16 | 住友ベークライト株式会社 | 多層延伸フィルム |
JP2692294B2 (ja) * | 1989-09-19 | 1997-12-17 | ダイアホイルヘキスト株式会社 | ポリエステルフィルムの熱処理方法 |
JP2552946B2 (ja) * | 1990-08-20 | 1996-11-13 | 呉羽化学工業株式会社 | 2軸延伸積層フィルム |
US6150011A (en) † | 1994-12-16 | 2000-11-21 | Cryovac, Inc. | Multi-layer heat-shrinkage film with reduced shrink force, process for the manufacture thereof and packages comprising it |
US6146726A (en) * | 1996-05-28 | 2000-11-14 | Kureha Kagaku Koygo K.K. | Heat-shrinkable multi-layer film |
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1998
- 1998-04-24 JP JP12975898A patent/JP4495264B2/ja not_active Expired - Lifetime
-
1999
- 1999-04-22 AT AT99917109T patent/ATE299435T1/de not_active IP Right Cessation
- 1999-04-22 WO PCT/JP1999/002150 patent/WO1999055528A1/en active IP Right Grant
- 1999-04-22 DE DE69926125.2T patent/DE69926125T3/de not_active Expired - Lifetime
- 1999-04-22 AU AU35349/99A patent/AU749877B2/en not_active Expired
- 1999-04-22 CN CNB998054100A patent/CN1172795C/zh not_active Expired - Lifetime
- 1999-04-22 US US09/673,956 patent/US6699549B1/en not_active Expired - Lifetime
- 1999-04-22 BR BRPI9909881-4A patent/BR9909881B1/pt not_active IP Right Cessation
- 1999-04-22 ES ES99917109T patent/ES2245507T3/es not_active Expired - Lifetime
- 1999-04-22 DK DK99917109T patent/DK1084035T3/da active
- 1999-04-22 EP EP99917109.3A patent/EP1084035B2/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102909924A (zh) * | 2005-10-12 | 2013-02-06 | 埃克森美孚石油公司 | 可密封包装结构及其涉及的应用 |
CN102781666A (zh) * | 2010-01-08 | 2012-11-14 | 株式会社吴羽 | 用于深拉成形的热收缩性多层膜及其制造方法 |
CN102781666B (zh) * | 2010-01-08 | 2014-10-22 | 株式会社吴羽 | 用于深拉成形的热收缩性多层膜及其制造方法 |
CN104169083A (zh) * | 2011-12-15 | 2014-11-26 | 温德默勒&霍勒沙两合公司 | 用于在封口的薄膜包装内包装物品的薄膜产品 |
CN109831909A (zh) * | 2017-01-19 | 2019-05-31 | 株式会社吴羽 | 热收缩性多层膜 |
US11345124B2 (en) | 2017-01-19 | 2022-05-31 | Kureha Corporation | Heat-shrinkable multilayer film |
Also Published As
Publication number | Publication date |
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JPH11300914A (ja) | 1999-11-02 |
EP1084035A1 (en) | 2001-03-21 |
US6699549B1 (en) | 2004-03-02 |
BR9909881A (pt) | 2000-12-26 |
DK1084035T3 (da) | 2005-10-24 |
WO1999055528A1 (en) | 1999-11-04 |
ATE299435T1 (de) | 2005-07-15 |
AU3534999A (en) | 1999-11-16 |
DE69926125T2 (de) | 2006-05-11 |
BR9909881B1 (pt) | 2009-05-05 |
EP1084035B2 (en) | 2014-06-25 |
DE69926125T3 (de) | 2014-10-09 |
CN1300250A (zh) | 2001-06-20 |
ES2245507T3 (es) | 2006-01-01 |
DE69926125D1 (de) | 2005-08-18 |
JP4495264B2 (ja) | 2010-06-30 |
AU749877B2 (en) | 2002-07-04 |
EP1084035B1 (en) | 2005-07-13 |
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