CN104159744B - 可热封的尼龙薄膜和其制备方法 - Google Patents
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Abstract
一种复合薄膜,其包括尼龙底膜和包括一种或多种聚合物的粘合剂组合物的共延展层,其中所述一种或多种混合的聚合物以聚合形式包括:乙烯;一种或多种含酯单体,其占所述一种或多种聚合物的5‑50重量%;和一种或多种含羧酸单体和其任选的盐,其占所述一种或多种聚合物的0.5‑20重量%。一种制造的包装,其包括由所述复合薄膜制造的热封至托盘的盖子。一种由所述薄膜制造的袋子,其用于包装生的或处理过的肉。在所述包装或袋子中可以包含食物。
Description
背景技术
尼龙(聚酰胺)由于其优异的抗刺穿性而在包装领域被广泛使用。它们可以用于例如制造肉类或其它种类食物的抗刺穿袋子,但是用于制造袋子的方法通常涉及高温,尼龙薄膜通过此高温被焊接在一起以密封袋子。因此,尼龙薄膜不易被热封,特别是无法热封至其他基体上。
由于缺乏热封性,用于包装领域的尼龙薄膜通常被并入多层结构。通常,这些结构采用通过吹塑薄膜或挤压涂布的方式制备的乙烯(共)聚合物层。不幸地,所述方法易于形成相对厚的乙烯(共)聚合物层,并且能潜在地破坏复合薄膜的双法烘烤性能(dualovenability),因为乙烯共聚物通常不具有良好的热稳定性,并且也可能无法满足在双法烘烤烹饪领域使用的材料的提取需要(extraction requirement)。
尼龙薄膜曾一直用于制造储存和烹饪食物(特别是肉制品)用的袋子。由于缺乏好的密封性,所述袋子通常是通过在高温下将尼龙表面焊接在一起来制造的。这样的高温焊接通常会导致袋子有裂缝或小孔。由于低劣的密封性能,使用的袋子普遍是被三边密封的,并在填装了食物之后,用金属夹子闭合它们。食品加工人员之后则无法使用X射线或其他金属探测系统去探测食物中的异物。由于尼龙-尼龙焊接的高强度,通过焊接并且使用金属夹子制造的尼龙袋子在烹饪期间通常也不会自排气。
一个解决这些问题的潜在方法是通过溶液涂布,而不是吹塑薄膜或挤压成型,在尼龙上提供一层热封层。溶液涂布还使得到的涂层厚度范围较宽,这有利于剪裁其密封性能。然而,溶液涂布很难实施在尼龙基体上,因为已证明难于确定既能在尼龙上形成好的涂层同时还能给良好的热封性提供所需的粘合强度和内聚强度的组合物。因此,能够满足这些性能的组合物是具有商业价值的。
发明内容
一个方面,本发明提供一种复合薄膜,其包括尼龙底膜以及包含一种或多种聚合物的粘合剂组合物的共延展(coextensive)层,其中所述一种或多种混合在一起的聚合物以聚合形式包括:
a)乙烯;
b)一种或多种含酯单体,其占所述一种或多种聚合物的5-50重量%;和
c)一种或多种含羧酸单体和其任选的盐,其占所述一种或多种聚合物的0.5-20重量%。
另一方面,本发明提供一种包装,其包括由所述复合薄膜制造的盖子,其中所述盖子热封至托盘。
另一方面,本发明提供一种由所述复合薄膜制造的袋子,其适用于包装生的或处理过的肉。
另一方面,本发明提供一种包装食物的方法,其包括将本发明所述的复合薄膜热封至包含食物的托盘上。
另一方面,本发明提供一种包装食物的方法,其包括闭合由根据本发明所述的复合薄膜制造的袋子,其中所述袋子中包含食物。
发明详述
本发明提供一种通过溶液涂布在尼龙薄膜(包括可热成型的尼龙薄膜)上制造热封层的方法以及组合物。所得到的复合薄膜可以用于例如制造袋子,或托盘容器的盖子。特别地,它们可以制造适用于高温烹饪和食物重新加热的包装,例如带包装蒸煮肉的应用。
使用本发明所述的溶液涂布方法,可得到薄的热封涂层,而且例如当希望提供明确水平的剥离性能时,其密封强度也可以根据最终的使用需求而轻易剪裁。可得到厚度最多为15μm,或最多为10μm,或最多为5μm的涂层。这样的厚度很难或不可能通过常规的方法(例如层压、挤压涂布或复合挤压)得到。本发明者发现,带有由本发明所述复合薄膜制造的盖子的包装,以及由所述复合薄膜制造的袋子,在烤箱的烹饪周期中可以提供自排气能力。这个仅仅通过使用足够低的涂层厚度就可实现,其精确值取决于多个因素,包括涂层的具体构成和复合薄膜所热封的表面的具体构成。当达到足够高的温度时,通常在300°F(177℃)至450°F(204℃)的范围内,所得到的包装或袋子会排气。
粘合剂组合物
根据本发明所述的粘合剂组合物包括一种或多种聚合物,其中所述一种或多种混合的聚合物以聚合形式包括:
a)乙烯;
b)一种或多种含酯单体;和
c)一种或多种含羧酸单体和其任选存在的盐。
典型的含羧酸单体包括丙烯酸、甲基丙烯酸、马来酸和衣康酸。
典型的含酯单体包括乙酸乙烯酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯和/或其他的(甲基)丙烯酸烷基酯。在一些实施方式中,至少一部分含酯单体组分是聚丁二醇酯,例如聚丁二醇(甲基)丙烯酸酯。
已发现为了使粘合剂既具有足够的粘合强度又具有足够的内聚强度,以与尼龙薄膜有效粘合,同时还可以在常规的使用条件下进行有效的热封,对含羧酸单体和含酯单体的量的适当选择是很重要的。如果含羧酸单体的量太低,其与尼龙的粘合性会不好。然而,羧酸含量过量可能会导致适合热封形成的熔融起始温度过高,导致尼龙底膜在热封期间变形或基体变形。通过差示扫描量热法(DSC)测量到,常规粘合剂的熔融起始温度最高应为400°F。同时发现,酯含量过少会导致粘合剂层的内聚强度不足,含量过多会使熔融起始温度过低,导致粘合剂层很粘且很难掌控。
相应地,羧酸单体单元和其任选存在的盐通常占所混合的一种或多种聚合物的至少0.5重量%,或至少1重量%,或至少2重量%。它们通常占所述聚合物的至多20重量%,或至多10重量%,或至多7重量%,或至多5重量%。此处,羧酸单体单元和它们的盐的重量百分比是基于自由的、未中和的酸计算的。如果有中和羧酸单体单元的抗衡离子(例如盐)存在,其可以是任何形式的。典型的盐可以包括金属盐,例如钠盐或钾盐、或铵盐、或胺盐、或它们的结合。在本发明的一些实施方式中,少于50摩尔%、或少于30摩尔%、或少于20摩尔%、或少于10摩尔%、或少于5摩尔%的羧酸基团是以金属盐的形式存在。在本发明的一些实施方案中,少于50摩尔%、或少于30摩尔%、或少于20摩尔%、或少于10摩尔%、或少于5摩尔%的羧酸基团是以任何种类的盐的形式存在。在一些实施方案中,羧酸不以盐的形式存在。优选地,不含有阴离子表面活性剂。
在本发明的一些实施方案中,令人满意的粘合剂组合物中的聚合物不包含含有磺酸和/或膦酸和/或其盐的单体单元。
含酯单体通占所混合的一种或多种聚合物的至少5重量%、或至少10重量%、或至少15重量%的。它们通常占所述聚合物的至多50重量%、或至多40重量%、或至多30重量%。
在一些实施方式中,所有的乙烯、含酯单体单元和含羧酸单体单元在同一聚合物中。或者,所述粘合剂可以包括两种(或多种)聚合物,例如乙烯乙酸乙烯酯(“EVA”)共聚物和乙烯(甲基)丙烯酸(“E(M)AA”)共聚物。适宜的EVA共聚物可以以聚合形式包含任何相对量的乙烯和乙酸乙烯酯。通常地,所述EVA将含有至少5重量%、或至少15重量%含量的乙酸乙烯酯。通常地,所述乙酸乙烯酯的含量至多为35重量%或至多为25重量%。
适宜的E(M)AA共聚物可以以聚合形式含有任何相对量的乙烯和(甲基)丙烯酸。通常地,(甲基)丙烯酸的含量至少2重量%、或至少5重量%、和至多20重量%、或至多15重量%、或至多10重量%。所述的(甲基)丙烯酸可以由丙烯酸组成,或其可以由甲基丙烯酸或它们的结合组成。在一些EVA和E(M)AA用作粘合剂聚合物的实施方案中,EVA和E(M)AA的重量比可以至少为20:80、或至少为30:70、或至少为40:60。在那些相同的实施方式中,所述重量比至多可以为80:20、或至多为70:30、或至多为60:40。
在本发明的一些实施方式中,粘合剂还包括增粘剂。通常地,所述增粘剂在每100份的聚合物中以至少1份、或至少3份、或至少5份的水平存在。通常地,在每100份的聚合物中,所述量至多为30份、或至多20份、或至多15份。
可以使用任何现有技术中已知的增粘剂,例如第3,484,405号美国专利所公开的。这些增粘剂包括各种天然的或合成的树脂和松香材料,并且可以给组合物提供大量且有改进的粘性。增粘剂可以是液体、半固体到固体、或者固体,通常包括以有机化合物的混合物形式存在的复合无定形材料,所述无定形材料没有明确的熔点,也没由结晶的倾向。这样的增粘剂树脂在水中不可溶,且可以来源于植物或动物,或可以是合成树脂。适宜的增粘剂包括但不仅限于,对-香豆酮-茚树脂、萜烯树脂、丁苯树脂、聚丁二烯树脂、烃类树脂、松香以及其两种或多种的组合。
通常香豆酮-茚树脂的分子量在500-5000范围内。典型的此类树脂可以从EastmanChemical,Kingsport,TN以A100购得。
所述萜烯树脂包括苯乙烯化萜烯,且其分子量在600-6000范围内。可商购树脂的例子是以S-100(Pinova,Brunswick,GA)销售的。典型基于萜烯树脂的增粘剂可衍生自聚柠檬烯,并以C115获得。
低分子量(例如大约1300)的苯乙烯硬树脂也是适宜的,例如由Eastman Chemical以销售的产品。适宜的松香基树脂可以从树胶、木材或塔罗油松香中提取。所述增粘剂可以基于改性的松香,例如二聚松香、氢化松香、歧化松香、或松香酯,通常由含有2-6个羟基的多羟基醇与松香酯化来制备。典型的松香基增粘剂是氢化松香的甘油酯,其由Eastman Chemical以STAYBELITE#10商业销售。
本发明所述的粘合剂组分中还可以包括其他的添加剂,例如防粘连添加剂,如蜡。一种适宜的防粘连添加剂是芥酸酰胺。
一种适宜的粘合剂组合物包括下列组分,以固体为基准记录。该组合物可以在含有少量氨的水中分散,其固体含量大约在35重量%。在所述组合物中,丙烯酸占乙烯丙烯酸(EAA)和乙烯乙酸乙烯酯(EVA)结合的共聚物的大约3重量%,且乙酸乙烯酯占大约20重量%。
14%EAA共聚物,AA含量15-20重量%
63%EVA共聚物,VA含量24重量%
21%氢化松香酯增粘剂树脂
2%邻苯二甲酸二辛脂增塑剂,硬脂酰胺助滑添加剂,BHT抗氧化剂含有近似该组合物的粘合剂(作为35%的固体分散体),可以由Dow Chemical(Midland MI)以商品名ADCOTETM37T77E分散体获得。
尼龙基体
通常来说,适宜的尼龙基体可以是任何的尼龙或尼龙混合物。其可包括少量和尼龙相配的聚合物和添加剂。对于那些复合薄膜经受的温度仅高达220°F的应用,任何尼龙都具有足够的热稳定性,用耐热性以外的标准选择最理想的尼龙组合物。
对于那些复合薄膜将要经受甑式温度(retort-type temperatures)的应用,例如高达275°F,选择合适的尼龙聚合物多少有些限制,因为不是所有尼龙都可以抵挡所述工艺条件。适合用于此类条件的典型尼龙包括尼龙6、尼龙66、尼龙6/66共聚物、尼龙11、以及尼龙6和尼龙11的混合物。在一些适宜的尼龙混合物中,例如可热成型的混合物,可包含高达25重量%的尼龙12。在本发明的一些实施方案中,可以使用现有技术已知的例如溶液或挤压涂布的方式将聚偏二氯乙烯层施加于尼龙层。通常地,所述层随着尼龙层共延展,即形状和尺寸与整个尼龙薄膜表面相等。在尼龙和热封层之间或在热封层的对面提供这样的层可以提高对于水分和氧气的阻隔性能。
粘合剂组合物的涂布
所述的粘合剂组合物以水分散体被涂布,通常使用氨或挥发性胺来帮助其溶解和/或分散含羧酸粘合剂树脂。涂布可通过任何现有技术已知的涂布方法实施,例如使用迈尔棒(Myer rod)、传递凹印辊涂布机或刮板,随后干燥。在一些实施方案中,热封层随着尼龙薄膜共延展。
使用复合薄膜的包装
本发明还提供一种包装,其包括由本发明所述复合薄膜制造的盖子,所述盖子热封至底部(例如托盘)。通常在包装领域使用的典型托盘材料包括热成型聚酯、无定形PET、冲击改性PET、聚丙烯和聚苯乙烯。在其他的实施方案中,所述复合薄膜可以成型为袋子,例如用于包装生的或处理过的肉。
实施例
尼龙6,6薄膜上的粘合剂涂层
评价九种粘合剂组合物,每一种组合物被涂布至尼龙6,6薄膜上面,干燥并评价其热封强度。组合物的大致组分如下所示,其通过分析法和商业文献相结合而确定。
ADCOTETM37T77E-基于高分子量乙烯共聚物的水基分散体,其含有近似如上所述的组成。
2009-不含羧酸单体单元的EVA共聚物,其可由Paramelt BV,Costerstraat 18,P.O.Box 86,NL-1700AB Heerhugowaard商购获得。
Emulsion D791-乙酸盐含量大约为24重量%的EVA共聚物和EAA共聚物分散体,其可由Michelman,Inc.of Cincinnati,OH商购获得。
Emulsion D796-包括乙烯、含羧酸单体和丙烯酸甲酯的共聚物的阴离子分散体,其中丙烯酸甲酯的含量大约为20重量%。
Emulsion D797-包括乙烯、含羧酸单体和丙烯酸酯的共聚物的阴离子分散体,其中丙烯酸丁酯的含量大约为22重量%。
Emulsion D970-不含酯或羧酸单体单元的阴离子聚烯烃分散体。
2045-乙烯/甲基丙烯酸共聚物的金属盐,其中甲基丙烯酸的含量为20%,可由Paramelt BV获得。
2200-含有高含量聚丙烯且不含酯或羧酸单体单元的聚乙烯共聚物,其可由Paramelt BV获得。
2105-不含酯单体单元的EAA共聚物,其可由Paramelt BV获得。
ADCOTETM37T77E通常的涂布方法描述如下,其他涂层的涂布是类似的。
加入去离子水并搅拌,由此将ADCOTETM37T77E分散体(35%固体,来自DowChemicals)稀释至25%固体。使用4号迈尔棒将该溶液涂布至1mil厚的尼龙6,6薄膜上(N201,得自Exopack)。将湿的涂层置于180℃的烤箱中30秒钟以干燥。所得到薄膜的干涂层厚度为9微米。
热封强度的测量
使用Sentinel热封机(来自Packaging Industries Group Inc.的Model 12)将一半A4薄片大的、经涂布的尼龙薄膜自密封(涂布面对涂布面)。所述热封机的参数为:150℃(顶部夹板),40℃(底部夹板)/1秒/80psi。标记热封样品,并将其切成25mm宽的条,折叠部分被撕裂,然后通过 model4464测试机器上的剥离强度实验测量其热封强度。所述夹板被设置相隔50mm的距离。顶部夹板夹住一片密封样品,并以250mm/分钟的速度移动,同时底部夹板夹住另一片密封样品静止不动。记录分离两片薄膜所需的最大力。九种涂布样品中的每种都有五个密封样品被测试。所得结果如表1所示。
表1
*对比实施例
列在上面的对比实施例的组合物中没有酯单体单元和/或羧酸单体存在,然而本发明所述实施例,在分散体中存在的聚合物里随着乙烯同时包括这两种单体单元。可以看出,根据本发明所述薄膜测得的剥离强度明显大于对比例的。
尽管在此结合具体实施方式阐明和描述了本发明,所示的细节不意味着对本发明的限制。相反,在不背离本发明的情况下,可以在权利要求等效的范畴和范围内在细节上做各种修改。
Claims (17)
1.一种复合薄膜,其包括尼龙底膜和包括一种或多种聚合物的粘合剂组合物的共延展层,其中所述一种或多种合在一起的聚合物以聚合形式包括:
a)乙烯;
b)一种或多种含酯单体,其占所述一种或多种聚合物的5-50重量%;和
c)一种或多种含羧酸单体和任选存在的该羧酸的盐,其占所述一种或多种聚合物的0.5-20重量%;
其中所述粘合剂组合物的共延展层直接置于所述尼龙底膜的表面上。
2.根据权利要求1所述的复合薄膜,其中所述一种或多种含羧酸单体和任选存在的该羧酸的盐占所述一种或多种聚合物的2-5重量%。
3.根据权利要求1或2所述的复合薄膜,其中所述一种或多种含酯单体占所述一种或多种聚合物的15-30重量%。
4.根据权利要求1或2所述的复合薄膜,其中所述一种或多种聚合物包括:
a)乙烯-乙酸乙烯酯共聚物,其中乙酸乙烯酯的含量为5-35重量%;和
b)乙烯(甲基)丙烯酸共聚物和任选存在的其盐,其中(甲基)丙烯酸的含量为2-15重量%。
5.根据权利要求4所述的复合薄膜,其中乙酸乙烯酯的含量为15-25重量%。
6.根据权利要求4所述的复合薄膜,其中所述(甲基)丙烯酸和任选存在的其盐的含量为5-15重量%。
7.根据权利要求1或2所述的复合薄膜,其中少于50摩尔%的羧酸根是以其金属盐的形式存在。
8.根据权利要求1或2所述的复合薄膜,其中每100份所述一种或多种聚合物总重中,所述粘合剂组合物还包括1-30份的增粘剂。
9.根据权利要求8所述的复合薄膜,其中所述增粘剂是松香基增粘剂。
10.根据权利要求1或2所述的复合薄膜,其中所述粘合剂组合物还包括防粘连添加剂。
11.根据权利要求1或2所述的复合薄膜,其中还包括聚氯乙烯层。
12.一种包装,其包括由权利要求1至11任意一项所述的复合薄膜制造的盖子,其中所述盖子被热封至托盘。
13.根据权利要求12所述的包装,其中所述包装能够在烹饪周期中自排气。
14.一种袋子,其由根据权利要求1至11任意一项所述的复合薄膜制造,适用于包装生的或加工过的肉类。
15.根据权利要求14所述的袋子,其中所述袋子能够在烹饪周期中自排气。
16.一种包装食物的方法,其包括将根据权利要求1至11中任意一项所述的复合薄膜热封至包含食物的托盘上。
17.一种包装食物的方法,其包括通过热密封闭合由根据权利要求1至11中任意一项所述的复合薄膜制造的袋子,其中所述袋子中包含食物。
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- 2013-03-06 EP EP13712007.7A patent/EP2822763A2/en not_active Withdrawn
- 2013-03-06 WO PCT/US2013/029254 patent/WO2013134335A2/en active Application Filing
- 2013-03-06 JP JP2014561063A patent/JP6359975B2/ja not_active Expired - Fee Related
- 2013-03-06 CN CN201380012139.1A patent/CN104159744B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO2013134335A2 (en) | 2013-09-12 |
EP2822763A2 (en) | 2015-01-14 |
KR20140138869A (ko) | 2014-12-04 |
CN104159744A (zh) | 2014-11-19 |
WO2013134335A3 (en) | 2013-11-21 |
JP2015516312A (ja) | 2015-06-11 |
JP6359975B2 (ja) | 2018-07-18 |
US20150044403A1 (en) | 2015-02-12 |
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