CN101489787B - 非对称多层聚合物膜和标签材料及其标签 - Google Patents

非对称多层聚合物膜和标签材料及其标签 Download PDF

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CN101489787B
CN101489787B CN2007800269158A CN200780026915A CN101489787B CN 101489787 B CN101489787 B CN 101489787B CN 2007800269158 A CN2007800269158 A CN 2007800269158A CN 200780026915 A CN200780026915 A CN 200780026915A CN 101489787 B CN101489787 B CN 101489787B
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film
layer
top layer
polyethylene
polypropylene
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CN101489787A (zh
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C·J·布莱克威尔
K·O·海德森
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Avery Dennison Corp
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Abstract

用于给物品作标记的聚合物膜包括非对称多层膜,其包括特定表层和芯层,其组成解决了包括印刷油墨和粘合剂的粘合以及冲切性能(die-cuttability)在内的多种需要。该聚合物膜在向含有粘合剂的标签材料和粘合标签的转化方面提供了改进的性能。

Description

非对称多层聚合物膜和标签材料及其标签
相关申请的交叉参考
本申请要求在2006年7月17日提交的美国临时申请号60/807,554的权益。
技术领域
本发明涉及用于给物品作标记的非对称多层聚合物膜,并且进一步涉及包括所述聚合物膜在内的含有粘合剂的标签材料和粘合标签。
技术背景
粘合标签在给商业物品作标记方面具有广泛的应用,包括各种消费者和工业产品所用的塑料、纸、金属和玻璃容器。由于粘合标签的这种广泛应用,粘合标签的使用性能方面和/或制备粘合标签的加工方面的提高是有益的。
发明内容
在一种实施方式中,本发明涉及用于给物品作标记的非对称多层聚合物膜,其包括(A)印刷表层,其具有上表面和下表面并且包括至少一种聚乙烯——密度高达0.94g/cm3——以及至少一种聚丙烯;(B)芯层,其具有上表面和下表面并且包括至少一种聚丙烯共聚物、至少一种聚丙烯均聚物以及至少一种聚乙烯,其通过齐格勒-纳塔(Ziegler-Natta)或茂金属催化制备并且具有从0.86至0.98g/cm3的密度;和(c)粘合表层,其具有上表面和下表面并且包括至少一种接枝有不饱和羧酸或不饱和羧酸衍生物的聚烯烃,其中印刷表层(A)的下表面位于芯层(B)的上表面之上,并且粘合表层(C)的上表面位于芯层(B)的下表面之下。
在另一种实施方式中,粘合表层(a)还包括至少一种聚丙烯均聚物。
在本发明的另一种实施方式中,多层聚合物膜进一步包括(D)接合层(tie layer),其具有上表面和下表面并且包括至少一种聚丙烯共聚物、至少一种聚丙烯均聚物以及至少一种聚乙烯,其通过齐格勒-纳塔或茂金属催化制备并且具有从0.86至0.98g/cm3的密度,其中接合层的上表面与印刷表层(A)的下表面接触并且接合层的下表面与芯层(B)的上表面接触,并且芯层(B)进一步包括再生膜。
在本发明的另一种实施方式中,含有粘合剂的标签材料包括多层聚合物膜——所述多层聚合物膜包括层(A)、(D)、(B)、(C)和(E)粘合层,所述粘合层具有上表面和下表面,其中粘合层的上表面粘附地结合于该膜的粘合表层(C)的下表面。
本发明进一步的实施方式是粘合标签,其是从含有粘合剂的标签材料中冲切的,其中该标签材料包括聚合物膜——所述聚合物膜包括层(A)、(D)、(B)、(C),粘合层(E),和剥离衬垫(F),其中剥离衬垫可剥离地结合于粘合层(E)的下表面,并且粘合层(E)是压敏粘合层。
本发明的多层聚合物膜已经发现由于该膜的非对称层结构改进了粘合标签的使用性能以及制备包括该聚合物膜的粘合标签的工艺。
附图说明
图1是本发明的聚合物膜的横截面图,该聚合物膜包括三层。
图2是本发明的聚合物膜的横截面图,该聚合物膜包括四层。
图3是本发明的含有粘合剂的标签材料的横截面图。
具体实施方式
在本发明的一种实施方式中,多层聚合物膜包括(A)印刷表层,其具有上表面和下表面;(B)芯层,其具有上表面和下表面;和(c)粘合表层,其具有上表面和下表面,其中印刷表层(A)的下表面位于芯层(B)的上表面之上,并且粘合表层(C)的上表面位于芯层(B)的下表面之下。在本发明的另一种实施方式中,包括层(A)、(B)和(C)的聚合物膜进一步包括(D)接合层,其具有上表面和下表面,其中接合层的上表面与印刷表层(A)的下表面接触并且接合层的下表面与芯层(B)的上表面接触。术语“在……之上(overlie)”和“在……之下(underlie)”是指在第二层之上或之下的第一层可部分或完全覆盖第二层,并且第一层可与第二层直接接触或者一个或多个中间层可位于第一层和第二层之间。如本文所用的术语“非对称”是指多层膜的每一层的组成是不同的。
(A)印刷表层
印刷表层(A)包括至少一种聚乙稀(PE)和至少一种聚丙烯(PP)。该聚乙烯包括这样的聚乙烯,其密度高达约0.94g/cm3,或者约0.86或0.87至约0.94g/cm3。该聚乙烯可包括极低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)、线型低密度聚乙烯(LLDPE)、中密度聚乙烯(MDPE)、或任何前述聚乙烯的混合物。聚乙烯的混合物可以包括两种或多种同类型的聚乙烯,诸如举例来说两种线型低密度聚乙烯的混合物,或者可以包括两种或多种取自两种或多种不同类型的聚乙烯,诸如举例来说LLDPE和MDPE的混合物。VLDPE一般具有从0.88至0.915g/cm3的密度并且可以包括从乙烯和具有3至20个碳原子的α-烯烃共聚单体经过茂金属或齐格勒-纳塔(Z-N)催化制备的聚乙烯共聚物,其中共聚单体含量为4至25摩尔百分数以上。一般而言,茂金属催化剂相比Z-N催化剂在该聚合物中给出更均匀的支化和更大的均一性。LDPE一般具有从0.86或0.87至0.935的密度并且可包括聚乙烯共聚物,来自乙烯和一种或多种C3-C20α-烯烃共聚单体的聚乙烯共聚物,或者任何前述聚合物的混合物,其中LDPE是采用自由基催化高压下制备的。LDPE具有短链和长链分支。LLDPE一般具有从0.86或0.87至0.93g/cm3的密度并且可包括借助Z-N或茂金属催化从乙烯和一种或多种C3-C20α-烯烃共聚单体制备的聚乙烯共聚物,其中共聚单体含量为2.5至3.5摩尔百分数。LLDPE具有短链分支。MDPE一般具有0.925至0.94g/cm3的密度并且可包括借助Z-N或茂金属催化从乙烯和一种或多种C3-C20α-烯烃共聚单体制备的聚乙烯共聚物,其中共聚单体含量为1-2摩尔百分数。在本发明的实施方式中,印刷表层(A)包括来自齐格勒-纳塔催化的低粘度LLDPE和来自茂金属催化的LLDPE。来自Z-N催化的低粘度LLDPE可具有3-40、5-30或7-20的熔体指数,熔体指数是在190℃/2.16kg以g/10min为单位通过ASTM方法测量的。本文上述聚乙烯可从树脂供应商诸如DowChemical Co.和Exxon-Mobil Chemical Co.得到。有用的Z-N聚乙烯的特定实例包括来自Dow的Dowlex 2517;来自Huntsman的ChevronPhillips的L2101或L8148(熔体指数0.9)以及Marflex 7105DL(熔体指数0.5)。Dowlex 2517的密度为0.917g/cc且熔体指数25g/10min,并且L2101的熔体指数为24g/10min。茂金属催化的LLDPE的实例包括Exxon-Mobil EXACT 4049,(密度0.873g/cc且熔体指数4.5g/10min);Dow AFFINITY 8200G(密度0.870g/cc)以及AFFINITY KC8852(熔体指数3.0)。
印刷表层(A)还包括至少一种聚丙烯,其在一种实施方式中,具有1-40、2-30或4-20的熔体指数,熔体指数是在230℃/2.16kg以g/10min为单位通过ASTM方法D1238测量的。该聚丙烯可包括聚丙烯均聚物、聚丙烯共聚物或者任何前述聚合物的混合物。该聚丙烯可采用Z-N或茂金属催化剂制备。
许多有用的丙烯均聚物可从各种来源商业得到。一些有用的均聚物被列出,并描述在下表I中。表I商业丙烯均聚物商品                            熔体流动性  密度名称            公司            g/10min     (g/cm 3 )5390N           Dow Chemical    12.0        0.90SE66R           Dow Chemical    8.8         0.90H7010           Dow Chemical    12          NA3622            Atofina         12.0        0.903576X           Atofina         9.0         0.90Moplen HP400N   Basell          12.0        0.90P4G4K-038*      Huntsman        12          0.90P464K-173X*    Huntsman        12    0.909074*MED       Exxon Mobil     14    0.90*含有成核剂
在另一种实施方式中,该聚丙烯可以是丙烯共聚物,并且该丙烯共聚物包括丙烯和按重量计高达约40%的至少一种α-烯烃的聚合物,所述α-烯烃选自乙烯以及含有4至约12或者4至约8个碳原子的α-烯烃。有用的α-烯烃的实例包括乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯和1-辛烯。在一种实施方式中,用在本发明中的丙烯的聚合物包括丙烯与乙烯、1-丁烯、1-己烯或1-辛烯的聚合物。用在本发明中的丙烯α-烯烃聚合物包括无规共聚物以及嵌段共聚物,尽管无规共聚物一般而言是特别有用的。在一种实施方式中,该膜不含耐冲击共聚物。可以使用两种或多种丙烯共聚物的混合物以及丙烯共聚物与丙烯均聚物的混合物。
在一种实施方式中,丙烯共聚物是丙烯-乙烯共聚物,其中乙烯含量按重量计从约0.2%至约10%。在另一种实施方式中,乙烯含量按重量计从约3%至约10%,或者按重量计从约3%至约6%。关于丙烯-1-丁烯共聚物,按重量计高达约15%的1-丁烯含量是有用的。在一种实施方式中,1-丁烯含量一般可在按重量计约3%至约按重量计15%的范围内,并且在其它实施方式中,该范围为按重量计从约5%至约15%。丙烯-1-己烯共聚物可包含按重量计高达约35%的1-己烯。在一种实施方式中,1-己烯的量按重量计高达约25%。用在本发明中的丙烯-1-辛烯共聚物可含有按重量计高达约40%的1-辛烯。更经常地,丙烯-1-辛烯共聚物将含有按重量计高达约20%的1-辛烯。
用于制备本发明的膜面料的丙烯共聚物可通过本领域技术人员熟知的技术制备,并且许多这类共聚物是商业上可得到的。举例来说,用在本发明中的共聚物可采用单(活性)中心茂金属催化剂通过丙烯与α-烯烃例如乙烯或1-丁烯共聚而获得。
一些有用的商业上可得到的丙烯共聚物的列表见下表II。表II商业丙烯共聚物
  商业名称   来源   %乙烯   %1-丁烯   熔体流动速度(g/10min)   密度(g/cm3)
  DS4D05   Dow Chemical   ----   14   6.5   0.890
  DS6D20   Dow Chemical   3.2   ----   1.9   0.890
  DS6D81   Dow Chemical   5.5   ----   5.0   0.90
  SR4-189   Dow Chemical   ----   8   5.7   0.90
  P5M2K-070X   Huntsman   3.2   ----   ----   0.90
  TR3120C   Sunoco   NA   ----   12   NA
  R771-10N   Dow Chemical   NA   ----   10   NA
在一种实施方式中,基于重量,印刷表层包括约60%至约90%的至少一种聚乙烯以及约10%至约40%的至少一种聚丙烯。在另一种实施方式中,印刷表层包括约70%至约90%的至少一种聚乙烯以及约10%至约30%的至少一种聚丙烯。在另一种实施方式中,印刷表层包括约37-53%的低粘度ZN LLDPE、约23-37%的茂金属LLDPE和约10-40%的丙烯均聚物。
印刷表层(A)可进一步包括一种或多种额外的热塑性聚合物。一种或多种额外的热塑性聚合物可包括除了聚乙烯和聚丙烯之外的聚烯烃,烯烃-不饱和羧酸或不饱和羧酸衍生物共聚物,苯乙烯基聚合物或共聚物,聚氨酯,聚氯乙烯,聚碳酸酯,聚酰胺,氟塑料,聚(甲基)丙烯酸酯,聚丙烯腈,聚酯,或者任何前述聚合物的混合物。
印刷表层(A)可进一步包括一种或多种添加剂,如美国专利号6821592中所述。一种或多种添加剂可包括成核剂、防结快剂、加工助剂、润滑剂、抗静电剂、颜料、空化剂、无机填料、抗氧化剂或者任何前述添加剂的混合物。
在一种实施方式中,聚丙烯可以成核并且它们可含有一种或多种成核剂。在特别有用的实施方式中,成核剂被掺入到丙烯聚合物中。各种成核剂可被混合到本发明的膜制剂中,并且加入的成核剂的量应当是这样的量,其足以提供晶体结构期望的改进而对该膜期望的光学特性没有不利影响。一般期望的是,利用成核剂改进晶体结构并且提供大量显著更小的晶体或球粒以提高该膜的透明度(清晰度)。向膜制剂中加入的成核剂的量不应当对该膜的清晰度具有有害影响。混合到本发明膜制剂中的成核剂的量一般十分小并且在约500ppm以上、约750ppm以上或约850ppm以上。成核剂可以以高达约5000的量存在,或者高达约3000,或者高达约1000。
至今已经用于聚合物膜的成核剂包括矿物成核剂和有机成核剂。矿物成核剂的实例包括炭黑、硅石、高岭土和滑石。已经提出用于聚烯烃膜的有机成核剂之中包括脂肪族一元或二元酸或芳基烷基酸的盐,例如琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、苯乙酸铝和肉桂酸钠。芳香族和脂环族羧酸的碱金属和铝盐例如苯甲酸铝、苯甲酸钠或钾、β-萘酚钠、苯甲酸锂和叔丁基苯甲酸铝业也是有用的有机成核剂。Wijga在美国专利号3,207,735、3,207,736和3,207,738以及Wales在美国专利号3,207,737和3,207,739——全部在1966年9月21日取得专利权——提出脂肪族、脂环族和芳香族羧酸、二元羧酸和更高级多元羧酸、相应的酸酐和金属盐是聚烯烃有效的成核剂。它们进一步描述,苯甲酸类化合物尤其是苯甲酸钠是成核剂的最佳实施方式。
在一种实施方式中,成核剂是山梨糖醇衍生物或有机磷酸盐。取代的山梨糖醇衍生物是有用的成核剂,例如双(亚苄基)和双(烷基亚苄基)山梨糖醇,其中烷基含有约2至约18个碳原子。更具体地,山梨糖醇衍生物例如1,3,2,4-二亚苄基山梨糖醇和1,3,2,4-二对甲基亚苄基山梨糖醇对聚丙烯来说是有效的成核剂。有用的成核剂可从许多来源商业上得到的。Millad 8C-41-10、Millad 3988和Millad 3905是可从Milliken Chemical Co.得到的山梨糖醇成核剂。
山梨糖醇和木糖醇的其它缩醛也是聚烯烃和其它热塑料的典型成核剂。二亚苄基山梨糖醇(DBS)是由Hamada等首先作为聚烯烃有效的成核剂和澄清剂公开在美国专利号4,016,118中。自从那时起,大量山梨糖醇和木糖醇的缩醛已经被公开。代表性的美国专利包括Kawai等关于二(烷基亚苄基)山梨糖醇的美国专利号4,314,039;Mahaffey,Jr.关于具有至少一个氯或溴取代基的山梨糖醇二缩醛的美国专利号4,371,645;Kobayashi等关于二(甲基或乙基取代的亚苄基)山梨糖醇的美国专利号4,532,280;Rekers关于包括形成碳环的取代基的双(3,4-烷基亚苄基)山梨糖醇。这些专利在此被并入作为参考。
另一类成核剂由Nakahara等描述在美国专利号4,463,113中,其中环族双酚磷酸盐被作为聚烯烃树脂的成核剂和澄清剂公开。Kimura等然后在美国专利号5,342,868中描述向环族有机磷酯的碱性多价金属盐中加入碱金属羧酸盐可进一步提高这类添加剂的澄清效果。基于该项技术的化合物以商标名称NA-11和NA-21销售。这些专利在此被并入作为参考。
成核剂一般作为从树脂供应商得到的热塑性聚合物的部分引入到该膜的层中。在本发明的几种实施方式中,成核剂存在于该膜的一层中,所述膜可包括芯层或者表层中的一层,或者存在于该膜的两层或多层的任意组合中。
防结块剂可在热塑性聚合物基质中包括按重量计约3至80%的无机矿物或有机化合物的浓缩物,诸如举例来说在聚烯烃基质中按重量计5%的无定形硅石。在另一实例中,防结块剂可在聚烯烃中包括约2%至10%的丙烯酸酯聚合物。这类防结块剂的实例是Ampacet401960,其包括在丙烯均聚物中按重量计约5%的聚甲基丙烯酸甲酯(PMMA)。在一种实施方式中,该表层可包含约1至约10%的防结块剂。在另一实施方式中,防结块剂可以按重量计以约100至10,000、200至5,000或300至1,000ppm存在于本发明聚合物膜的一层或多层中,基于所述层的重量。防结块剂以及润滑剂、加工助剂和抗静电剂由于表面特性提供了膜和派生的标签的性能上的改进。因此当存在于膜中时,这些添加剂一般存在于所述表层之一或两者中。
颜料可包括无机颜料,其包括二氧化钛、碳酸钙、滑石、氧化铁、炭黑或任何前述无机颜料的混合物;有机颜料;或任何前述颜料的混合物。颜料可在热塑性基质中包括按重量计约20至80%的无机颜料和/或有机颜料浓缩物。该颜料浓缩物可按重量计以约0.5至20%存在于本发明聚合物膜的一层或多层中,基于所述层的重量,以提供给膜色彩和/或使膜变得不透明。不透明膜将一般具有至少70%、至少75%或至少80%的不透明度。该颜料浓缩物当存在于膜中时一般在芯层中。
在本发明的一种实施方式中,印刷表层(A)基于重量包括35-55%的低粘度Z-N LLDPE、20-40%的茂金属LLDPE、10-30%的聚丙烯均聚物和1-10%的防结块浓缩物。
在本发明膜的印刷表层(A)中的聚乙烯-聚丙烯掺合物提供这样的表面,所述表面对于派生的标签来说具有耐磨性并且能接纳多种印刷技术,包括UV固化的墨水、水基墨水、溶剂基墨水、热转移墨水和烫印。印刷墨水将粘附于印刷表层(A)的表面上,无需特别的涂敷以使得墨水粘附,尽管特别的涂敷可以被施用以进一步增加性能。
(B)芯层
芯层包括至少一种聚丙烯共聚物、至少一种聚丙烯均聚物以及至少一种聚乙烯,其通过齐格勒-纳塔或茂金属催化制备并且具有从0.86或0.87至0.98g/cm3的密度。聚丙烯共聚物和均聚物可包括在印刷表层(A)部分如上述的聚丙烯。聚丙烯共聚物可包括按重量计含有1-7%α-烯烃共聚单体的聚丙烯无规共聚物,所述α-烯烃包含乙烯和C4-C20α-烯烃,其中该共聚物一般用Z-N催化剂制备。在本发明的另一种实施方式中,芯层包括聚丙烯无规共聚物和聚丙烯均聚物、或者成核的聚丙烯无规共聚物和聚丙烯均聚物,其中聚丙烯无规共聚物的共聚单体是乙烯。
在芯层中所用的聚乙烯可包括这样的聚乙烯,其通过齐格勒-纳塔或茂金属催化而制备并且具有从0.86或0.87至0.98g/cm3的密度。在另一种实施方式中,在芯层中所用的聚乙烯具有从约0.87至约0.92的密度。芯层的聚乙烯可包括LLDPE、MDPE、高密度聚乙烯(HDPE)或任何前述聚乙烯的混合物。芯层可包括在印刷表层(A)部分上述的LLDPE或MDPE。芯层可包括这样的HDPE,其一般具有0.94以上至0.98g/cm3的密度。该HDPE可包括聚乙烯均聚物、聚乙烯共聚物——其一般含有5摩尔百分数以下的C3-C20共聚单体、或任何前述聚合物的混合物。该HDPE可用包括Z-N和茂金属催化剂在内的过渡金属催化剂制备。在本发明的实施方式中,芯层包括LLDPE或茂金属催化剂制备的LLDPE。
芯层可包括一种或多种热塑性聚合物和/或一种或多种添加剂,如上面印刷表层(A)部分所述。在本发明的实施方式中,芯层不含有不透明颜料,并且该膜是清晰的,具有小于10%、小于8%或小于6%的不透明度。在本发明的另一实施方式中,芯层含有不透明颜料,并且该模式不透明的,具有至少70%、至少75%或至少80%的不透明度。
在本发明的一种实施方式中,芯层包括约50%至约85%的至少一种丙烯共聚物、约5%至约25%的至少一种丙烯均聚物和约5%至约25%的至少一种聚乙烯。
在本发明的另一种实施方式中,芯层包括约70%至约85%的聚丙烯共聚物、约5%至约25%的聚丙烯均聚物和约5%至约25%的线型低密度聚乙烯。
在仍是另一种实施方式中,芯层包括按重量计约65-755%的至少一种丙烯共聚物、按重量计约10-20%的至少一种丙烯均聚物和按重量计约10-20%的至少一种聚乙烯。
在本发明的另一种实施方式中,芯层基于重量包括50-90%的聚丙烯共聚物、5-25%的聚丙烯均聚物和5-25%的聚乙烯,其通过齐格勒-纳塔或茂金属催化而制备并且具有从0.86或0.87至0.98g/cm3的密度。
芯层也包括按重量级高达约15%或甚至20%的一种或多种颜料。上述任一种颜料都可使用。
在本发明膜的芯层(B)中的聚丙烯-聚乙烯掺合物允许膜具有标签加工所必需的硬度和拉伸强度,同时通过赋予更整齐的切割和简化的冲膜操作提高了冲切以完善包括旋转冲模在内的冲膜切割。
在本发明的另一种实施方式中,芯层(B)可进一步包括再生膜,其中本发明膜在一种实施方式中进一步包括接合层(D),如后面的具体实施方式中描述。再生膜可包括来自先前制备的发明膜的修边或废料,其中修边或废料可以在与新的芯层树脂再生前重新研磨或重新粒化。再生膜可基于重量以0.5-20%、1-10%或1-7%用于芯中替换新掺合的树脂。因为再生膜一般主要构成芯树脂,所以再生膜在芯层中的使用可有利于消除由于废料和修边的损失。再生膜可基于替换一种或多种芯层树脂而被使用,所述芯层树脂包括至少一种丙烯共聚物、至少一种丙烯均聚物和至少一种聚乙烯,其具有约0.914至0.95g/cc的密度。在本发明的一种实施方式中,再生膜用于替换每一种芯聚合物。
(C)粘合表层
粘合表层包括接枝有不饱和羧酸或不饱和羧酸衍生物的至少一种聚烯烃。聚烯烃可包括聚烯烃均聚物,其由C2-C20烯烃制备,诸如举例来说聚乙烯、聚丙烯和聚异丁烯;聚烯烃共聚物,其由两种或多种C2-C20烯烃制备,诸如举例来说乙烯-丙烯共聚物;或者任何前述聚合物的混合物。不饱和羧酸或不饱和羧酸衍生物可以是含有至少一个碳碳双键和羧酸基团的任何有机化合物或其衍生物,其包括酯和酸酐。不饱和羧酸或不饱和羧酸衍生物可包括例如马来酸、富马酸、衣康酸、丙烯酸、丙烯酸甲酯或马来酸酐。聚烯烃可以通过自由基反应、在约180℃的高温下的热反应或者通过在美国专利号6300419中所述的挤压反应器与不饱和羧酸或其衍生物接枝。在接枝的聚烯烃中羧酸或酸衍生物的含量可以为按重量计0.1-10%。在本发明的实施方式中,粘合表层包括马来酸酐接枝的聚丙烯。接枝聚烯烃可从包括Equistar和DuPont在内的几个供应商得到。有用的接枝聚烯烃的具体实例包括来自Mitsui的Admer QF551A(熔体流动速度5.0)、来自Equistar的Plexar PX6006(熔体流动速度4.0)和来自DuPont的Bynel 50E561(熔体流动速度4)。
粘合表层还可包括一种或多种额外的热塑性聚合物和/或一种或多种添加剂,如上面印刷表层(A)部分所述。在一种实施方式中,除了接枝聚烯烃外,粘合表层包括至少一种丙烯均聚物。上述用于印刷表层的任何丙烯均聚物都可被用于粘合表层中。在一种实施方式中,粘合表层可含有按重量计约10至约90%的上述接枝聚烯烃以及按重量计10至90%的至少一种丙烯均聚物。
在本发明的实施方式中,粘合表层包括上述防结块浓缩物。
在本发明的实施方式中,粘合表层包括,基于重量,10-80%的接枝有不饱和羧酸或不饱和羧酸衍生物的聚烯烃,15至85%的丙烯均聚物和1-10%的防结块浓缩物。
粘合表层的接枝聚烯烃通过在冲切终止时允许沿剥离衬垫整齐的断开而提高了冲切,所述剥离衬垫在本说明书的后面被描述。粘合表层的接枝聚烯烃还提供粘合剂粘附或锚定的表面,而不需要允许粘合剂粘附的特定涂层,尽管特定涂层可以应用以进一步提高性能。粘合剂在粘合表层上的锚定是充分的,以致于派生的标签的复位是可能的,因为粘合剂转移是最低的。
(D)接合层
在本发明的实施方式中,当本发明膜的芯层(B)进一步包括再生膜时,本发明膜进一步包括接合层(D),所述接合层(D)包括至少一种聚丙烯共聚物、至少一种聚丙烯均聚物,和至少一种聚乙烯,其通过齐格勒-纳塔或茂金属催化而制备,具有从0.86至0.98g/cm3的密度。在一种实施方式中,除了接合层不包括再生膜外,接合层具有与上述芯层一样的常规组成。接合层也提供硬度、拉伸强度和冲切性能。
膜构建和加工
本发明多层聚合物膜的层可以通过包括从线型或环型冲模中挤出层的步骤,通过从线型或环型冲模中共挤出两层或多层,通过两个或多个预制的层的层压,或者前述步骤的任意组合而制备。在本发明的实施方式中,该膜通过从线型冲模中共挤出而制备。
在一种实施方式中,聚合物膜可以随后通过在纵向(在膜制造期间膜前进的方向)和横向(与纵向正交或垂直的方向)上将其双轴拉伸或者在纵向上将其单轴拉伸而定向。在本发明的实施方式中,该膜通过将其拉伸约2至9倍、3至9倍或者4至6倍只在纵向上定向。定向的膜也可以被热固化或退火以提供给膜二维稳定性以防止或最小化收缩或扭曲。可用于制造膜的共挤出、定向和退火步骤被描述在美国专利7,217,463中。该膜也可以在印刷表层(A)的表面或者印刷表层(A)和粘合表层(C)的表面上进行处理以进一步提高墨水或粘合剂与表层的粘合。表面处理可包括电晕放电处理、火焰处理、等离子体处理、用墨水或粘合剂接受材料例如丙烯酸涂层涂布,或者任何前述处理的组合。在本发明的实施方式中,该膜在一个表层或两个表层上进行电晕处理,或者该膜在一个表层或两个表层上进行火焰处理。
只在纵向上使膜定向一般增加纵向上的拉伸模量或硬度。这种增加的纵向硬度提供给从该膜制备的标签在标记物品中适当的可分配性和良好的印刷配准。这种只在纵向上定向的膜一般在横向(TD)上相比纵向(MD)具有明显较低的拉伸模量或硬度,其提供给派生标签与要标记的物品表面具有好的一致性。在本发明的实施方式中,TD与MD拉伸模量比小于0.75、0.65或0.6。
制造——其可包括例如共挤出或共挤出和定向——后,该膜可具有范围在0.5至10密耳(12.7-254微米)、1-7密耳(25.4-177.8微米)或1.5-4密耳(38.1-101.6微米)的总厚度。芯层(B)或者组合的芯层(B)和接合层(D)一般比表层(A)和(C)显著更厚。在本发明的实施方式中,表层是薄的,以允许该膜具有一致性和清晰度。表层可以是膜厚度的1-20%、2-15%、2-8%。芯层或者组合的芯层和接合层可以占该膜厚度的60-98%、70-96%或84-96%。该接合层可以是芯层厚度的0.1-0.5倍。
图1和图2图解了本发明的聚合物膜,其中薄的表层(A)和(C)分别位于厚的芯层(B)或者组合的接合层(D)和芯层(B)之上和之下。
膜实施例
下面非限定性的实施例进一步描述并阐明了本发明的一些实施方式。
实施例1:
2.5密耳(63.5微米)膜通过共挤出、纵向定向和提供二维稳定性的退火而制备。印刷表层(A)占膜厚的4%,并且基于重量包括47%的Z-N LLDPEDowlex 2517、28%的茂金属LLDPE EXACT 4049、21%的成核聚丙烯均聚物P4G4K-173X和5%的防粘结浓缩物Ampacet 401960。
芯层(B)占膜厚的92%,并且基于重量包括70%的成核聚丙烯无规共聚物P5M2K-070X、15%的茂金属LLDPE EXACT 4049和15%的成核聚丙烯均聚物P4G4K-173X。
粘合表层(C)占膜厚的4%,并且基于重量包括97%的马来酸酐接枝的聚丙烯Plexar PX6006和3%的防粘结浓缩物Ampacet401960。
实施例2:
2.5密耳(63.5微米)膜通过共挤出、纵向定向和提供二维稳定性的退火而制备。印刷表层(A)占膜厚的4%,并且基于重量包括46%的HuntsmanL2101、28%的茂金属LLDPE AFFINITY 8200G、21%的成核聚丙烯均聚物DowH7010-12NA和5%的防粘结浓缩物Ampacet 401960。
芯层(B)占膜厚的92%,并且基于重量包括68%的成核聚丙烯无规共聚物P5M2K-070X、14.5%的茂金属AFFINITY 8200G、14.5%的成核聚丙烯均聚物P4G4K-173X和3%的颜料浓缩物。
粘合表层(C)占膜厚的4%,并且基于重量包括97%的马来酸酐接枝的聚丙烯Plexar PX6006和3%的防粘结浓缩物Ampacet401960。
该膜是不透明的,具有至少70%的不透明度。
实施例3:
2.5密耳(63.5微米)膜通过共挤出、纵向定向和提供二维稳定性的退火而制备。印刷表层(A)占膜厚的4%,并且基于重量包括47%的Dowlex2517、27%的EXACT 4049、21%的成核聚丙烯均聚物P4G4K-173X和5%的防粘结浓缩物Ampacet 401960。
接合层(D)占膜厚的22%,并且基于重量包括70%的成核聚丙烯无规共聚物P5M2K-070X、15%的茂金属LLDPE EXACT 4049和15%的成核聚丙烯均聚物P4G4K-173X。
芯层(B)占膜厚的70%,并且基于重量包括62%的成核聚丙烯无规共聚物P5M2K-070X、13%的茂金属LLDPE EXACT 4049、13%的成核聚丙烯均聚物P4G4K-173X和12%的再生膜。
粘合表层(C)占膜厚的4%,并且基于重量包括97%的马来酸酐接枝的聚丙烯Admer QF551A和3%的防粘结浓缩物Ampacet401960。
实施例4:
2.5密耳(63.5微米)膜通过共挤出、纵向定向和提供二维稳定性的退火而制备。印刷表层(A)占膜厚的4%,并且基于重量包括46%的Dowlex2517、28%的茂金属LLDPE EXACT 4049、21%的成核聚丙烯均聚物P4G4K-173X和5%的防粘结浓缩物Ampacet 401960。
接合层(D)占膜厚的22%,并且基于重量包括70%的成核聚丙烯无规共聚物P5M2K-070X、15%的茂金属LLDPE EXACT 4049和15%的成核聚丙烯均聚物P4G4K-173X。
芯层(B)占膜厚的70%,并且基于重量包括64%的成核聚丙烯无规共聚物P5M2K-070X、14%的茂金属LLDPE EXACT 4049、14%的成核聚丙烯均聚物P4G4K-173X、5%的再生膜和3%的颜料浓缩物。
粘合表层(C)占膜厚的4%,并且基于重量包括97%的马来酸酐接枝的聚丙烯Admer QF551A和3%的防粘结浓缩物Ampacet401960。该膜是不透明的,具有至少70%的不透明度。
实施例5:
2.5密耳(63.5微米)膜通过共挤出、纵向定向和提供二维稳定性的退火以及印刷表层的电晕放电处理而制备。
印刷表层(A)占膜厚的4.5%,并且基于重量包括47%的LLDPE Dow Dowlex 2517、27%的聚乙烯塑性体ExxonMobil EXACT4049、21%的成核聚丙烯均聚物Huntsman P4G4K-173X和5%的防粘结浓缩物Ampacet 401960。
接合层(D)占膜厚的21%,并且基于重量包括70%的成核聚丙烯无规共聚物Huntsman P5M4K-072X、15%的聚乙烯塑性体ExxonMobil EXACT 4049和15%的成核聚丙烯均聚物HuntsmanP4G4K-173X。
芯层(B)占膜厚的70%,并且基于重量包括59.5%的成核聚丙烯无规共聚物Huntsman P5M4K-072X、12.75%的聚乙烯塑性体ExxonMobil EXACT 4049、12.75%的成核聚丙烯均聚物HuntsmanP4G4K-173X和15%的再生膜。
粘合表层(C)占膜厚的4.5%,并且基于重量包括15%的马来酸酐接枝的聚丙烯均聚物Chemtura Polybond 3150、80%的成核聚丙烯均聚物Huntsman P4G4K-173X和5%的防粘结浓缩物Ampacet401960。
实施例6:
2.5密耳(63.5微米)膜通过共挤出、纵向定向和提供二维稳定性的退火以及印刷表层的电晕放电处理而制备。
印刷表层(A)占膜厚的17%,并且基于重量包括47%的LLDPE Dow Dowlex 2517、27%的聚乙烯塑性体ExxonMobil EXACT4049、21%的成核聚丙烯均聚物Huntsman P4G4K-173X和5%的防粘结浓缩物Ampacet 401960。
接合层(D)占膜厚的15.8%,并且基于重量包括56%的聚丙烯无规共聚物Huntsman 43S2A——其具有0.9g/cm3的密度和1.9g/10分钟的熔体流动速度、15%的聚乙烯塑性体ExxonMobil EXACT 4049、18%的颜料浓缩物Colortech 11609-31——其是在聚丙烯载体中按重量计70%的二氧化钛、和11%的成核聚丙烯均聚物HuntsmanP4G4K-173X。
芯层(B)占膜厚的50.2%,并且基于重量包括50.4%的聚丙烯无规共聚物Huntsman 43S2A、13.5%的聚乙烯塑性体ExxonMobilEXACT 4049、9.9%的成核聚丙烯均聚物Huntsman P4G4K-173X、16.2%的颜料浓缩物Colortech 11609-31和10%的再生膜。
粘合表层(C)占膜厚的17%,并且基于重量包括15%的马来酸酐接枝的聚丙烯均聚物Chemtura Polybond 3150、80%的成核聚丙烯均聚物Huntsman P4G4K-173X和5%的防粘结浓缩物Ampacet401960。
该膜是不透明的,具有至少70%的不透明度。
(E)粘合层
本发明也涉及含有粘合剂的标签材料,其包括本发明的膜——其包括层(A)、(B)和(C);或者(A)、(D)、(B)和(C)以及粘合层(E),所述粘合层(E)具有上表面和下表面,其中粘合层的上表面粘附地结合于该膜的粘合表层(C)的下表面。
粘合层可直接涂布在粘合表层的下表面上,或者粘合剂可从衬垫中转移,其中膜与该衬垫结合。典型地,粘合层具有范围在约0.1至约2密耳(2.5至50微米)的厚度。适于使用的粘合剂是在本领域通常可得到的那些。一般地,这些粘合剂包括压敏粘合剂、热激活粘合剂、热熔粘合剂等。压敏粘合剂是特别有用的。这些包括丙烯酸粘合剂以及其它弹性体例如天然橡胶或合成橡胶,其包含苯乙烯、丁二烯、丙烯腈、异戊二烯和异丁烯的聚合物或共聚物。压敏粘合剂包括丙烯酸基、硅树脂基和橡胶基压敏粘合剂。压敏粘合剂在本领域是熟知的,并且任何已知的粘合剂可以与本发明的面料一起使用。在一种实施方式中,压敏粘合剂基于丙烯酸酯的共聚物,诸如举例来说2-乙基己基丙烯酸酯与极性共聚单体例如丙烯酸。
(F)剥离衬垫
在本发明的一些实施方式中,含有粘合剂的标签材料包括本发明膜——其包括层(A)、(B)和(C);或者(A)、(D)、(B)和(C)、粘合层(E)以及剥离衬垫(F),其中剥离衬垫可剥离地结合于粘合层(E)的下表面。剥离衬垫可包括单层或多层膜,其中衬垫的膜可包括纸膜、聚合物膜例如举例来说聚烯烃膜、或任何前述膜的混合物。剥离衬垫通常包括剥离衬垫膜上的剥离涂层例如举例来说有机硅氧烷聚合物,其也被称为硅树脂,所以剥离衬垫可随后在标记过程期间从粘合层上去除。在本发明的实施方式中剥离衬垫结合于粘合层以随后将粘合剂转移至粘合表层的下表面。当本文所述的本发明的多层膜与含有粘合剂的衬垫组合时,粘合层被结合于多层膜的下表面。随后,当衬垫或载体被去除以使粘合剂暴露时,粘合剂与粘合表层永久地保持结合。
本发明还涉及粘合标签,其是从上述含有粘合剂的标签材料中冲切的,所述含有粘合剂的标签材料包括本发明膜——其包括层(A)、(B)和(C);或者(A)、(D)、(B)和(C)、粘合层(E)以及剥离衬垫(F)。
含有粘合剂的标签材料构建和加工
本发明的聚合物膜包括多层膜,其可与压敏粘合剂一起被用于给物品作标记。该物品可以是任何成形的容器,包括瓶、壶、罐或桶。该物品可以由纸、纸板、玻璃、金属、塑料或其混合物制成。该物品可以是任何成形的容器,其用于包装消费品或工业品。聚合物膜一般被转化成含有粘合剂的标签材料,然后转化成用于给物品作标记的粘合标签。
聚合物膜可通过首先将该膜切成适合于给物品作标记的宽度而转化成含有粘合剂的标签材料。切成的膜然后与压敏粘合剂和剥离衬垫组合以制成如图3所示的含有粘合剂的标签材料。粘合层(E)可以首先与剥离衬垫(F)结合,首先与切成的聚合物膜——其包括层(A)、(B)和(C);或者(A)、(D)、(B)和(C)——组合,或者同时与衬垫和膜结合。含有粘合剂的标签材料典型地如下转化成粘合标签:采用任何印刷手段诸如举例来说用合适的印刷墨——包括水基墨、溶剂基墨和UV活化的墨——通过平板印刷术(胶印)印刷所述标签材料。可选地,切成的膜可以在与粘合剂和剥离衬垫组合前印刷。印刷后,保护性清漆可以被施用到该膜或标签材料的印刷表面上,其也增加清晰度。印刷的标签材料然后可以被冲切成一系列单个粘合标签,其可以用于在标记操作中给商业物品作标记。在作标记操作中,一系列冲切标签可以从与冲切标签相连的聚合物膜基质和下面的剥离衬垫上一个一个地剥离掉。
在具体实施方式中所涉及的每个文件在此被并入作为参考。本申请中在具体实施方式和所附的权利要求中使用的所有数量都应当理解为被词“约”所修饰,除了实施例和另外明确指明的地方之外。在具体实施方式和所附的权利要求中的所有范围和比值界限都是可组合的。
尽管本发明已经在具体实施方式和所附的权利要求中被介绍,但是应当理解在阅读本申请后,本发明的各种修饰对于本领域技术人员来说将变得明显。因此,落入所附权利要求和/或具体实施方式的范围内的这些各种修饰都应当认为是本发明的部分。

Claims (24)

1.用于给物品作标记的聚合物膜,其包括:
(A)印刷表层,其具有上表面和下表面,并且包括至少一种密度高达0.94g/cm3的聚乙烯以及至少一种聚丙烯;
(B)芯层,其具有上表面和下表面,并且包括至少一种聚丙烯共聚物、至少一种聚丙烯均聚物以及至少一种聚乙烯,其通过齐格勒-纳塔或茂金属催化制备并且具有0.86至0.98g/cm3的密度;和
(c)粘合表层,其具有上表面和下表面,并且包括至少一种接枝有不饱和羧酸或不饱和羧酸衍生物的聚烯烃,其中所述印刷表层(A)的所述下表面位于所述芯层(B)的所述上表面之上,并且所述粘合表层(C)的所述上表面位于所述芯层(B)的所述下表面之下,
其中所述芯层包括,基于重量,50%至85%的至少一种丙烯共聚物、5%至25%的至少一种丙烯均聚物和5%至25%的至少一种聚乙烯。
2.权利要求1的膜,其中在所述芯层(B)中的所述至少一种聚乙烯具有0.870至0.98g/cm3的密度。
3.权利要求1的膜,其中所述粘合表层(C)还包括至少一种丙烯均聚物。
4.权利要求1的膜,其中所述粘合表层包括按重量计10至90%的至少一种接枝有不饱和羧酸或不饱和羧酸衍生物的聚烯烃以及10至90%的至少一种丙烯均聚物。
5.权利要求4的膜,其中所述接枝有不饱和羧酸的聚烯烃是马来酸酐接枝的聚丙烯。
6.权利要求1的膜,其中所述膜通过所述层(A)、(B)和(C)的共挤出来制备。
7.权利要求1的膜,其中所述膜被定向。
8.权利要求7的膜,其中所述膜在纵向上单轴定向。
9.权利要求1的膜,其中所述印刷表层(A)包括至少一种线型低密度聚乙烯和至少一种聚丙烯均聚物。
10.权利要求1的膜,其中所述芯层(B)的所述聚乙烯包括至少一种线型低密度聚乙烯。
11.权利要求1的膜,其中所述印刷表层(A)包括基于重量60%至90%的至少一种聚乙烯以及10%至40%的至少一种聚丙烯。
12.权利要求1的膜,其中所述印刷表层(A)包括,基于重量,60%至90%的至少一种线型低密度聚乙烯以及10%至40%的至少一种丙烯均聚物。
13.权利要求1的膜,其中所述印刷表层还包括,基于重量,1至10%的至少一种防结块剂。
14.权利要求2的膜,其中所述芯层包括,基于重量,50%至85%的所述聚丙烯共聚物、5%至25%的所述聚丙烯均聚物和5%至25%的所述线型低密度聚乙烯。
15.权利要求1的膜,其中所述粘合表层(C)包括马来酸酐接枝的聚丙烯。
16.权利要求1的膜,其进一步包括(D)接合层,其具有上表面和下表面并且包括至少一种聚丙烯共聚物、至少一种聚丙烯均聚物以及至少一种聚乙烯,其通过齐格勒-纳塔或茂金属催化制备并且具有0.86至0.98g/cm3的密度,其中所述接合层的所述上表面与所述印刷表层(A)的所述下表面接触,并且所述接合层的所述下表面与所述芯层(B)的所述上表面接触,并且所述芯层(B)进一步包括再生膜。
17.权利要求16的膜,其中所述接合层中所述聚乙烯的密度为0.870至0.98g/cm3
18.权利要求1的膜,其中所述膜是透明的。
19.权利要求1的膜,其中所述芯层还包含颜料。
20.权利要求1的膜,其中所述膜是不透明的。
21.含有粘合剂的标签材料,其包括:
权利要求1的膜;和
(E)粘合层,所述粘合层具有上表面和下表面,其中所述粘合层的所述上表面粘附地结合于所述膜的所述粘合表层(C)的所述下表面。
22.含有粘合剂的标签材料,其包括:
权利要求16的膜;和
(E)粘合层,所述粘合层具有上表面和下表面,其中所述粘合层的所述上表面粘附地结合于所述膜的所述粘合表层(C)的所述下表面。
23.权利要求22的标签材料,其进一步包括剥离衬垫(F),其中所述剥离衬垫可剥离地结合于所述粘合层(E)的所述下表面,并且所述粘合层(E)是压敏粘合层。
24.粘合标签,从权利要求23的标签材料冲切得到。
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US20080199647A1 (en) 2008-08-21
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EP2043860A1 (en) 2009-04-08
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US8105686B2 (en) 2012-01-31
KR101400573B1 (ko) 2014-05-28
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AU2007275336B2 (en) 2012-03-22
CN101489787A (zh) 2009-07-22

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