CN101484315A - 用于热熔粘合剂标记和标签原料以及此种标签的多层聚合膜 - Google Patents

用于热熔粘合剂标记和标签原料以及此种标签的多层聚合膜 Download PDF

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CN101484315A
CN101484315A CNA200780025121XA CN200780025121A CN101484315A CN 101484315 A CN101484315 A CN 101484315A CN A200780025121X A CNA200780025121X A CN A200780025121XA CN 200780025121 A CN200780025121 A CN 200780025121A CN 101484315 A CN101484315 A CN 101484315A
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CN101484315B (zh
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C·J·布莱克威尔
K·O·亨德森
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Avery Dennison Corp
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Abstract

聚合膜，用于标记物品，其包括：核心层(A)，印刷表皮层(B)，印刷表皮层(B)包括聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯或任何前述聚合物的混合物以及——以层(B)的重量为基准——至少10％的以重量计的聚烯烃弹性体、烯烃－不饱和羧酸或酸衍生物共聚物、或任何前述聚合物的混合物，和粘合剂表皮层(C)，粘合剂表皮层(C)包括聚丙烯均聚物，其中该聚合膜被定向。包括有粘合剂的标签原料，和从所述包括有粘合剂的标签原料冲切出粘合剂标签，包括所述聚合膜，其对于压敏热熔粘合剂应用是特别有用的。

Description

用于热熔粘合剂标记和标签原料以及此种标签的多层聚合膜
相关申请的交叉参考
【0001】本申请权利要求2006年6月20日提交的美国临时申请第60/805,231的权益。
发明领域
【0002】本发明涉及多层聚合膜用于标记物品，以及进一步涉及包括粘合剂的标签原料以及包括所述聚合膜的标签。该膜、标签原料和标签与热熔粘合剂一起使用是特别有用的。
发明背景
【0003】热熔粘合剂提供了方便的和经济的方法，以便标记给予消费者的商品例如玻璃、金属和塑料容器和工业产品。热熔粘合剂很容易在它们的固体形式下操作，通常具有无限的储藏期限，对环境是友好的、且成本效益的，因为它们不含有溶剂，且能够快速地形成黏合结合，而没有任何附助的过程。热熔粘合剂的一个缺点是它们的损伤标签的趋势。多种相对低分子重量的添加剂一般在热熔粘合剂中存在，能够迁移到标签的聚合膜中，且产生标签的污点、膨胀和扭曲，这减损了它的功能和外观。这种添加剂的迁移还可以渐渐地导致热熔粘合剂失去粘性或粘附，特别是在高服务温度下，其可以导致标签的部分或全部的分离。热熔粘合剂还可以产生标签的热扭曲，其缺少抗热能力。
【0004】本发明的聚合膜最小化或消除了热熔粘合剂之添加剂的迁移且是抗热的，因此，派生的标签不会受损坏且保持粘附到容器上，甚至在高服务温度时。本发明的聚合膜进一步提供了需要产生高质量的标签之性能，其包括适印性、印模-可截割性，用于可分配性的足够的硬度，以及对物品或容器的适应性。
发明概述
【0005】本发明包括用于标记物品的聚合膜，其包括：(A)核心层，具有上表面和下表面且包括聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯或任意前述聚合物的混合物；(B)印刷表皮层，其包括聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯或任意前述聚合物的混合物，以及以层(B)重量为基础的以重量计的至少10％的聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生共聚物、或任意前述聚合物的混合物，，其中该印刷表皮层覆盖所述核心层的所述上表面；和，(C)粘合剂表皮层，其包括聚丙烯均聚物，其中粘合剂表皮层具有上表面和下表面，其中所述粘合剂表皮层的所述上表面位于所述核心层的所述下表面之下；其中层(C)的组成成分不同于层(A)的组成成分，以及该聚合膜是被定向的。
【0006】在本发明的实施方式中，所述聚合膜的核心层(A)进一步包括聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生共聚物，或任意前述聚合物的混合物。
【0007】在本发明的另一个实施方式中，在粘合剂标签中使用的包含粘合剂的标签原料，包括：上面所描述的本发明的聚合膜，其包括层(A)、(B)和(C)；(D)粘合剂层，其具有上表面和下表面，其中所述粘合剂层的所述上表面被黏性地接合到层(C)的所述下表面；以及(E)释放衬垫，其中该释放衬垫可释放性地粘附到所述粘合剂层(D)的所述下表面。
【0008】在本发明的进一步实施方式中，粘合剂标签是从上面所描述的——包括层(A)、(B)、(C)、(D)和(E)的含有粘合剂的标签原料——中被冲切出的。
附图简述
【0009】图1是本发明的聚合膜的横截面视图。
【0010】图2是本发明的含有粘合剂的标签原料的横截面视图。
发明详述
【0011】本发明的聚合膜包括：核心层(A)，核心层具有上表面和下表面，(B)印刷表皮层，该印刷表皮层位于核心层的上表面之上；和
(C)粘合剂表皮层，粘合剂表皮层位于核心层的下表面之下。术语之上和之下意味着印刷表皮层和粘合剂表皮层可以结合到或直接接触到核心层；或一个或多个中间层，例如，举例来说，粘结层可以位于表皮层和核心层之间。
(A)核心层(Core Layer)
【0012】核心层(A)包括聚丙烯均聚物，聚丙烯共聚物，高密度聚乙烯——具有的密度为0.94g/cm3或更高——，或任意前述聚合物的混合物。作为在整个本申请中使用的混合物包括相同种类的两种或多种成分，或相同种类的一种或多种成分和一种或多种不同种类的一种或多种成分。例如在层(A)中的聚合物的混合物可以包括两种或多种聚丙烯均聚物，两种或多种聚丙烯共聚物，两种或多种高密度聚乙烯，或一种或多种聚丙烯均聚物和/或一种或多种聚丙烯共聚物和/或一种或多种高密度聚乙烯。该聚丙烯均聚物和聚丙烯共聚物和高密度聚乙烯提供硬性膜，用于需要硬性膜的应用中。聚丙烯均聚物包括热塑性聚合物，其具有的密度为大约0.9g/cm3以及熔体指数(也作为熔体流动速率所熟知)为大约0.5到40g/10分钟，由ASTM Standard D1238所测量。聚丙烯均聚物可以通过——使用Ziegler-Natta或金属茂催化剂——由聚合丙烯单体的聚合而制备，且从多个树脂供应商，包括ExxonMobil，Huntsman和DowChemical，是可以获得的。聚丙烯均聚物可以包括：晶体聚丙烯均聚物，其包括等规聚丙烯均聚物；间规聚丙烯均聚物；或任意前述聚丙烯均聚物的混合物。聚丙烯均聚物的混合物可以是两种或多种等规聚丙烯均聚物，两种或多种间规聚丙烯均聚物，或一种或多种等规聚丙烯均聚物和一种或多种间规聚丙烯均聚物。等规和间规聚丙烯均聚物是高结晶的，其在甲苯中具有少量或没有溶解性，且分别具有的熔点为大约150-175℃和大约120-135℃。等规聚丙烯均聚物所具有的在13C核磁共振(NMR)波谱法基础上的等规立构规整性，如在美国专利第5476914中所描述，可以为大于大约70％、80％或90％。间规聚丙烯均聚物所具有的、在13C NMR波谱法基础上的间规立构规整性，如在美国专利第5476914中所描述，可以为大于大约70％、80％或90％。等规聚丙烯均聚物可以通过Ziegler-Natta或金属茂催化剂制备，且从多个树脂供应商，包括ExxonMobil、Huntsman、BASF、Amoco、Chisso和Solvay，可以获得。一种有用的聚丙烯均聚物是Huntsman P4G4K-173X，其是核化聚丙烯均聚物，具有0.9g/cm3的密度、和在230℃/2.16kg时的ASTM D1238熔体指数为12g/10分钟。间规聚丙烯均聚物，其比等规聚丙烯均聚物具有更少的晶体，可以用如美国专利第5476914号所描述的立体硬性金属茂催化剂制备，且可以从树脂供应商Atofina，从Finaplas
Figure A200780025121D0008125736QIETU
系列的间规聚丙烯均聚物中获得。
【0013】聚丙烯共聚物包括热塑性聚合物，其具有大约或小于0.9g/cm3的密度，大约0.5到40g/10分钟的熔体指数，以及具有大约120到150℃熔点的高程度结晶度。聚丙烯共聚物可以被制备，是通过聚合丙烯单体和一种或多种α-烯烃共聚用单体，使用催化剂，例如Ziegler-Natta或金属茂催化剂。该α-烯烃共聚用单体可以包括乙烯和α-烯烃，其具有4到30或4到12个碳原子。该α-烯烃共聚单体含量，在聚丙烯共聚物中，以重量为基础，可以在从0.1到40％，0.2到20％，0.3到10％，或者1到7％的范围中。在本发明的一个实施方式中，聚丙烯共聚物是聚丙烯随机共聚物，其从Ziegler-Natta催化剂中被制备。在本发明的另一实施方式中，聚丙烯随机共聚物是丙烯-乙烯共聚物，其包含以重量计的大约1到7％的乙烯共聚物。聚丙烯共聚物可以从多个树脂供应商，包括ExxonMobil、Dow Chemical和Huntsman获得。一种有用的聚丙烯均聚物是HuntsmanP5M4K-070X，其是核化的聚丙烯均聚物，包含3.2％重量的乙烯，且具有0.9g/cm3的密度，和在230℃/2.16kg下的的ASTM D1238熔体指数为12g/10分钟。
【0014】高密度聚乙烯可以从多个树脂供应商获得，包括DowChemical和Atofina。有用的高密度聚乙烯是Dow Chemical HDPE12450N和HDPE 17450N，其具有的在190℃/2.16kg时的ASTMD1238熔体指数分别为12g/10分钟和17g/10分钟。
【0015】在本发明的实施方式中，核心层(A)进一步包括一种或多种附加的热塑性聚合物。该一种或多种热塑性聚合物包括其他聚烯烃、烯烃-不饱和羧酸或酸衍生共聚物、以苯乙烯为基础的聚合物或共聚物、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、聚酯或任意的前述聚合物的混合物。
【0016】在本发明的实施方式中，核心层(A)进一步包括聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生共聚物，或任意前述聚合物的混合物。该混合物可以包括两种或多种聚烯烃弹性体，两种或多种烯烃-不饱和羧酸或酸衍生共聚物，或一种或多种聚烯烃弹性体和一种或多种烯烃-不饱和羧酸或酸衍生物共聚物。该聚烯烃弹性体和烯烃-不饱和羧酸或酸衍生共聚物，与聚丙烯以及高密度聚乙烯聚合物结合起来，提供更加可以变形的膜，用于需要顺应性的应用。
【0017】该聚烯烃弹性体，包括：弹性的均聚物，或C2-C30烯烃单体的共聚物，或前面所述任意聚烯烃弹性体的混合物。聚烯烃弹性体包含硬的或晶体的和软的或不定形的片段。聚烯烃弹性体是在热塑性聚合物和硫化橡胶之间的中间体，以结晶度和弹性为基础而言。聚烯烃弹性体比硫化橡胶更多结晶和更少弹性，且比热塑性聚合物典型地更少结晶和更低熔解以及更具弹性，其中热塑性聚合物例如是聚丙烯均聚物或共聚物，它们是高度结晶的。聚烯烃弹性体具有大约0.84到0.935g/cm3的密度，大约0.5到40g/10分钟的熔体指数，具有的熔点为大约35到160℃、大约35到120℃、或大约40到110℃，以及ASTM D638屈服伸长为大于40％、或60％或130％或200％。聚烯烃弹性体大体上可以如下所述被制备，是通过聚合烯烃单体或两种或多种不同烯烃单体的混合物，以分别形成均聚聚烯烃弹性体或共聚聚烯烃弹性体，也已知为烯烃共聚物弹性体，从而予以制备。烯烃单体可以包括：烯烃，其具有单个的双键，例如，举例而言，为乙烯；脂肪族多烯，其具有两个或多个双键，以包括共轭的和非共轭的二烯烃，例如，举例来说，1，3-丁二烯和1，4戊二烯；或前述烯烃单体的任何混合物。烯烃可以包括：内部烯烃，例如，举例，2-丁烯；α-烯烃，也已知为1-烯烃，例如，举例来说，乙烯和丙烯和1-辛烯；或任何前述烯烃的混合物。均聚聚烯烃弹性体可以被制备，是通过聚合烯烃单体，例如，举例而言，丙烯，成为等规立构聚烯烃的嵌段中和无规立构聚烯烃的嵌段中，以便于形成聚烯烃弹性体链。在本发明的一个实施方式中，聚烯烃弹性体可以包括低密度聚乙烯均聚物，是通过自由基催化作用而被制备的、且具有0.915到0.925g/cm3的密度。共聚的聚烯烃弹性体可以被制备，是通过聚合烯烃单体和一种或多种烯烃共聚单体而被制备，制备中使用金属茂催化剂，其中该弹性体的烯烃共聚单体含量——以摩尔百分比为基础——可以是大约1.5-30％，2-25％，2.5-20％或5-20％。在本发明的实施方式中，该烯烃共聚物弹性体包括两种或更多α-烯烃单体，或从两种或多种α-烯烃单体被制备，其具有2-30个，2-20个，2-12个或2-8个碳原子。在本发明的另一个实施方式中，该共聚聚烯烃弹性体包括：乙烯-α-烯烃共聚体弹性体，例如，举例而言，乙烯-α-烯烃共聚体弹性体，其中α-烯烃可以包括1-丁烯、1-戊烯、4-甲基-1-戊烯、1-已烯、1-辛烯、或任何前述α-烯烃的混合物；丙烯-α-烯烃共聚物弹性体；或任意前述共聚物弹性体的混合物。在本发明的实施方式中，聚烯烃弹性体包括：中等密度聚乙烯、线性低密度聚乙烯、极低密度聚乙烯、低密度聚乙烯——通过自由基催化作用而被制备，聚乙烯塑性体，聚丙烯共聚物弹性体，或任意前述聚合物的混合物。聚烯烃弹性体是可以从几个树脂供应商获得的，包括从ExxonMobil来源的Exact
Figure A200780025121D0008125736QIETU
系列和Vistamaxx
Figure A200780025121D0008125736QIETU
系列的弹性体，以及从Dow来源的Affinity
Figure A200780025121D0008125736QIETU
系列和Versify
Figure A200780025121D0008125736QIETU
系列的弹性体。有用的聚烯烃弹性体包括ExxonMobil Exact
Figure A200780025121D0008125736QIETU
系列的聚乙烯塑性体，其是通过下述方法被制备的，是通过聚合乙烯和25摩尔％或更少的少量的α-烯烃共聚用单体而被制备，使用金属茂催化剂，例如Exact
Figure A200780025121D0008125736QIETU
8203，其具有辛烯共聚单体和0.882g/cm3的密度以及在190℃/2.16kg时的ASTMD1238熔体指数为3g/10分钟。有用的聚烯烃弹性体还包括Dow Chemical Versify
Figure A200780025121D0008125736QIETU
系列的聚丙烯共聚物弹性体，其是通过聚合丙烯与少量的乙烯，例如Versify
Figure A200780025121D0008125736QIETU
3200，其具有0.876g/cm3的密度和在190℃/2.16kg时的ASTM D1238熔体指数为8g/10分钟，进行聚合而制备。
【0018】在本发明的实施方式中，烯烃-不饱和羧酸或酸衍生共聚物包括烯烃-不饱和羧酸共聚物，烯烃-不饱和羧酸盐酯共聚物，烯烃-不饱和羧酸共聚物的金属盐，或任意前述共聚物的混合物。烯烃-不饱和羧酸或酸衍生共聚物包括共聚物，其包括烯烃单体和不饱和羧酸或酸衍生共聚单体，其中该烯烃-不饱和羧酸或酸衍生共聚物可以被制备，从烯烃单体和该不饱和羧酸或酸衍生共聚单体制备。烯烃单体可以包括内烯烃，例如2-丁烯；和/或α-烯烃，例如乙烯，并且可以具有2个到30个碳原子。不饱和羧酸或酸衍生共聚单体可以包括不饱和羧酸，例如，举例而言，甲基丙烯酸和丙烯酸，不饱和羧酸酯，例如，举例而言醋酸乙烯酯和乙酸乙酯和甲基丙烯酸乙酯，或任意前述共聚单体的混合物。共聚单体，以重量为基础，可以以1-40％，4-30％或6-25％存在于共聚物中。在本发明的几个实施方式中，烯烃-不饱和羧酸或酸衍生共聚物可以包括：乙烯-醋酸乙烯酯共聚物；乙烯-甲基丙烯酸烷基酯共聚物；乙烯-甲基丙烯酸共聚物；乙烯-甲基丙烯酸共聚物的金属盐(也已知为离聚物)；以及任意前述共聚物的混合物。烯烃-不饱和羧酸或酸衍生共聚物可以具有0.91-0.96g/cm3的密度，0.5到40g/10分钟的熔体指数，35-160℃或35-120℃或40-110℃的熔点，且可以从树脂供应商处获得，包括ATPlastics和DuPont。有用的烯烃-不饱和羧酸或酸衍生共聚物，包括A.T.PlasticsAteva
Figure A200780025121D0011093605QIETU
系列的乙烯-醋酸乙烯酯共聚物，例如Ateva
Figure A200780025121D0011093605QIETU
1231，其包含12wt.％的醋酸乙烯酯，且具有0.932g/cm3的密度和在190℃/2.16kg时的ASTMD1238熔体指数为3g/10分钟；以及，Ateva
Figure A200780025121D0011093605QIETU
1821，其包含18wt.％的醋酸乙烯酯，且具有0.938g/cm3的密度和在190℃/2.16kg时的ASTMD1238熔体指数为3g/10分钟。DuPont Surlyn
Figure A200780025121D0011093605QIETU
系列的离聚物树脂也是有用的，该离聚物树脂包含乙烯-甲基丙烯酸共聚物的金属盐，——例如Surlyn
Figure A200780025121D0011093605QIETU
1601——是钠盐。
【0019】在本发明的实施方式中，聚烯烃弹性体和烯烃-不饱和羧酸或酸衍生共聚物存在于核心层(A)中的数量——以核心层(A)的重量为基准——按重量可以是至少10％，10到50％，10到40％，或10到30％。在本发明的实施方式中，聚丙烯均聚物和聚丙烯共聚物以及存在于核心层(A)中的高密度聚乙烯的数量——以核心层(A)的重量为基准——按重量可以是达到90％，50到90％，60％到90％，或70％-90％。聚烯烃弹性体和/或烯烃-不饱和羧酸或酸衍生共聚物在聚合膜的核心层和/或印刷表皮层中的存在，可以提高聚合膜的性能，以增加抗撕裂性、抗冲击性、对容器的顺应性上、以及在衍生标签的可印刷性而言。
【0020】在本发明的实施方式中，核心层(A)进一步包括一种或多种添加剂，如美国专利第6821592号中所描述的。该一种或多种添加剂包括成核剂、抗结块剂、加工助剂、滑爽剂、抗静电剂、色素、成穴剂、无机填料、抗氧化剂或任意前述添加剂的混合物。该添加剂可以被引入到膜中或膜的层中，作为由制造商提供的可商业获得的树脂的一部分，其中该树脂至少包括一种热塑型聚合物和一种或多种添加剂。可替代地，该添加剂可以被引入到膜或膜的层中，作为由添加剂浓缩物供应商提供的可商业获得的添加剂浓缩物的一部分，其中该添加剂浓缩物包括处于热塑性聚合物基体或载体中的一种或多种添加剂。成核剂可以包括无机或矿物质的成核剂，例如，诸如二氧化硅；有机成核剂，诸如羧酸的金属盐或β-成核剂，或任意前述成核剂的混合物。成核剂可以存在于本发明的聚合膜的一个或多个层中，其——以层的重量为基准——可以以100到10000，或200到5000，或300到1000ppm(百万分比)的重量范围存在。成核剂大体上被引入到膜的作为热塑性聚合物的一部分的层中，如同从树脂供应商那儿所得到的那样被引入。在本发明的几个实施方式中，成核剂存在于膜的一层中，其可以包括核心层或表皮层之一；或存在于膜的两层或多层的任意组合中。抗结块剂可以包括如下浓度，其占热塑性聚合物基体中的无机矿物质重量的大约3到80％，例如，举例而言，在聚烯烃基体中的不定形硅石以重量计为5％。抗结块剂可以存在于本发明的聚合膜的一层或多层中，其以如下重量范围——以层的重量为基准——，可以以100到10000，或200到5000，或300到1000ppm(百万分比)的重量存在。抗结块剂，以及滑爽剂、加工助剂、抗静电剂，提供了膜和衍生标签在性能上的提高，原因在于表面性质。因此，当存在于膜中，这些添加剂大体上存在于一层或两层表皮层中。颜料可以是无机颜料，其包括二氧化钛、碳酸钙、云母、氧化铁、炭黑或任意前述无机颜料的混合物；有机颜料；或任意前述颜料的混合物。颜料可以包括浓缩物，其中在热塑性基体中的无机颜料和/或有机颜料以重量计为大约20到80％。颜料浓缩物可以存在于本发明的一层或多层聚合膜中，其——以层的重量为基准——可以以大约0.5到20％的重量范围存在，以便给膜提供颜色和/或使膜不透明。不透明膜大体上具有至少70％，至少75％，或至少80％的不透明度。颜料浓缩物——当在膜中存在时，一般处于核心层中。
(B)印刷表皮层(Print Skin Layer)
【0021】印刷表皮层(B)包括聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯或任意前述聚合物的混合物，以及——以层(B)的重量为基准——至少10％以重量计的聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生共聚物、或任意前述聚合物的混合物。印刷表皮层的聚合物本文被描述为在核心层A)之上。聚烯烃弹性体和烯烃-不饱和羧酸或酸衍生共聚物——当存在于本印刷表皮层中时，提高了聚合膜的性能，以便包括衍生标签的适印性。印刷表皮层(B)的组合物不同于核心层(A)的组合物，因为印刷表皮层和核心层对膜提供了不同的功能和性能。
【0022】在本发明的几个实施方式中，印刷表皮层(B)包括——以印刷表皮层的重量为基准——至少10％，10到50％，10到40％，或10到30％的以重量计的聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生共聚物、或任意前述聚合物的混合物。在本发明的几个实施方式中，印刷表皮层(B)包括——以印刷表皮层的重量为基准——达到90％，50到90％，或70到90％的以重量计的聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯或任意前述聚合物的混合物。
【0023】在本发明的实施方式中，印刷表皮层(B)进一步包括一种或多种附加的热塑性聚合物，如本文上面对核心层(A)所描述。
【0024】在本发明的实施方式中，印刷表皮层(B)进一步包括一种或多种添加剂或添加剂浓缩物，如本文上面对核心层(A)所描述。在本发明的另一个实施方式中，印刷表皮层包括成核剂、抗结块剂、加工助剂、滑爽剂、抗静电剂、抗氧化剂或任意前述添加剂的混合物。
(C)粘合剂表皮层(Adhesive Skin Layer)
【0025】粘合剂表皮层(C)包括聚丙烯均聚物，其中粘合剂表皮层(C)的组合物不同于核心层(A)的组合物。因为粘合剂表皮层和核心层对膜提供了不同的功能和性能，所以粘合剂表皮层的组成不同于核心层的组成。层(C)的组成不同于层(A)的组成，基于以下原因：(i)聚丙烯聚合物的类型和/或数量，(ii)一种或更多附加的热塑性聚合物和/或聚烯烃弹性体和/或烯烃-不饱和羧酸或酸衍生共聚物的类型或数量，如本文上面对核心层(A)所描述，(iii)一种或多种添加剂的类型和/或数量，如本文上面对核心层(A)所描述，或(iv)任意前述情况(i)-(iii)的组合。该粘合剂表皮层的作用是提供表面，用于将粘合剂层黏附性地结合到该粘合剂表皮层的所述表面，其中该粘合剂层包括粘合剂，如本文下面对粘合剂标签原料所描述。在本发明的实施方式中，该粘合剂表皮层提供表面，用于将粘合剂层黏附地结合到该粘合剂表皮层的所述表面，其中该粘合剂层包括热熔粘合剂、且该粘合剂表皮层使热变形以及添加剂或热熔粘合剂成分的迁移得以消除或最小化，因此该发明的膜和从该膜衍生的标签在性能方面没有受损伤或降低。
【0026】该层(C)的聚丙烯均聚物包括聚丙烯均聚物，如本文上面对核心层(A)所描述。在本发明的实施方式中，该层(C)的聚丙烯均聚物包括等规聚丙烯均聚物，间规聚丙烯均聚物，或任意前述聚丙烯均聚物的混合物。在本发明的另一个实施方式中，等规聚丙烯均聚物具有大于70％、80％、90％或95％的等规立体规整性。在本发明的另一个实施方式中，间规聚丙烯均聚物具有大于70％、80％、90％或95％的间规立体规整性。在本发明的实施方式中，粘合剂表皮层(C)包括——以重量为基准——至少70％、80％、90％或95％的聚丙烯均聚物。在本发明的实施方式中，层(C)主要由下列物质组成：聚丙烯共聚物，和——以重量为基准的——至少70％的聚丙烯均聚物或聚丙烯共聚物，——以重量为基准——至少70％的聚丙烯共聚物，以及至少一种添加剂或添加剂浓缩物，其中该添加剂和添加剂浓缩物如本文上面对核心层(A)和本文下面对粘合剂表皮层(C)所描述。在本发明的其他实施方式中，层(C)主要由下列物质组成：聚丙烯共聚物，和——以重量为基准——至少80％的聚丙烯均聚物或聚丙烯共聚物，——以重量为基准——至少80％的聚丙烯均聚物，以及至少一种添加剂或添加剂浓缩物。在本发明的实施方式中，层(C)主要由下列物质组成：至少一种聚丙烯均聚物或至少一种聚丙烯均聚物和至少一种添加剂或添加剂浓缩物。在本发明的几个实施方式中，聚丙烯共聚物具有——以重量为基准——少于10％、少于6％、少于4％或少于2％的共聚单体含量，其中该共聚单体是丙烯以外的烯烃。
【0027】在本发明的实施方式中，粘合剂表皮层(C)进一步包括一种或多种附加热塑性聚合物，如本文上面对核心层(A)所描述。
【0028】在本发明的实施方式中，粘合剂表皮层(C)进一步包括一种或多种添加剂或添加剂浓缩物，如本文上面对核心层(A)所描述。在本发明的实施方式中，粘合剂表皮层(C)包括抗结块剂、滑爽剂、加工助剂、抗静电剂、成核剂、抗氧化剂或任意前述添加剂的混合物。在本发明的实施方式中，粘合剂表皮层(C)包括至少一种或多种添加剂或添加剂浓缩物，其中该添加剂或添加剂浓缩物不包括成穴剂。
膜成形和加工
【0029】本发明多层聚合膜的层可以通过下列步骤被制备，包括：从线性的或环形模口进行层挤压，从线性或环形模口进行两层或多层的共挤压，两侧或多层前面形成的层的层压，一层或多层被涂层到前面形成的单层或多层结构上，或前面所述步骤的任意组合。在本发明的实施方式中，膜是通过从线性模板进行共挤压被制备。
【0030】聚合膜可以被定向，通过：将它双轴向地进行拉伸，按机器的方向(在膜制造期间，该膜所前进的方向)和按横向的方向(与机器的方向正交或者垂直的方向)；或将它单轴向地拉伸，按机器的方向或按横向的方向进行拉伸。通常，该膜被定向，通过加热伸长它的长度和/或宽度几倍并随后将它退火而被定向，其中热伸长和退火在膜的软化温度下或附近***作，或从90到175℃下***作。在本发明的几个实施方式中，该膜被定向，通过在机器的方向，或者通过在机器方向和横向方向一起拉伸该膜2到12倍、2到10倍、2到9倍、3到9倍、或4到6倍。在本发明的实施方式中，该膜被定向，通过仅仅在机器方向，拉伸该膜2到12倍、2到10倍、2到9倍、3到9倍、或4到6倍。该定向膜随后可以被加热定型或被退火，以便对膜提供尺寸稳定性，从而以便：当在形成衍生的标签的加工期间中，暴露给升高的服务应用温度中时，以及在后来的标签服务中时，防止或最小化收缩或变形。共挤压、取向和退火过程——其可以被用于生产膜——，被在美国专利申请公布第US2004/0033349号中予以描述。
【0035】通常仅仅按机器的方向导向膜，增加了在机器方向上的拉伸模量或硬度。这个增加的机器方向硬度提供了标签——从所述膜而被制备——具有足够的硬度，以便在物品的标记过程中具有适合的可分配性和优良的印刷对准。这个膜，——仅仅按机器的方向被定向——，与机器方向(machine direction(MD))相比，在横向方向(transverse direction(TD))上一般具有实质上更低的拉伸模量或硬度，这给衍生标签提供了具有足够的柔韧性，以便对将要被标记物品之表面有良好的适应性。在本发明的实施方式中，该TD比MD的拉伸模量比例小于0.75、0.65或0.6。
【0032】该膜的下列生产，其可以包括：例如，共挤压，或共挤压和定向，或共挤压和定向和退火，可以具有如下总厚度，范围从0.5-10密尔(12.7-254微米)，1-7密尔(25.4-177.8微米)或1.5-4密尔(38.1-101.6微米)。本发明膜的核心层(A)大体上是更厚层，相比较于表皮层(B)和(C)或在该膜中可能存在的任意连接层而言。核心层(A)的厚度可以大于膜厚度的50％，65％到98％，70到98％，或85到98％。表皮层(B)的厚度可以相同于或不同于表皮层(C)的厚度。表皮层(B)和(C)厚度，独立地可以是膜厚度的少于50％，少于40％，1到30％，1到15％，1到10％，或2到5％。连接层可以存在于膜中，位于核心层(A)和一种或两种表皮层(B)和(C)之间，以提高表皮层或各个表皮层到核心层的粘附作用或结合作用。连接层包括任意聚合物，包括热塑性聚合物或聚烯烃弹性体或任意前述聚合物的混合物，如本文上面对核心层(A)所描述以及贯穿本申请，连接层提高了粘附性，且可以包括聚烯烃和烯烃-不饱和羧酸或酸衍生共聚物和/或聚烯烃弹性体的掺混物，例如，举例而言，聚丙烯均聚物或共聚物和乙烯-醋酸乙烯共聚物的掺混物。连接层的厚度大体上相同于表皮层的厚度。位于表皮层和核心层之间的任意连接层的组成不同于核心层和所述表皮层的组成，因为这些层的每一个给所述膜提供了不同的功能和性能。
【0033】在本发明的实施方式中，存在于膜的层中的每一种热塑性聚丙烯均聚物和/或共聚物，可以独立地具有以g/10分钟为单位的熔体流动速率，当通过ASTM Standard D1238在230℃/2.16Kg下测定时，至少为4；4到35；6到30；至少8；或8到25。从膜中衍生的标签包括高熔体流动速率(至少4或至少8g/10分钟)的聚丙烯均聚物和/或共聚物，通常具有提高的可冲切性。
【0034】本发明的膜包括印刷表皮层(B)，其在印刷表皮层内，包括至少10％重量的聚烯烃弹性体，烯烃-不饱和羧酸或酸衍生物共聚物，或任何前述的聚合物混合物，以印刷表皮层的重量为基准。聚烯烃弹性体和烯烃-不饱和羧酸或酸衍生物共聚物，可以提高可印刷性和/或允许提高关于墨粉粘附到从该膜衍生的标签上的印刷适性。该膜还可以被处理，是在印刷表皮层(B)的表面上或在两层表皮层的表面上被处理，以进一步提高墨水或粘合剂层粘附到表皮层的能力。表面处理包括电晕放电处理；火焰处理；等离子体处理；用墨水-或粘合剂-接受材料进行涂层，例如，丙烯酸涂层；或任何前述处理的组合。
【0035】在本发明的几个实施方式中，核心层(A)包括聚丙烯均聚物，聚丙烯共聚物，高密度聚乙烯，或任何前述聚合物的混合物；印刷表皮层(B)包括聚丙烯均聚物，聚丙烯共聚物，高密度聚乙烯或任何前述聚合物的混合物以及至少10％重量——以层(B)的重量为基准——的聚烯烃弹性体，烯烃-不饱和羧酸或酸衍生物共聚物，或任何前述聚合物的混合物。在本发明的几个实施方式中，核心层(A)包括聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯或任何前述聚合物的混合物以及聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生物共聚物、或任何前述聚合物的混合物；印刷表皮层(B)包括聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯、或任何前述聚合物的混合物以及至少10％——以层(B)的重量为基准——聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生物共聚物、或任何前述聚合物的混合物。
【0036】图1示例了本发明的聚合膜，其中，相对薄的表皮层(B)和(C)分别覆盖在和下衬至相对厚的核心层(A)。
粘合剂标签原料(Adhesive Label Stock)和粘合剂标签构成(AdhesiveLabel Construction)
【0037】本发明的聚合膜包括多层分层的膜，其与粘合剂层一起被使用，以便标记物品。该物品可以是任意形状的容器，包括瓶子、壶、广口瓶或鼓。该物品可以由纸、纸板、玻璃、金属、塑料或它们的混合物制造。该物品可以是任意形状的容器，被用于包装日用或工业产品。在本发明的实施方式中，该膜包括层(A)、层(B)和层(C)，进一步包括粘合剂层(D)，其具有上和下表面，其中粘合剂层的上表面被粘附地结合到粘合剂表皮层(C)的下表面。在本发明的另一个实施方式中，粘合剂层包括本文下面所描述的粘合剂。聚合膜通常被转化成包括有粘合剂的标签原料以及随后转化成粘合剂标签，其被用于标记物品。该聚合膜可以被转化成包括有粘合剂的标签原料，是通过最初将该膜裂缝方式切开、成为适合于对物品进行标记的宽度。该裂缝方式切开膜随后与粘合剂层和释放衬垫被一起组合起来，以形成含有粘合剂的标签原料，如图2中示例性图解所示的那样。粘合剂层可以与释放衬垫最初组合，与裂缝方式切开聚合膜最初组合，或与衬垫和膜同时组合。在图2中，粘合剂层(D)具有上表面和下表面，其中粘合剂层(D)的上表面被粘附性地结合到聚合膜的粘合剂表皮层(C)的下表面，该聚合膜包括层(A)、(B)和(C)，且释放衬垫(E)被可释放地粘附到粘合剂层(D)的上表面。该释放衬垫可以包括单层或多层膜，其中该衬垫的膜可以包括纸膜、聚合膜，例如，举例而言，聚烯烃膜或任何前述膜的混合物。释放衬垫膜通常在该释放衬垫膜上包括释放涂层，例如，举例来说，有机硅氧烷聚合物，其也称作硅树脂，因此，该释放衬垫后来可以在标记过程期间，从粘合剂层上被去除。粘合剂层包括粘合剂，其包括一种或多种热塑性聚合物，以包括有一种或多种弹性聚合物。在本发明的一个实施方式中，粘合剂层包括压敏粘合剂。在本发明的实施方式中，粘合剂层包括压敏粘合剂，其包括液体粘合剂、乳液粘合剂、或热熔粘合剂。
【0038】压敏热熔粘合剂一般包括弹性聚合物，其包括天然橡胶和/或合成聚合物和附加成分，例如，举例而言，增粘剂，如美国专利第6214935号所描述。热熔粘合剂包括烯烃-不饱和羧酸酯共聚物，例如，举例来说，乙烯-醋酸乙烯酯共聚物和乙烯-丙烯酸乙酯共聚物，苯乙烯聚合物和/或共聚物和/或嵌段共聚物，例如，举例来说，苯乙烯-异戊二烯-苯乙烯嵌段共聚物和苯乙烯-丁二烯-苯乙烯嵌段共聚物，聚烯烃，聚酰胺，聚酯，聚氨酯，例如，举例而言，活性聚氨酯，和前述聚合物的任何混合物。热熔粘合剂进一步包括增粘剂；增塑剂；蜡；改性助剂，包括抗氧化剂和光引发剂；以及填料和增强剂和增容剂和成核剂和任何前述添加剂的混合物，以及任何前述成分的混合物。在本发明的一种实施方式中，粘合剂层包括热熔粘合剂，其包括苯乙烯嵌段共聚物。
【0039】包含粘合剂的标签原料典型地转变为粘合剂标签，是通过最初印刷该标签原料，使用任意的印刷方法，例如，举例而言，使用带有合适的印刷墨水，包括，例如水性墨水和溶剂型墨水和UV活化墨水进行的胶版印刷。可替代地，裂缝膜可以被印刷，是在与热熔粘合剂和释放衬垫结合之前进行印刷。该经过印刷的标签原料随后被冲切成一系列的单个的粘合剂标签，其可以在标记操作方式中被用于标记商品。在标记操作中，一系列的冲切粘合剂标签可以从聚合膜基体被一个接一个地剥离下来，该聚合膜与冲切标签和下衬释放衬垫接壤。
实施例
【0040】下面的非限定实施例进一步描述和示例了本发明。
【0041】实施例1：制备2.5密尔(63.5微米)膜，是通过共挤压、通过在机器方向拉伸5.3倍进行定向、退火、和电晕放电处理印刷表皮层而制备。核心层(A)占膜厚度的92％，且包括——以重量为基准——100％的聚丙烯共聚物。印刷表皮层(B)占膜厚度的4％，且包括——以重量为基准——80％的聚丙烯共聚物、10％的聚乙烯弹性体、和2％的抗结块剂。粘合剂表皮层(C)占膜厚度的4％，且包括——以重量为基准——98％的聚丙烯均聚物和2％的抗结块剂。
【0042】实施例2：2密尔(50.8微米)膜被制备，如实施例1所示那样进行制备。核心层(A)占膜厚度的80％，且包括——以重量为基准——90％的聚丙烯均聚物和10％的聚乙烯弹性体。印刷表皮层(B)占膜厚度的9％，且包括——以重量为基准——89％的聚丙烯均聚物、10％的聚乙烯弹性体和1％的抗结块剂。粘合剂表皮层(C)占膜厚度的11％，且包括——以重量为基准——98％的聚丙烯均聚物和2％的抗结块剂。
【0043】实施3：2.5密尔(mil)(63.5微米)膜被制备，如实施例1所示那样制备。核心层(A)为74％的膜厚度，且包括——以重量为基准——90％聚丙烯共聚物和10％聚乙烯弹性体。印刷表皮层(B)为11％的膜厚度，且包括——以重量为基准——61％聚丙烯共聚物、36％聚乙烯弹性体和3％抗结块剂。粘合剂表皮层(C)为15％的膜厚度，且包括——以重量为基准——98％聚丙烯均聚物和2％抗结块剂。
【0044】实施例4：2密尔(50.8微米)膜被制备，如实施例1所示那样进行制备。核心层(A)是80％的膜厚度，且包括——以重量为基准——90％聚丙烯共聚物和10％聚乙烯弹性体。印刷表皮层(B)是9％的膜厚度，且包括——以重量为基准——89％聚丙烯共聚物、10％聚乙烯弹性体、和1％抗结块剂。粘合剂表皮层(C)是11％的膜厚度，且包括——以重量为基准——98％聚丙烯均聚物和2％抗结块剂。
【0045】实施例5：2.5密尔(63.5微米)膜被制备，如实施例1所示那样制备。核心层(A)是92％的膜厚度，且包括——以重量为基准——100％聚丙烯共聚物。印刷表皮层(B)是4％的膜厚度，且包括——以重量为基准——88％聚丙烯共聚物、10％聚乙烯弹性体、和2％抗结块剂。粘合剂表皮层(C)是4％的膜厚度，且包括——以重量为基准——98％聚丙烯均聚物和2％抗结块剂。
【0046】实施6：2密尔(50.8微米)膜被制备，正如实施例1所示那样进行制备。核心层(A)占74％的膜厚度，且包括——以重量为基准——90％聚丙烯共聚物和10％聚乙烯弹性体，印刷表皮层(B)占11％的膜厚度，且包括——以重量为基准——61％聚丙烯均聚物、36％聚乙烯弹性体、和3％抗结块剂。粘合剂表皮层(C)占15％的膜厚度，且包括——以重量为基准——83％聚丙烯均聚物、15％聚丙烯共聚物和2％抗结块剂。
【0047】实施例7：2密尔(50.8微米)膜被制备，正如实施例1所示那样进行制备。核心层(A)是78％的膜厚度且包括——以重量为基准——90％聚丙烯共聚物和10％聚乙烯弹性体。印刷表皮层(B)是12％的膜厚度且包括——以重量为基准——88％聚丙烯共聚物、10％聚乙烯弹性体、和2％抗结块剂。粘合剂表皮层(C)是10％的膜厚度且包括——以重量为基准——78％聚丙烯均聚物、20％聚丙烯共聚物和2％抗结块剂。
【0048】实施例8：2.5密尔(63.5微米)膜被制备，如实施例1所示那样进行制备。核心层(A)是77％的膜厚度，且包括——以重量为基准——100％聚丙烯均聚物。印刷表皮层(B)是15％的膜厚度，且包括——以重量为基准——88％聚丙烯共聚物、10％线性低密度聚乙烯、和2％抗结块剂。粘合剂表皮层(C)是8％的膜厚度，且包括——以重量为基准——93％聚丙烯均聚物、5％聚丙烯共聚物和2％抗结块剂。
【0049】实施例9-20是单层粘合剂表皮膜，它们是在试验性流水线上被制备的，是通过挤压、在机器方向上被拉伸5倍而被定向、以及退火而制备的。就热熔粘合剂性能，实施例9-20的膜——在抵抗膨胀和变形方面，采用矿物油——被进行评估，这模拟了热熔粘合剂的添加剂迁移。表I列举了实施例9-20之膜的热熔粘合剂性能。
表I
 
实施例 组成成分a 等级@16小时 等级@42小时
9 80％RCP1+20％HPP1 1 4
10 50％RCP1+50％HPP1 1 2
11 20％RCP1+80％HPP1 1 1
12 100％HPP1 1 1
13 100％RCP1 1 4
14 50％GMAH1+48％RCP2+2％AB 5 5
15 98％GMAH1+2％AB 5 5
16 68％RCP2+30％PT+2％AB 1 5
17 77％GMAH1+21％HPP2+2％AB 1 4
18 40％GMAH2+55％HPP2+5％AB 2 4
19 15％GMAH3+80％HPP2+5％AB 1 3
20 95％GAA+5％AB 2 3
a组成成分是以重量为基准的。
RCP1是Basell XL451J聚丙烯无规共聚物，其具有的熔体流动速率(melt flow rate(MFR))为3.9.
HPP1是Basell SR257M聚丙烯均聚物，具有的MFR为2.0。
GMAH1是Mitsui Admer QF551A聚丙烯均聚物，其用0.5％马来酸接枝，其具有的MFR为5.7。
RCP2是Huntsman P5M4K-072X核化聚丙烯无规共聚物，其具有的MFR为10.0。
AB是Ampacet 401960抗结块剂，其在聚丙烯均聚物载体中包含3％的聚(甲基丙烯酸甲酯)，且具有的MFR为7.2。
PT是在聚丙烯均聚物载体中的ExxonMobil Exxelor PA609A多萜树脂(polyterpene rosin)。
HPP2是Huntsman P4C4K-173X核化聚丙烯均聚物，其具有的MFR为12.0。
GMAH2是Chemtura Polybond 3150聚丙烯均聚物，用0.5％马来酸接枝；且具有的VFR为50.0。
GMAH3是Chemtura Polybond 3200聚丙烯均聚物，用1.0％马来酸接枝；且具有的MFR为115.0。
GAA是Chemtura Polybond 1001聚丙烯均聚物，用6％马来酸接枝且；具有的MFR为40.0。
b由于使用矿物油而产生的添加剂迁移所致膜变形的评价等级如下：
1＝平的(没有可辨认的翘曲)，
2＝低翘曲，
3＝中等翘曲，
4＝高翘曲，
5＝卷曲的。
【0050】在本详细说明中所参考的每个文献被并入此处，以作参考。在本详细说明书和附属的权利要求中所使用的，本申请中的所有数量，均被理解为：受词语“大约”所修饰，除了在实施例中和明白地指明是其他的情形以外的情况中。在详细说明书中和附属权利要求中的所有范围和比例限定，是可以组合的。
【0051】虽然本发明已经被展现在本详细说明书和附属权利要求中，但是应该可以理解到的是：在阅读本申请后，本发明的各式各样的修改对于本领域的那些技术人员来说将是明显的。因此这些众多的修改，——其落在附属权利要求和/或详细说明书的范围之内——，被认为是本发明的一部分。

Claims (14)

1.聚合膜，用于标记物品，其包括：
(A)核心层，具有上表面和下表面，且包括聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯、或任何前述聚合物的混合物；
(B)印刷表皮层，包括：聚丙烯均聚物、聚丙烯共聚物、高密度聚乙烯、或任何前述聚合物的混合物；和——以层(B)的重量为基准——至少10％的聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生物共聚物、或任何前述聚合物的混合物，其中印刷表皮层覆盖核心层的上表面；和
(C)粘合剂表皮层，包括聚丙烯均聚物，其中粘合剂表皮层具有上表面和下表面，其中粘合剂表皮层的上表面下衬在核心层的下表面之下；其中，层(C)的组成不同于层(A)的组成，且该聚合膜是被定向的。
2.如权利要求1所述的膜，其中，层(C)的所述聚丙烯均聚物是等规聚丙烯均聚物，其具有大于90％的等规立构规整度。
3.如权利要求1所述的膜，其中，层(C)的所述聚丙烯均聚物是间规聚丙烯均聚物，其具有大于90％的间规立构规整度。
4.如权利要求1所述的膜，其中，层(C)的所述聚丙烯均聚物是等规聚丙烯均聚物和间规聚丙烯均聚物的混合物。
5.根据前述权利要求中任何一项所述的膜，其中所述层(C)进一步包括成核剂、抗结块剂、滑爽剂、加工助剂、抗静电剂、抗氧化剂或任何前述添加剂的混合物。
6.根据前述权利要求中任何一项所述的膜，其中，层(A)，或层(A)和(B)，包括成核剂。
7.根据前述权利要求中任何一项所述的膜，其中，层(A)进一步包括聚烯烃弹性体、烯烃-不饱和羧酸或酸衍生物共聚物、或任何前述聚合物的混合物。
8.如权利要求7所述的膜，其中所述聚烯烃弹性体包括中等密度聚乙烯、线性低密度聚乙烯、极低密度聚乙烯、通过自由基催化制备的低密度聚乙烯、聚乙烯塑性体、聚丙烯共聚物弹性体、或任何前述聚合物的混合物。
9.如权利要求7所述的膜，其中所述烯烃-不饱和羧酸或酸衍生物共聚物包括烯烃-不饱和羧酸共聚物、烯烃-不饱和羧酸酯共聚物、烯烃-不饱和羧酸共聚物的金属盐、或任何前述的共聚物的混合物。
10.根据前述权利要求中的任何一项所述的膜，其中，层(C)的厚度占聚合膜厚度的1％到30％。
11.根据前述权利要求中的任何一项所述的膜，其中所述膜被定向，是通过——以机器方向或以机器和横向的方向，拉伸所述膜2倍到12倍而定向。
12.包含粘合剂的标签原料，用于在粘合剂标签中使用，其包括：
前述权利要求中的任何一项所述的膜；
(D)粘合剂层，具有上表面和下表面，其中该粘合剂层的上表面被可粘附性地结合到层(C)的下表面；和
(E)释放衬垫，其中释放衬垫被可释放性地黏结到粘合剂层(D)的下表面。
13.权利要求12所述的包含粘合剂的标签原料，其中所述粘合剂层包括热熔粘合剂。
14.粘合剂标签，是从权利要求12或13中的任何一个所述的标签原料冲切而来。
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BRPI0713492A2 (pt) 2012-01-24
AU2007261011A1 (en) 2007-12-27
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