CN104334670B - 湿胶水 - Google Patents

湿胶水 Download PDF

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CN104334670B
CN104334670B CN201380029620.1A CN201380029620A CN104334670B CN 104334670 B CN104334670 B CN 104334670B CN 201380029620 A CN201380029620 A CN 201380029620A CN 104334670 B CN104334670 B CN 104334670B
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N·西索斯基
I·尤尔
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Abstract

提供了一种水性粘合剂组合物，其包含特定乳液聚合物和环氧硅烷，其中所述粘合剂组合物基本上不含交联剂。也提供了一种提供带有纸标签的基材的方法，所述粘附的标签具有耐冰水性，以及一种从所述基材除去纸标签的方法。

Description

湿胶水
本发明涉及水性粘合剂组合物，通常称为湿胶水粘合剂。更具体地，本发明涉及水性粘合剂组合物，其包含：a)乳液聚合物，以所述乳液聚合物的重量计，所述乳液聚合物包含作为共聚单元的10-35重量％的羧酸单体和至少一种第二烯键式不饱和单体；和b)以所述乳液聚合物的重量计，0.1-4重量％的环氧硅烷；其中所述粘合剂组合物基本上不含交联剂。本发明也涉及提供带有可除去纸标签的基材的方法，以及从带有可除去纸标签的基材除去纸标签的方法。
用于纸标签应用的基于碱-可溶胀丙烯酸类聚合物的湿胶水粘合剂通常施加到玻璃饮料瓶上。当放入冰水浴中时标签必须粘附在瓶上，且在回收操作时可很容易地除去，所述回收操作通常使用高温和苛性溶液。基于该化学物质的湿胶水组合物具有差的耐冰水浴性，且需要例如加入天然产物例如酪蛋白或淀粉来提高耐冰水浴性。
US专利申请公开第20010021452号公开了一种压敏粘合剂，其由丙烯酸类聚合物、硅烷偶联剂和具有特定溶胶和凝胶成分的交联剂形成。仍需要这样的粘合剂组合物，其具有标签应用中所需的耐冰水性和可除去性之间的平衡。本发明的粘合剂组合物提供了这些性能之间的平衡。
在本发明的第一个方面中，提供一种水性粘合剂组合物，其包含：a)乳液聚合物，所述乳液聚合物包含作为共聚单元的10-35重量％羧酸单体和至少一种第二烯键式不饱和单体，所述含量以所述乳液聚合物的重量计；和b)0.1-4重量％的环氧硅烷，所述含量以所述乳液聚合物的干重量计；其中所述粘合剂组合物基本上不含交联剂。
在本发明的第二个方面中，提供了一种用来提供带有可除去纸标签的基材的方法，该方法包括：(a)形成本发明第一方面的水性粘合剂组合物；(b)将所述水性粘合剂组合物施涂于所述纸标签；(c)将带有粘合剂的纸标签施加到所述基材。
在本发明的第三个方面中，提供了一种从带有可除去纸标签的基材除去纸标签的方法，所述方法包括：(a)提供本发明所述第二方面的带有可除去纸标签的基材；以及(b)使所述可除去标签与碱溶液接触，接触的时间和温度足以除去所述标签。
本发明涉及一种水性粘合剂组合物。在本文中，“水性组合物”是指水和以该介质的重量为基准计的0-30重量％的能与水混溶的化合物。
所述水性粘合剂组合物(或者水性纸标签粘合剂组合物)包括乳液聚合物，所述乳液聚合物包括作为共聚单元的10-35重量％(优选15-30重量％)的羧酸单体和至少一种第二烯键式不饱和单体，所述含量以所述乳液聚合物的重量计。该乳液聚合物属于通常称为碱可溶胀聚合物的这类聚合物。合适的羧酸单体包括例如丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、富马酸、马来酸、衣康酸单甲酯、富马酸单甲酯、富马酸单丁酯以及马来酸酐。优选的羧酸单体是(甲基)丙烯酸。
所述至少一种共聚的第二单烯键式不饱和单体不包括羧酸单体，且包括例如(甲基)丙烯酸酯单体，其包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、脲基官能(甲基)丙烯酸酯和乙酰乙酸酯、(甲基)丙烯酸的乙酰胺或氰基乙酸酯；苯乙烯或取代的苯乙烯；乙烯基甲苯；丁二烯；乙酸乙烯酯或其它乙烯基酯；乙烯基单体，例如氯乙烯、偏二氯乙烯、N-乙烯基吡咯烷酮；(甲基)丙烯腈；和N-羟烷基(甲基)丙烯酰胺。在本文中，在另一个术语前面使用术语“(甲基)”，例如整篇说明书中使用的(甲基)丙烯酸酯或(甲基)丙烯酰胺，分别表示丙烯酸酯和甲基丙烯酸酯或丙烯酰胺和甲基丙烯酰胺。优选聚合物的主链主要是丙烯酸类或苯乙烯-丙烯酸类组合物。
任选地，低含量的多烯键式不饱和单体(例如(甲基)丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、丁二烯、二(甲基)丙烯酸1,4-丁二醇酯、二(甲基)丙烯酸1,2-乙二醇酯、二(甲基)丙烯酸1,6-己二醇酯和二乙烯苯可加入到所述乳液聚合物中。一般可使用例如0-0.5％这样的含量的多烯键式不饱和单体，但必须选择该含量以免对所述组合物的粘合性造成不利影响。
在形成本发明的第一聚合物的方法中常用的乳液聚合技术是本领域众所周知的，例如美国专利第4,325,856号；第4,654,397号；以及第4,814,373号所揭示的。可使用常规表面活性剂，例如阴离子和/或非离子乳化剂，例如以下的酸的碱金属或铵盐：烷基或乙氧基化烷基硫酸，烷基磺酸，脂肪酸；磷酸酯/盐表面活性剂，例如RHODOFACTM RS-610和RHODOFACTM RS-960，以及乙氧基化的烷基酚。以全部单体的重量计，表面活性剂的用量通常为0.1-6重量％。可以使用热引发法或氧化还原引发法。可以采用常规自由基引发剂(也称为催化剂)，例如过氧化氢、叔丁基过氧化氢或叔戊基过氧化氢、以及过硫酸铵和/或碱金属过硫酸盐，以单体的总重量为基准计，所述自由基引发剂的含量通常为0.01-3.0重量％。使用相同引发剂和合适还原剂(也称为活化剂，例如甲醛合次硫酸氢钠、连二亚硫酸钠、异抗坏血酸、硫酸羟胺和亚硫酸氢钠)的组合的氧化还原体系可以类似的含量使用，任选地与金属离子如铁和铜组合，还任选地包含用于金属的络合剂。可以使用硫醇之类的链转移剂，以降低聚合物的分子量。
这些单体可以单独地加入或者以单体混合物的形式加入，可以以净相形式加入，或者以在水中的乳液的形式加入。在某些实施方式中，本发明的单体加入两段或更多段中。
例如，可使用如美国专利第4,384,056号和第4,539,361号所揭示的产生多峰粒度分布的方法。
使用纽约州霍尔兹维尔的布鲁克哈文仪器公司(Brookhaven Instrument Corp.,Holtsville,NY)提供的布鲁克哈文BI-90型粒度计(Brookhaven Model BI-90Particle Sizer)测定，所述水性乳液聚合物颗粒的平均粒径通常为30-500纳米，优选为75-300纳米，更优选为90-250纳米。
本发明的水性粘合剂组合物包括0.1-4重量％，优选1.5-3.0重量％的环氧硅烷，所述含量以所述乳液聚合物的干重量计。本文中的"环氧硅烷"包括缩水甘油醚氧基(glycidoxy)烷基三甲氧基硅烷。优选的是3-缩水甘油醚氧基丙基三甲氧基硅烷。
所述水性粘合剂组合物的pH通常为3-11，优选为6-10。水性粘合剂组合物的任意pH调节优选用氨进行。所述水性粘合剂组合物的合适粘度范围为50,000cp-120,000cp(Brookfield粘度,RVT心轴7,转速20rpm),优选80,000cp-120,000cp。
除了乳液聚合物，所述水性粘合剂组合物可包含成膜或非成膜溶液或第二乳液聚合物，其含量为0-200重量％，以本发明所述的第一乳液聚合物的重量计，例如脲(urea)和源自植物或动物的天然产物以及源自其中的材料，例如淀粉和酪蛋白。如果任选的第二乳液聚合物是这样的乳液聚合物，其包含作为共聚单元的10-35重量％羧酸单体和至少一种第二烯键式不饱和单体(以所述乳液聚合物的重量计)，那么羧酸的含量基于乳液聚合物的总组成计算。其他组分包括任选的有机或无机颜料或增量剂(extender)以及常规助剂，例如乳化剂、聚结剂(coalescing agent)、增塑剂、防冻剂、缓冲剂、中和剂、增稠剂、光敏组分、流变改性剂、保湿剂、湿润剂、杀生物剂、增塑剂、消泡剂、UV吸收剂、荧光增亮剂、光或热稳定剂、杀生物剂、螯合剂、分散剂、着色剂、防水剂和抗氧剂。
所述水性粘合剂组合物基本上不含交联剂，即基本上不含能够交联乳液聚合物的独立化合物或组合物。所述水性粘合剂组合物的环氧硅烷组分明确不属于本文所述的“交联剂”。本文所述的“基本上不含交联剂”表示交联剂含量小于0.001重量份，以所述乳液聚合物的干重量计。本文中的“交联剂”包括多官能蜜胺化合物、多官能环氧化合物、多官能异氰酸酯化合物等。
在本发明提供带有可除去纸标签的基材的方法中，所述粘合剂组合物施加到纸标签上。本文中的“纸标签”包括由各种形式的纸、涂覆的纸、印刷的纸、带有金属化涂层或箔的纸形成的标签。可使用常规湿粘合剂施涂方法。所述纸标签上的水性粘合剂组合物可优选施加到基材上，所述基材是例如玻璃和聚合物材料。通常在环境条件例如0-35℃进行干燥。
在从带有可除去纸标签的基材上除去纸标签的方法中，所述可除去纸标签接触碱溶液，接触的时间和温度足以除去所述标签。本文中的“可除去性”是通过下述“洗掉测试”详细I和试验测试方法的结果来判断的。
试验测试方法
耐冰水性
用梅耶(Meyer)棒将湿粘合剂施加到标签，干含量为5-8g/m2。使用尺寸为60×80mm的标签。
粘附到玻璃瓶的标签在室温存放4天。存放后，瓶中装入水，并浸在冰水浴中。记录标签变得可分离的时间。在本试验中，5天或以上的值评为“合格”。
洗掉测试
本试验用于测试粘合剂在热、碱水溶液中的可分离性。
“洗掉能力”是指粘合剂在1.0-2.0％的氢氧化钠溶液中在65-75℃条件下快速完全分离的能力。
使用尺寸为60×80mm的标签。
粘附到玻璃瓶上的标签在标准气候条件下存放至少24小时：23℃±2℃,50％RH±5％RH。存放后，瓶中装入测试温度的水，且立即浸入测试温度的氢氧化钠溶液中。
记录标签分离的时间，以及标签分离后的粘合剂位置。在本试验中，等于或小于的值评为“合格”。
以下实施例用来说明本发明。
所用的缩写
丙烯酸乙酯 EA
丙烯酸丁酯 BA
丙烯酸2-乙基己酯 EHA
甲基丙烯酸甲酯 MMA
甲基丙烯酸丁酯 BMA
甲基丙烯酸 MAA
苯乙烯 Sty
水性乳液聚合物组成(重量计):
乳液聚合物A＝p(50EA/3Sty/25MMA/18MAA)
乳液聚合物B＝p(80EA/20MAA)
乳液聚合物C＝p(62EA/38MAA)
乳液聚合物D＝p(56EA/5EHA/36MAA)
实施例1-2和比较例A-B。水性粘合剂组合物的形成和评估
水性粘合剂组合物用3号棒在湿的24g/m2的水平施加到纸标签，并在室温条件下干燥4天。
SILQUESTTM A-187是购自美国俄亥俄州哥伦布市的短瞬特别化学品有限公司(Momentive Specialty Chemicals Inc)的环氧官能硅烷。
本发明的水性粘合剂组合物(实施例1-2)显示出所需水平的耐冰水性和洗掉性能。

Claims (3)

1.一种水性粘合剂组合物，所述水性粘合剂组合物包含：
a)碱可溶胀性乳液聚合物，所述乳液聚合物包含作为共聚单元的10-35重量％的羧酸单体和至少一种第二烯键式不饱和单体，以所述乳液聚合物的重量计；以及
b)0.1-4重量％的环氧硅烷，以所述乳液聚合物干重量计；
其中所述粘合剂组合物基本上不含交联剂。
2.一种提供带有可除去纸标签的基材的方法，所述方法包括：
(a)形成权利要求1所述的水性粘合剂组合物；
(b)将所述水性粘合剂组合物施涂于纸标签；
(c)对所述施涂的粘合剂组合物进行干燥，或者任其干燥。
(d)将所述带有标签的粘合剂施加到所述基材上。
3.一种从带有可除去纸标签的基材上除去纸标签的方法，所述方法包括:
(a)提供权利要求2所述的带有可除去纸标签的基材；以及
(b)使所述可除去标签与碱溶液接触，所述接触的时间和温度足以除去所述标签。
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