CN109715710B - 用于结合异种材料的丙二酸酯和氰基丙烯酸酯粘合剂 - Google Patents

用于结合异种材料的丙二酸酯和氰基丙烯酸酯粘合剂 Download PDF

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CN109715710B
CN109715710B CN201780057663.9A CN201780057663A CN109715710B CN 109715710 B CN109715710 B CN 109715710B CN 201780057663 A CN201780057663 A CN 201780057663A CN 109715710 B CN109715710 B CN 109715710B
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adhesive
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CN109715710A (zh
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迈克尔·恰普利茨基
肯·马其赫
吕源
凯文·希克斯
奥斯丁·奥康纳
詹森·沃克
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Zephyros Inc
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Abstract

本发明提出了一种方法，包括提供第一基底和第二基底，将引发剂设置于所述第一基底或第二基底的表面上，所述引发剂包括用于引发可聚合粘合剂聚合的物质，将可聚合粘合剂设置于所述第一基底和第二基底的表面上。所述粘合剂包括单官能、双官能或多官能亚甲基丙二酸酯或氰基丙烯酸酯，并接触所述第一基底和第二基底。

Description

用于结合异种材料的丙二酸酯和氰基丙烯酸酯粘合剂
技术领域
本发明涉及可聚合的粘合剂，其在与引发剂或特定表面接触时产生聚合反应。所述粘合剂可用于将两个表面粘合在一起，并且当所述粘合剂暴露于一种刺激时，两个表面可容易地分离。
背景技术
聚合物粘合剂经常用于层压结构中。然而，这种粘合剂通常难以去除，并且需要时间和/或化学品来去除残留物。因此，当层压结构需要频繁地进行改动以获得收益时(例如，当所述层压结构本质上是装饰性的或用作广告表面时)，这种粘合剂的使用是不受欢迎的。
美国专利号为8609885、8884051和9181365的专利，以及美国专利公开号2014/0329980和2015/0056879的专利申请与本发明相关，并且出于所有目的通过引用结合在此。
尽管有上述教导，目前仍然需要一种粘合剂，用于有效地在表面上进行粘附，并且可简单地去除，同时只留下很少或没有残留物。
发明内容
本发明满足了上述需求中的一个或多个，本发明的方法提出了一种粘合层压结构的方法，包括提供第一基底和第二基底，将引发剂设置于第一基底的第一表面上，所述引发剂包括一种用于引发可聚合粘合剂的聚合的物质。所述方法还可包括将可聚合粘合剂设置于第二基底的第一表面上，该粘合剂包括单官能、双官能或多官能亚甲基丙二酸酯或氰基丙烯酸酯，并使第一基底的第一表面与第二基底的第一表面接触，使得引发剂引起粘合剂的聚合。
所述第一基底可以是一个膜层。所述膜层可以是聚氟乙烯膜。所述粘合剂可以在与第二基底接触时被热活化。所述方法可包括在粘合剂与引发剂接触后5分钟、3分钟或甚至1分钟内使粘合剂聚合。所述第二基底可选自单板、刨花板、蜂窝板、白板、聚合物材料、膜层或其组合。
所述引发剂可以是苯甲酸钠。所述第二基底可包括苯氧基组分。可以重新加热层压结构以从第二基底上移除第一基底，使粘合剂仅与第二基底接触，在第一基板上只残留极少量的粘合剂残留物。所述方法可以包括从第一基底上移除第二基底，而基本上在第一基底上没有残留粘合剂残留物。
所述方法可包括通过对粘合剂施加刺激从而从第一基底上移除第二基底。所述方法可以包括通过向粘合剂施加热量，UV光线或化学物质从而从第一基底上移除第二基底。所述第一表面或第二表面中的一个或多个可以是交通工具的面板，例如公共汽车、火车、船或飞机。所述第一表面或第二表面中的一个或多个可以接收广告或装饰材料。所述粘合剂可以是热塑性材料。在第一基底与第二基底分离时，所述粘合剂仅与第二基底接触，并且第一基底基本上不含任何剩余的粘合剂。所述方法可以包括将第一基底与第二基底接触之前在第一基底和第二基底中的一个或多个添加纹理的步骤。
本发明还涉及一种粘合层压结构的方法，包括提供第一基底和第二基底，并将可聚合粘合剂设置于第二基底的第一表面上，所述粘合剂包括单官能、双官能或多官能亚甲基丙二酸酯或氰基丙烯酸酯。所述方法还可包括使第一基底的第一表面与第二基底的第一表面接触，其中第一基底的材料成分与粘合剂反应并引起粘合剂的聚合。请求保护的所述方法可包括将引发剂添加到第一基底的步骤。
具体实施方式
本文提供的解释和说明旨在使本领域其他技术人员熟悉本发明，其原理和实际应用。如上所述的本发明的具体实施方案并非旨在穷举或限制本发明。应参考所附权利要求以及这些权利要求所赋予的等同物的全部范围来确定本发明的范围。所有文章和参考文献的公开内容，包括专利申请和出版物，出于所有目的通过引用并入。也可能从权利要求中获取其他组合，并通过引用结合到本书面描述中。
本申请要求申请日为2016年9月19日的美国临时申请号62/396,559的优先权，该申请的内容为了所有目的通过引用结合于此。
在此描述的粘合材料可包括具有如下化学式的二羰基化合物：
Figure GDA0002025224940000031
其粘度为约50cps至约500cps，并通过以下方式之一引发：(i)在加入或不加入引发剂的前提下于室温自发聚合(例如，在约1分钟内)；或者(ii)在加入或不加入引发剂的前提下于特定的延迟时间后在室温下聚合。可以使用引发剂。
所述引发剂可以是酸。所述引发剂可以是酸的盐或酯。所述引发剂可以是羧酸。所述引发剂可包括碳酸、甲酸、苯甲酸、乙酸、丙酸、己酸和这些酸的盐或酯中的一种或多种。所述引发剂可用于加速反应时间，但该特性不是必需的。然后所述引发剂可用于控制聚合速率。在某些情况下，通过加热可以加速聚合，但该特性不是必需的。
可以将粘合剂施加到不含任何引发剂的基底上。施加粘合剂的基底可以是非反应性基底(例如，包含不会使粘合剂过早聚合的材料)。可以将所述引发剂(如果存在的话)施加到基底上，该基底最终将粘合到含有粘合剂的基底上。或者，所述基底可以由反应性材料形成(例如，包括将使粘合剂聚合的材料)。因此，所述粘合剂可以施加于基底上而不用担心过早聚合。
接收粘合剂或用粘合剂粘合到另一基底上的基底(例如，第一基底和第二基底)可包括不同的材料。它们可能具有金属性。它们可能是聚合物。它们可能是复合材料。它们可含有一种或多种增强材料(例如增强纤维)。所述基底可以是层压材料。它们可以是装饰材料。一个或多个基底可以是基本上柔性的(例如，能够卷起或折叠)。所述基底可以是单板、刨花板、蜂窝板、白板、膜层或其组合。所述基底可包括一种或多种热塑性改性剂，例如包含侧羟基部分的聚醚。特别理想的热塑性聚醚是苯氧基树脂。如本文所用，苯氧基树脂是多羟基醚，具有沿聚合物主链和侧羟基基团的醚键。酚类双官能环氧树脂和双官能酚的反应产物(例如双酚A环氧树脂与双酚A的反应产物)是一种有用的苯氧基树脂。也可以直接由双酚(例如双酚A)和环氧氯丙烷合成一种类似的材料。末端环氧基团可以开环以产生末端α二醇基团。所述苯氧基树脂的重均分子量为至少约5,000，更优选至少约25,000，更优选至少约50,000至约100,000，更优选小于约75,000，更优选小于约60,000。其它热塑性聚醚在其主链中包括芳族醚/胺重复单元，例如聚醚胺，聚(氨基醚)，单乙醇胺和二缩水甘油醚的共聚物，以及它们的组合等。
在使用丙二酸酯和氰基丙烯酸酯时，用于配制粘合剂的许多化学组分可能会使粘合剂不稳定。因此，粘合剂可仅包含丙二酸酯、氰基丙烯酸酯或其某些组合。然而，许多材料也可以改善粘合剂的物理特性而不损害粘合剂的聚合能力。因此，粘合剂可以包括一种或多种另外的单体，一种或多种聚合物，或一种或多种填料(例如颜料)。粘合剂也可能不需要引发剂聚合。作为一个实例，粘合剂可在与某些基底(例如，第一基底)接触时聚合。或者，取决于温度或可用的光线，粘合剂可随时间聚合。引发剂可以仅用于增加粘合剂聚合的速度。
所述粘合剂可包括一种或多种另外的单体。所述单体可选自丙烯酸酯、丙烯酸、丙烯酸乙酯、甲基丙烯酸酯、氰基丙烯酸乙酯、乙烯、环氧乙烷、丙烯腈、1,3-丁二烯、丙烯酸丁酯、氰基丙烯酸丁酯、环丁烯、二环戊二烯、3,4-二甲氧基苯乙烯、甲基丙烯酸缩水甘油酯、苯乙烯、(羟乙基)甲基丙烯酸酯、N-(2-羟丙基)甲基丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸、甲基丙烯腈、2-氯丙烯酸甲酯、2-氟丙烯酸甲酯、丙烯酸甲酯、氰基丙烯酸甲酯、异氰酸甲酯、甲基丙烯酸甲酯、1,8-辛二醇、辛烯、辛基氰基丙烯酸酯、2-辛基氰基丙烯酸酯、三亚甲基碳酸酯、苯二胺、四氟乙烯、乙酸乙烯酯、氯乙烯、乙烯基醚、或它们的任意组合。
本发明的粘合剂材料还可包括一种或多种填料，包括但不限于颗粒材料(例如粉末)、珠粒、微球等。可以使用的填料包括二氧化硅、玻璃、滑石、颜料、着色剂、玻璃珠或气泡。合适的填料还包括但不限于硅灰石、滑石、蛭石、叶蜡石、锌蒙脱石、皂石、绿脱石、蒙脱石或其混合物。可以使用一种或多种矿物类或石头类填料如碳酸钙、碳酸钠等作为填料。诸如云母的硅酸盐矿物可用作填料。
当使用时，按重量计粘合剂中填料的量可以为2％至大于30％或更高，但更优选的是约8％至25％。根据一些实施方案，按重量计，粘合剂可包含约0％至约3％，更优选略小于1％的二氧化硅或类似的填料。粉末(例如约0.01至约50微米，更优选约1至25微米平均粒径)矿物型填料可占约5％至40％重量，更优选占约10％至约25％重量。
可以将几种另外的聚合物掺入粘合剂中，例如通过共聚合、共混或其它方式加入。可以适当地掺入粘合剂材料中的其他聚合物包括但不限于卤化聚合物、聚碳酸酯、聚酮、聚氨酯、聚酯、硅烷、砜、烯丙基、烯烃、苯乙烯、乙酸酯、乙烯乙酸乙烯酯、丙烯酸酯、甲基丙烯酸酯、环氧树脂、硅氧烷、酚醛树脂、橡胶、聚苯醚、邻苯二甲酸酯或其混合物。其他潜在的聚合物材料可以是或可包括但不限于聚乙烯、聚丙烯、聚苯乙烯、聚烯烃、聚丙烯酸酯、聚(环氧乙烷)、聚(乙烯亚胺)、聚酯、聚氨酯、聚硅氧烷、聚醚、聚磷腈、聚酰胺、聚酰亚胺、聚异丁烯、聚丙烯腈、聚(氯乙烯)、聚(甲基丙烯酸甲酯)、聚(乙酸乙烯酯)、聚(偏二氯乙烯)、聚四氟乙烯、聚异戊二烯、聚丙烯酰胺、聚丙烯酸、聚甲基丙烯酸酯和聚缩醛。每种单体或全部单体的用量，包括丙二酸酯和氰基丙烯酸酯组分(如果存在的话)，按重量计可以为0.05％至大于80％或更高，但更优选的是约1％至60％，或甚至为5％至40％。
所述粘合剂可以包括一种或多种另外的聚合物(例如，共聚物)，其通常为但不一定是共聚物或三元共聚物，其可以包括各种不同的聚合物，例如热塑性塑料、弹性体、热固性塑料、热固性树脂或其组合等。可以适当地掺入粘合剂中的聚合物包括但不限于卤化聚合物、聚碳酸酯、聚酮和聚氨酯、聚酯、硅烷、砜、烯丙基、烯烃、苯乙烯、丙烯酸酯、甲基丙烯酸酯、环氧树脂、硅氧烷、酚醛树脂的聚合物、橡胶、聚苯醚、对苯二甲酸盐、乙酸盐(例如EVA)、丙烯酸盐、甲基丙烯酸盐(例如乙烯丙烯酸甲酯聚合物)或其混合物。其他潜在的聚合物材料可以是或可包括但不限于聚烯烃(例如聚乙烯，聚丙烯)、聚苯乙烯，聚丙烯酸酯，聚环氧乙烷、聚(乙烯亚胺)、聚酯、聚氨酯、聚硅氧烷、聚醚、聚磷腈、聚酰胺、聚酰亚胺、聚异丁烯、聚丙烯腈、聚氯乙烯、聚(甲基丙烯酸甲酯)、聚乙酸乙烯酯、聚(偏二氯乙烯)、聚四氟乙烯、聚异戊二烯、聚丙烯酰胺、聚丙烯酸、聚甲基丙烯酸酯。尽管不是必需的，但粘合剂可能包括一种或多种乙烯聚合物或共聚物，例如乙烯丙烯酸酯，乙酸乙烯酯等。乙烯甲基丙烯酸酯和乙烯乙酸乙烯酯是两种优选的乙烯共聚物。当使用时，按重量计，一种或多种另外的聚合物占粘合剂约0.1％至约50％，更优选约1％至约20％，甚至更优选约5％至约15％。
所述粘合剂可以提供以下好处中的一个或多个。粘合剂可以在其他粘性材料上形成无粘性表面。粘合剂可以将第二材料(例如，膜)粘附到基底上。粘合剂可以允许第二基底与第一基底脱粘，且第一基底上只有极少量残留物。粘合剂可以为第一基底提供足够的粘合力，所述第一基底包括通常难以进行粘附的材料。
如本文所用，除非另有说明，否则本发明可以从一个种类(名单)中排除任何组成；和/或马库什分组的任何组成可以从分组中排除。
除非另有说明，否则本文所述的任何数值包括以一个单位为增量的从较低值到较高值的所有值，条件是在任何较低值和任何较高值之间存在至少2个单位的间隔。作为一个例子，如果提及了组分的量、性质或过程变量的值，例如温度、压力、时间等，例如为1至90，优选从20到80，更优选从30到70，意思是中间范围值，例如15到85,22到68,43到51,30到32等均在本说明书的教导内。同样地，各个中间值也在本教导内。对于小于1的值，视情况将一个单位视为0.0001,0.001,0.01或0.1。这些仅作为实例，用以说明所列举的最低值和最高值之间的数值的所有可能组合应被认为在本申请中以类似方式明确陈述。可以看出，本文中表示为“重量份”的量也考虑了以重量百分比表示的相同范围。因此，在“至少'x'重量份所得组合物”的类似表达中也考虑了以所得组合物的重量百分比表示相同所述量的“x”的范围。
除非另有说明，否则所有范围包括端点和端点之间的所有数字。结合范围使用“约”或“近似”适用于范围的两端。因此，“约20至30”旨在涵盖“约20至约30”，包括至少指定的端点。
所有文章和参考文献的公开内容，包括专利申请和出版物，出于所有目的通过引用结合到本文中。术语“基本上由…组成”应包括所指出的元素，成分，组分或步骤，以及不会对组合的基本和新颖特征产生实质影响的其他元素成分、组分或步骤。术语“包含”或“包括”用以描述本发明的元素、成分、组分或步骤的组合，还涵盖由所述元素、成分、组分或步骤组成或基本上由其组成的实施方案。
可以通过单个集成元件、成分、组件或步骤提供多个元件、成分、组件或步骤。或者，单个整合元件、成分、组分或步骤可以分成单独的多个元素、成分、组分或步骤。描述元素、成分、组分或步骤的“一”或“一个”并非旨在排除额外的元素、成分、组分或步骤。
应理解，以上描述旨在是说明性的而非限制性的。除了提供的示例之外，许多实施例以及许多应用在阅读以上描述后对于本领域技术人员而言将是显而易见的。因此，本发明的范围不应参考以上描述来确定，而应参考所附权利要求以及这些权利要求所赋予的等同物的全部范围来确定。所有文章和参考文献的公开内容，包括专利申请和出版物，出于所有目的通过引用并入。在此公开的主题的任何方面在以下权利要求中的省略不构成对这样的主题的免责声明，也不应该认为发明人不认为这样的主题是所公开的发明主题的一部分。

Claims (25)

1.一种粘合层压结构的方法，包括：
提供第一基底和第二基底；
将引发剂设置于第一基底的第一表面上，所述引发剂包括用于引发可聚合粘合剂聚合的物质；
将可聚合粘合剂设置于第二基底的第一表面上，所述粘合剂包括单官能、双官能或多官能亚甲基丙二酸酯或氰基丙烯酸酯；
使第一基底的第一表面与第二基底的第一表面接触，使得引发剂引起粘合剂的聚合；
所述第一基底是膜层；
所述第二基底包括苯氧基成分；
所述粘合剂是热塑性材料。
2.根据权利要求1所述的方法，其中所述膜层是聚氟乙烯膜。
3.根据前述权利要求1或2所述的方法，其中所述粘合剂在与所述第二基底接触时被热活化。
4.根据权利要求1或2所述的方法，包括在使所述粘合剂与所述引发剂接触后5分钟、3分钟或甚至1分钟内聚合所述粘合剂。
5.根据权利要求1或2所述的方法，其中所述第二基底选自单板、刨花板、蜂窝板、白板、聚合物材料、膜层或其组合。
6.根据权利要求1或2所述的方法，其中所述引发剂是苯甲酸钠。
7.根据权利要求1或2所述的方法，包括从所述第一基底上移除所述第二基板，同时所述第一基底没有粘合剂残留物。
8.根据权利要求1或2所述的方法，包括对所述粘合剂施加刺激从而从所述第一基底上移除所述第二基底。
9.根据权利要求1或2所述的方法，包括向所述粘合剂施加热量、UV光线或化学物质从而从所述第一基底移除所述第二基底。
10.根据权利要求1或2所述的方法，其中所述第一表面或第二表面中的一个或多个是交通工具的面板。
11.根据权利1或2所述的方法，其中所述第一表面或第二表面中的一个或多个接收广告或装饰材料。
12.根据权利要求1或2所述的方法，其中在将所述第一基底与所述第二基底分离时，所述粘合剂仅与所述第二基底接触，并且所述第一基底不含任何剩余的粘合剂。
13.根据权利要求1或2所述的方法，包括在将所述第一基底与所述第二基板接触之前在所述第一基底和第二基底中的一个或多个添加纹理的步骤。
14.一种粘合层压结构的方法，包括：
提供第一基底和第二基底；
将可聚合粘合剂设置于第二基底的第一表面上，所述粘合剂包括单官能、双官能或多官能亚甲基丙二酸酯或氰基丙烯酸酯；
使所述第一基底的第一表面与第二基底的第一表面接触，其中所述第一基底的材料成分与粘合剂反应并引起粘合剂的聚合；
所述第二基底是膜层；
所述粘合剂是热塑性材料。
15.根据权利要求13所述的方法，其中所述粘合剂的聚合时间为至少5分钟、至少15分钟、至少30分钟、或甚至至少60分钟。
16.根据权利要求15所述的方法，其中所述膜层是聚氟乙烯膜。
17.根据权利要求14或15所述的方法，其中暴露于至少200℉、至少220℉或甚至至少250℉的温度时，所述第一基底和粘合剂可以很容易地从所述第二基底上移除，且只有很少或没有残留物留在所述第二基底上。
18.根据权利要求14或15所述的方法，其中在与所述第二基底接触之前将引发剂设置于所述第一基底上。
19.根据权利要求14或15所述的方法，其中所述第二基底包括苯氧基成分。
20.根据权利要求14或15所述的方法，其中所述层压结构可以被重新加热以从所述第二基底上移除所述第一基底，所述粘合剂仅与所述第一基底接触且所述第二基底上只残留极少量的粘合剂残留物。
21.根据权利要求14或15所述的方法，包括通过对所述粘合剂施加刺激从而从所述第一基底上移除所述第二基底。
22.根据权利要求14或15所述的方法，包括通过向所述粘合剂施加热量、UV光线或化学物质从而从所述第一基底上移除所述第二基底。
23.根据权利要求14或15所述的方法，其中所述第一表面或第二表面中的一个或多个是交通工具的面板。
24.根据权利要求14或15所述的方法，其中所述第一表面或第二表面中的一个或多个接收广告或装饰材料。
25.根据权利要求14或15所述的方法，包括在将所述第一基底与所述第二基底接触之前在所述第一基底和第二基底中的一个或多个添加纹理的步骤。
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