CN107735257A - 低能耗表面基材的热粘合 - Google Patents

低能耗表面基材的热粘合 Download PDF

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CN107735257A
CN107735257A CN201680038637.7A CN201680038637A CN107735257A CN 107735257 A CN107735257 A CN 107735257A CN 201680038637 A CN201680038637 A CN 201680038637A CN 107735257 A CN107735257 A CN 107735257A
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material layer
polymeric substrate
polymeric
adhesive
stimulation
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CN107735257B (zh
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肯尼斯·A·马其赫
杰弗里·R·阿普费尔
肯尼斯·S·马库赫
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Ze Feross Ltd
Zephyros Inc
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Ze Feross Ltd
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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

一种方法，包括准备熔点为约130℃至约190℃的聚合物基材，将材料层置于基材上，所述材料层包含一种或多种聚合物材料，所述材料在至少约100℃液化以与聚合物基材的软化部分混合。使一个或多个基底和材料层受到刺激，温度升高到一个或多个基底和材料层中的预定温度区间，以使得材料层的一种或多种聚合物材料与聚合物基材的软化部分相混合。

Description

低能耗表面基材的热粘合
技术领域
本申请涉及用于粘合聚合物基底的方法和相关粘合剂，包括将材料层设置在基底上，其中所述材料层包含一种或多种聚合物材料，其在至少约100℃温度时液化，使其处于升高的温度时，聚合物基材软化并与材料层混合。
背景技术
为了减轻大多数交通工具重量，运输工具中使用越来越多的聚合物材料。这些聚合物材料的粘附性一直是个问题。无论将两种聚合物材料彼此粘合，还是将聚合物材料与不同的非聚合物材料相粘合，足够的粘附性都是挑战性的，正如粘合和固化的时机一样。通常，热活化粘合剂用于在整个车辆的多个位置。这些热活化粘合剂设置在烤漆炉中，在一定温度下粘合和固化。然而，设置于车辆内的许多位置的粘合剂，其必须烤漆周期外进行粘附和/或固化。为了克服时机问题和粘附聚合物材料的困难，经常会用到既费时又费力的焊接工艺。
因此，在典型的烤漆循环之外需要粘合及粘附过程，同时还使得两个聚合物基材和/或聚合物基材与第二不相似基材之间的实现高强度粘合
发明内容
本发明涉及粘合聚合物基材，通过使用包括金属填料的粘合剂得到，将其暴露于升高的温度时，一部分聚合物基材软化，并且至少一部分粘合剂液化与软化的聚合物基材部分相混合。
本本申请进一步设想一种方法，其包括制备聚合物基材；所述基材具有约130℃至约190℃的熔点，并且在所述基材设置材料层；其中所述材料层包含一种或多种在至少约100℃的温度时液化的聚合物材料，其可与聚合物基材的软化部分混合。该方法可以进一步包括：使一个或多个基材和材料层受到刺激，将温度升高至一个或多个基材和材料层中的预定区域中，以使得材料层中的一种或多种聚合物材料与聚合物基材的软化部分相混合。材料层可以包括粘合剂材料或由粘合剂材料组成。可选择材料层和聚合物基底，以使它们具有相近的熔化温度。每个聚合物基材和材料层的熔融温度可高于80℃。每个聚合物基材和材料层的熔融温度可高于90℃。每个聚合物基材和材料层的熔融温度可高于100℃。每个聚合物基底和材料层的熔化温度可高于120℃。
刺激可包括射频场。材料层可以包含一种或多种乙烯组分和丙烯组分。刺激可激活材料层的组成部分。材料层可以包括金属填料。刺激可激活金属填料。金属填料可以包含锰锌铁氧体。金属填料可以包含铁铁素体。金属填料可以包含铁粉。聚合物基材可以是热塑性塑料。聚合物基材可以包含聚丙烯。材料层可以具有粘合性质。聚合物基材可以通过材料层粘合到第二聚合物基材上。材料层可以是薄膜。材料层可以位于粘合剂层和聚合物基材之间。聚合物基材可以是运输车辆的内部板。材料层在受到刺激时可形成泡沫。材料层可与受到刺激时接触形成泡沫层的粘合剂相接触。聚合物基材可以包含金属组分。材料层可以包含聚合物组分和环氧树脂组分，其中聚合物组分与聚合物基材混合，但环氧树脂组分不与聚合物基材混合。聚合物基材可以包含聚丙烯，并且材料层包含一种或多种乙烯组分，其中，乙烯组分受到刺激时液化并与聚合物基材的聚丙烯共混。金属填料可以包括镍。金属填料可以包括锰锌铁氧体，铁铁素体或镍其中的一种或多种的组合。材料层可以形成为网格。材料层可以是柔性层。材料层可包括占材料层至少约20％的重量比例填料。材料层可以包括占材料层至少约30％的重量比例的填料。材料层可以包括占材料层至少约40％的重量比例的填料。
具体实施方式
这里给出的描述和说明旨在使本领域的技术人员熟悉本发明，其原理及其实际应用。本发明中具体实施方式并非旨在穷举或限制本发明。本发明的保护范围应该参照权利要求，以及权利要求的等同实施方式来确定。所有公开的文献和参考材料，包括专利申请和出版物，其公开内容作为参考引用于本文中。另外的权利要求中也概括了其他的组合方式，这些组合方式也记载下述的书面描述中作为参考。
本申请要求美国申请号为62/188,865，申请日为2015年7月6日的优先权，并且优先权文本的全部内容以引用方式与本申请相结合。
本申请涉及一种粘合聚合物基材的制备方法，该方法省略了焊接步骤。用于粘合的聚合物材料可以是聚酰胺，聚烯烃(例如聚乙烯，聚丙烯或其他)，聚碳酸酯，聚酯(例如聚对苯二甲酸乙二醇酯)，环氧基材料，热塑性聚氨酯或其任何组合。优选的聚合物基材可以是聚丙烯材料。用于粘合聚合物基材的粘合剂(例如，材料层)可以是可发泡的粘合剂。当暴露于刺激物时，粘合剂可以起泡，固化或其任何组合。这种刺激物可以包括热量(可以通过感应加热来施加)，光，电，压力，冷却，湿度等。如本文所述，固化通常表示粘合剂材料的任何硬化，硬化，固化等。
为了有效地将粘合剂材料粘合到聚合物基材上，可将一部分粘合剂与一部分聚合物基材的相混合。更具体地，在激活粘合剂时，粘合剂开始软化和/或液化，并与聚合物基材的软化部分混合。粘合剂中的特定组分可易与聚合物基材液化及混合。在实施例中，粘合剂包括乙烯组分，其在粘合剂活化时，可与一部分的聚合物基材的液化及混合。聚合物基材还可以包括可与粘合剂的相应聚合物组分软化并混合的材料。这种材料可以是聚合材料。在实例中，聚合物基材包括聚丙烯组分，其可软化与粘合剂组分相混合，该组分可以是如上所述的乙烯组分。
可在粘合剂的选定区域，基底或其任何组合处给予必要的刺激。因此软化可沿聚合物基材整体或仅沿着基材的一部分而发生。在与部分粘合剂的相接触的小区域基底上，可选择性地给予刺激。在实施例中，在一个或多个粘合剂或聚合物基底中，施加射频或中频范围的磁场。磁场通过感应加热的方式来加热材料。在一个或多个第一聚合物基底，粘合剂或第二聚合物基底(其通过粘合剂粘附到第一聚合物基底)上给予刺激。
因此，一种或多种粘合剂或聚合物基材可包括有助于加热材料的金属填充材料。这样的金属填充材料可包括任何合适的金属填充物，具体可以包括镍，铁氧体，锌，锰或铁中的一种或任意组合。金属填料可包含大部分的粘合剂。磁性填料可占总粘合剂至少10％的重量比例。磁性填料可以以总粘合剂的至少20重量％的量存在。磁性填料可占总粘合剂的至少30％的重量比例。磁性填料可占总粘合剂的至少40％的重量比例。磁性填料可占总粘合剂的不超过80％的重量比例。磁性填料可占总粘合剂的不超过60％的重量比例。磁性填料可占总粘合剂的不超过50％的重量比例。
粘合剂的形式可以根据应用的需要而变化。选择合适的粘合剂的形式，使得在活化时，粘合剂的厚度相对均匀。可选择适当的粘合剂的形式，使基底表面(其可以是A级表面)的通读被最小化或基本消除。粘合剂可是膜形式。粘合剂可是网状。粘合剂可以是柔性的，使得它可应用于弯曲的基底上。粘合剂可以是干燥的可触摸的，也可是粘性的。粘性粘合剂可包括处理层或表面处理，使得粘合剂在应用一个或多个基材时，易于处理。
粘合剂材料通常包括一种或多种聚合物，包括共聚物和三元共聚物，其可以包括各种不同的聚合物，例如塑料，热塑性塑料，弹性体，热固性塑料，热固性塑料，及其组合等。例如，但不限于，包含适量聚合物的聚合物混合剂，包括卤化聚合物，聚碳酸酯，聚酮，聚氨酯，聚酯，硅烷，砜类，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，橡胶，聚苯醚，邻苯二甲酸酯，乙酸酯(例如EVA)，丙烯酸酯，甲基丙烯酸酯(例如乙烯丙烯酸甲酯聚合物)或其混合物。其它可能的聚合物材料可包括但不限于聚烯烃聚苯乙烯(例如聚乙烯，聚丙烯)，聚丙烯酸酯，聚(氧化乙烯)，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，聚氯乙烯，聚甲基丙烯酸甲酯，聚醋酸乙烯酯，聚偏氯乙烯，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。粘合剂可以包括乙酸乙烯酯(例如乙烯乙酸乙烯酯)，丙烯酸酯和/或甲基丙烯酸酯(例如，丙烯酸丁酯和/或丙烯酸甲酯的共聚物)和环氧/弹性体加合物中的一种或多种。例如，但不限于，粘合剂也可以是基于EVA的材料，包括可具有α-烯烃的乙烯共聚物或三元共聚物。作为共聚物或三元共聚物，聚合物可以由两种或三种不同的单体组成，例如，具有高化学活性的小分子，其能够与类似分子连接。在一个实施方案中，粘合剂包括乙烯共聚物，乙烯和丙烯酸丁酯的共聚物或其一些组合。
在使用时，这些聚合物可包含小部分或更大部分的粘合剂材料(例如高达85％重量份数或更高)。优选地，所述一种或多种聚合物占粘合剂材料的约0.1％至50％的重量比例，更优选约20％至40％的重量比例，甚至更优选约25％至35％的重量比例。
粘合材料还可以包括粘合促进剂，包括但不限于环氧材料，丙烯酸酯，烃树脂等。粘合促进剂所占比例可为至少约2％的重量比例，至少约5％或甚至至少约9％的重量比例。粘合促进剂占比例可为少于约20％的重量比例，小于约15％或甚至至少约10％的重量比例。
可将一种或多种固化剂和/或固化剂促进剂添加到粘合剂材料中。固化剂和固化剂促进剂的量可根据所需的蜂窝状结构的类型，粘合剂材料的期望膨胀量(如果有的话)，期望的膨胀速率，粘合剂材料的期望结构性质，期望的固化条件(例如，加工条件)等而改变。材料组合物中的固化剂或固化剂促进剂范围可为约0.01％至50％重量分数，或甚至1％至20％重量分数。
合适的固化剂例如包括过氧化物固化和/或交联剂。其它合适的固化剂可从下述组份中得到，例如脂族，芳族胺中，或其各自的加合物，酰氨基胺，聚酰胺，脂环族胺，酸酐，多羧酸聚酯，异氰酸酯，酚基树脂(例如苯酚或甲酚酚醛清漆树脂，苯酚萜烯，聚乙烯苯酚或双酚A甲醛共聚物，双羟基苯基烷烃等)或其混合物。特定的固化剂包括改性和未改性的聚胺或聚酰胺，如三亚乙基四胺，二亚乙基三胺四乙烯戊胺，氰基胍，双氰胺等。另一种可能的固化剂是二酰肼，特别是间苯二甲酸二酰肼。还可提供用于制备粘合剂的固化剂促进剂(例如改性或未改性的脲如亚甲基二苯基双脲，咪唑或其组合)。另一种固化剂促进剂是二季戊四醇五丙烯酸酯(SR-399)。
可将一种或多种发泡剂添加到粘合剂材料中用于产生惰性气体，所述惰性气体根据需要在活性材料内形成开放和/或封闭的蜂窝状结构。通过这种方式，可以降低由该材料生产的产品的密度。此外，材料膨胀可提高座椅的能力，减震或者两者兼而有之。
发泡剂可以包括一个或多个含氮基团，例如酰胺，胺等。合适的发泡剂的包括偶氮二甲酰胺，二亚硝基五亚甲基四胺，4,4'次氧化双(苯磺酰肼)，三肼三嗪和N，N'-次二甲基-N，N'-次二亚硝基对苯二甲酰胺。
活性材料中也可具有用于发泡剂的促进剂。各种促进剂可用于提高发泡剂生成惰性气体的速率。一种优选的发泡剂促进剂是金属盐，或者是氧化物，金属氧化物如氧化锌。其他优选的促进剂包括改性和未改性的噻唑或咪唑。
粘合剂材料还可以包括一种或多种填充剂。优选地，填料包括通常不与粘合剂材料中的其它组分发生反应的材料。虽然在粘合剂材料内的填料通常以相对较低重量的占据一定空间，填料使活性材料具有预期的性质如强度和耐冲击性。
填料包括二氧化硅，硅藻土，玻璃，粘土(例如包括纳米粘土)，滑石，颜料，着色剂，玻璃珠或气泡，玻璃纤维，碳纤维或陶瓷纤维，尼龙或聚酰胺纤维(例如Kevlar)抗氧化剂等。这些填料，特别是粘土，在材料流动时可辅助活性材料自流平。用于填料的粘土包括来自高岭石，伊利石，绿泥石，绿泥石或海泡石基团的粘土，其可进行煅烧。合适的填料包括但不限于滑石，蛭石，叶蜡石，锌蒙脱石，皂石，绿脱石，蒙脱土或其混合物。粘土还可以包括少量的其他成分，例如碳酸盐，长石，云母和石英。填料还可以包括氯化铵，例如二甲基氯化铵和二甲基苄基氯化铵。也可使用二氧化钛。
在一个实施例中，填料可以为一种或多种矿物或石类型的填料如碳酸钙，碳酸钠等。在另一个优选实施例中，硅酸盐矿物如云母可以用作填料。
当使用时，活性材料中的填料占活性材料的重量比例可为：10％至少于90％以下，但优先地，为20％至55％。根据一些实施例，活性材料可包括约0％至约3％，优选地略小于1％重量比例的粘土或类似填料。粉状无机型填料(例如：约0.01至约50，更优选约1至25微米平均粒径)所占重量比例约1％至70％，更优选约5％至约20％。
表1中列出的以下实施例用于说明本发明，但并不意在限制保护范围。除非另有说明，所有份数和百分数均以重量比例计。
虽然本发明描述了材料层(例如，粘合剂层)和聚合物基材，也可使用其它的基材和和粘合剂层。这些附加层可以提供额外的力度，稳定性，粘附性，支持或类似。
本发明中所指的成份的重量份数是指100重量份中的具体提及的组合物所占的份数。在本申请中列举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，并且任何较低值和较高值之间存在至少两个单位的间隔。例如，如果所述组分的量或过程变量的值，例如温度，压力，时间等，例如1-90，优选20-80，更优选为在本说明书是，该范围具体包括 等范围。对于小于1的数值，可用适当的单位例如0.0001,0.001,0.01或0.1。这些具体的例子意在说明所列举的最低值和最高值之间的数值的所有可能的组合，本申请所述的最高值中也以类似的方式进行说明。除非另有说明，所有范围都包括端点，以及端点之间的所有数字。与范围有关的“约”或“近似”适用于范围的两端点。因此，“约20至30”旨在覆盖“约20至约30”，包括至少指定的端点。用于描述组合的术语“基本上由...组成”应该包括所确定的要素，成分，组分或步骤，以及不显著影响组合的基本特性和新颖特性的其他要素成分，组分或步骤。本文中使用术语“包括”或“包括”来描述元素、成分、组分或步骤的组合，也包括到基本上由元素、成分、组分或步骤组成的实施例。多个元素、成分、组分或步骤可以通过单个整合的元素、成分、组分或步骤得到。或者，单个集成元件、成分、组件或步骤可以分成单独的多个元素、成分、组分或步骤。用于描述元件、成分、部件或步骤的“一”或“一个”，并非旨在排除其他元件，成分，部件或步骤。

Claims (28)

1.一种方法，包括：
准备聚合物基材，所述基材具有约130℃至190℃的熔点；
将材料层设置于所述基材上，所述材料层包含一种或多种聚合物材料，所述聚合物材料在至少约100℃的温度时液化，并与所述聚合物基底的软化部分混合；
使一个或多个所述基底和所述材料层受到刺激，使得温度升高到所述一个或多个基底和材料层中的预定温度区间，使得所述材料层中的一种或多种聚合物材料与聚合物基材的软化部分相混合。
2.根据权利要求1所述的方法，其特征在于：所述刺激包括无线电频率电磁场或中频电流。
3.根据权利要求1或2所述的方法，其特征在于：所述材料层包含一种或多种乙烯组分和丙烯组分。
4.根据权利要求1至3中任一项所述的方法，其特征在于：所述刺激可激活所述材料层的组分。
5.根据权利要求1至4中任一项所述的方法，其特征在于：所述材料层包括金属填料。
6.根据权利要求5所述的方法，其特征在于：所述刺激可激活所述金属填料。
7.根据权利要求1至6中任一项所述的方法，其特征在于：所述金属填料包含锰锌铁氧体。
8.根据权利要求1至7中任一项所述的方法，其特征在于：所述金属填料包含铁铁素体。
9.根据权利要求1至8中任一项所述的方法，其特征在于：所述聚合物基材是热塑性塑料。
10.根据权利要求1至9中任一项所述的方法，其特征在于：所述聚合物基材包含聚丙烯。
11.根据权利要求1至10中任一项所述的方法，其特征在于：所述材料层具有粘合性质。
12.根据权利要求1至11中任一项所述的方法，其特征在于：所述聚合物基材通过所述材料层粘附至第二聚合物基材。
13.根据权利要求1至12中任一项所述的方法，其特征在于：所述材料层是膜。
14.根据权利要求1至13中任一项所述的方法，其特征在于：所述材料层位于粘合剂层和所述聚合物基材之间。
15.根据权利要求1至14中任一项所述的方法，其特征在于：所述聚合物基材是运输车辆的内部板。
16.根据权利要求1至15中任一项所述的方法，其特征在于：所述材料层受到所述刺激时形成泡沫。
17.根据权利要求1至16中任一项所述的方法，其特征在于：所述材料层与受到所述刺激时形成泡沫层的粘合剂相接触。
18.根据权利要求1至17中任一项所述的方法，其特征在于：所述聚合物基材包含金属组分。
19.根据权利要求1至18中任一项所述的方法，其特征在于：所述材料层包括聚合物组分和环氧树脂组分，所述聚合物组分与所述聚合物基材混合，所述环氧树脂组分不与所述聚合物基材混合。
20.根据权利要求1至19中任一项所述的方法，其特征在于：所述聚合物基材包含聚丙烯，所述材料层包含一种或多种乙烯组分，所述乙烯组分受到所述刺激时液化，并与所述聚合物基材中的聚丙烯相混合。
21.根据权利要求1至20中任一项所述的方法，其特征在于：所述金属填料包括镍。
22.根据权利要求1至21中任一项所述的方法，其特征在于：所述金属填料包括锰锌铁氧体，铁铁素体或镍其中的一种或多种的组合。
23.根据权利要求1至22中任一项所述的方法，其特征在于：所述材料层成型为网状物。
24.根据权利要求1至23中任一项所述的方法，其特征在于：所述材料层是柔性层。
25.根据权利要求1至24中任一项所述的方法，其特征在于：所述材料层包括占所述材料层至少约20％重量比例的填料。
26.根据权利要求1至25中任一项所述的方法，其特征在于：所述材料层包括占所述材料层至少约30％重量比例的填料。
27.根据权利要求1至24中任一项所述的方法，其特征在于：所述材料层包括占所述材料层至少约40％重量比例的填料。。
28.一种由权利要求1至28中任一项所述的方法形成的一种车辆内部板。
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