CN101048446B - 无底漆粘合的方法 - Google Patents

无底漆粘合的方法 Download PDF

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CN101048446B
CN101048446B CN200580037208XA CN200580037208A CN101048446B CN 101048446 B CN101048446 B CN 101048446B CN 200580037208X A CN200580037208X A CN 200580037208XA CN 200580037208 A CN200580037208 A CN 200580037208A CN 101048446 B CN101048446 B CN 101048446B
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tackiness agent
solvent
polycarbonate substrate
assembly
coating
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CN101048446A (zh
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S·Z·迈赫迪
M·N·伯里斯
M·M·亨德森
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Dow Chemical Co
DDP Specialty Electronic Materials US LLC
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Dow Global Technologies LLC
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Abstract

本发明涉及将塑料组件连接到另一个组件的方法，其中在塑料组件上不存在底漆的情况下使用粘合剂将塑料组件与其它组件粘合且粘合剂基本上不含溶剂。在一个实施方案中，在基材上不存在底漆的情况下使用包含硅的聚氨酯粘合剂；或使用基本上不含溶剂的粘合剂，将涂覆的透明或半透明聚碳酸酯基材与框架连接。本发明还涉及根据公开的方法制备的粘合制品。

Description

无底漆粘合的方法
优先权声明
本申请要求2004年10月28日提交的美国临时申请60/622,927的权益，该文献在此引入作为参考。
发明领域
本发明涉及粘合剂粘合两个或两个以上组件的方法。更特别地，该方法可用于将至少一个涂覆的塑料组件粘结到另一个组件上。本发明还涉及由此体系粘合的制品。
发明背景
粘合剂广泛用于整个制品的连接组件。然而，已知的粘合剂体系存在几个缺点。特别地，许多传统粘合剂难以将不同的材料粘结在一起(如塑料到金属或两种不同类型的塑料)。
底漆或粘合促进剂过去一直用于处理表面以促进粘合。底漆具有几个缺点。例如，底漆可劣化它们对应工件的整体性或质量。例如，底漆对涂覆或涂漆基材的施加可劣化或破坏涂料或油漆。在一个特定的情况下，底漆(或粘合剂)组合物中的溶剂可引起塑料组件上涂料或油漆的裂纹或脱层。溶剂的使用也导致在使用之后溶剂的处理和/或回收的问题。溶剂的使用通常要求使用热量以驱出溶剂以进行粘合剂的干燥或固化。
本发明人认识到对一个或多个解决这些问题的方案。
发明概述
本发明涉及将塑料组件粘合到另一个组件的方法，其中在塑料组件上不存在底漆的情况下使用粘合剂，或采用基本上不含溶剂的粘合剂将塑料组件粘合到其它组件。在一个实施方案中，在基材上不存在底漆的情况下使用聚氨酯粘合剂；或使用基本上不含溶剂的粘合剂将涂覆的透明或半透明聚碳酸酯基材连接到框架。本发明还涉及根据公开的方法制备的粘合制品。
发明详述
本发明涉及在至少一个组件上不存在底漆的情况下使用基本上不含溶剂的粘合剂或粘合剂，将至少第一组件和第二组件粘合在一起的方法。在一个实施方案中，基本上不含溶剂的粘合剂可用于将第一组件粘合到第二组件。在另一个实施方案中，通过在第一组件上不存在底漆的情况下使用粘合剂，粘合剂可用于将第一组件粘合到第二组件。在优选的实施方案中，无底漆的第一组件与基本上不含溶剂的粘合剂结合使用。
第一组件通常由塑料构成，尽管这不是必须的，其可以包括热塑性塑料，热固性塑料，橡胶，弹性体，或其组合。增强、未增强，填充和未填充塑料也可用于组件。
优选的聚酰胺、聚苯乙烯、聚酯、乙烯基类、丙烯酸类、甲基丙烯酸类、丙烯腈类、聚烯烃、聚碳酸酯、或其混合物。更优选地，材料选自丙烯酸类或聚碳酸酯。
在一个优选的实施方案中，第一组件的材料是透明或半透明聚碳酸酯且可以使用任何合适的技术(如辊压、挤出、模塑等)成形。在一个实施方案中，使用反应注塑(RIM)。此外，材料可以包含一种或多种添加剂，如色调剂、着色剂、耐擦划剂、UV&热量吸收剂、粘合促进剂及其组合。
可以由一种或多种涂料，如色调剂、硬涂料、偏振涂料、耐擦划涂料、耐化学品涂料、反射涂料、辐射吸收涂料(如UV涂料)，其组合等涂覆第一组件。优选地，由涂料涂覆聚碳酸酯，该涂料改进它的硬度、强度和/或耐辐射性而基本上不模糊聚碳酸酯的透明度或半透明性且不易在不利的温度或压力条件下或在化学环境下从组件出现裂纹、剥落、剥离、或脱层。在一个优选的实施方案中，第一组件进一步包括在组件周界周围的不透明带或区域而组件的剩余部分持续是透明或半透明的。
第二组件可以是与第一组件相同的材料。另外，第二组件可以由任何合适的材料构成，该材料包括金属(如钢)、合金、复合材料、陶瓷、层压材料、上述塑料、其组合等。
第二组件可以包括一个或多个表面处理，如以上讨论的涂覆。此外，第二组件也可以由底漆或油漆涂覆。
在一个实施方案中，每个组件的表面可任选地在涂料，粘合剂或底漆的施加之前经过初步处理。这个任选的处理可包括清洁和脱脂，等离子体涂覆，用另一种表面处理(如油漆)的涂覆，及其组合。
用于将组件粘合在一起的粘合剂可以是对于希望应用的任何合适粘合剂。粘合剂可以是水性粘合剂，溶剂型粘合剂或其它类型。粘合剂可以是单组分粘合剂或多组分粘合剂(如双组分粘合剂)。多组分粘合剂可同时使用组分(如环氧类)或按顺序。多组分粘合剂可以是空气固化，湿固化，热固化，辐射固化(如IR或UV)，射频固化，溶剂损失固化，或其它固化的。多组分粘合剂可以是熔体流动的，液体，膜，粉末，糊剂，带，泡沫，凝胶，或其它类型。多组分粘合剂可以是压敏RTV粘合剂，或热熔粘合剂。多组分粘合剂可以是某些应用中的结构粘合剂。应当认识到此处术语粘合剂的使用不希望对于本发明的范围排除底漆或其它粘结剂。
可以使用在固化之后可承受车窗使用条件(如用于汽车挡风玻璃)的任何粘合剂。优选这样的粘合剂在约-40℃和约150℃之间的温度下不分解或分层。尽管不是关键的，在一个实施方案中，粘合剂的获得的拉伸强度为至少约70psi(约500kPa)，更优选约145psi(约1MPa)，更优选约420psi(约3MPa)。在一些应用中，获得的拉伸强度可以高至约4000psi(约28MPa)，更优选至少约6500psi(约45MPa)，和更优选至少约9000psi(62MPa)。认识到在一些应用中，粘合剂的强度可大于至少一个，和优选多于一个的单个结合组件的强度。
优选使用的粘合剂产生搭接剪切强度为约至少300psi的接合；更优选接合的搭接剪切强度为约至少400psi；最优选接合的搭接剪切强度为约至少500psi或更高。这样的搭接剪切强度提供具有足够强度的接合以用于汽车的挡风玻璃。
进一步认识到，优选的粘合剂能够承受曝露于水或清洁溶液。任选地，粘合剂也能够在上述温度和压力下承受曝露于烃材料(如天然或合成油)，氯化钙，刹车油，二醇冷却剂等。
在另一个实施方案中，粘合剂可以是按需固化粘合剂，其要求单独的操作以引起粘合剂开始固化。在一个实施方案中，这通过使用包覆的固化剂达到，该固化剂在组装期间被破裂。在另一个实施方案中，这通过脱除保护涂层以曝露粘合剂于环境条件而达到。可以通过将粘合剂曝露于热量、红外或紫外光源，或曝露于剪切力量等而开始固化。当然，总是可能使用不具有按需要固化能力的粘合剂。
可以使用选自任何合适粘合剂族的粘合剂，如聚酯、聚酰胺、聚氨酯、polyanthuses、聚醚、聚烯烃、环氧类、乙烯醋酸乙烯酯、尿烷类、丙烯酸类、硅烷、硫醚、氟硅氧烷、氟碳、其组合等。粘合剂可以是高温环氧树脂、高温丙烯酸树脂、聚酰亚胺、混合聚酰亚胺/环氧树脂粘合剂、环氧酚醛清漆/丁腈橡胶粘合剂、聚硫醚环氧化物等。用于可能的粘合剂的例示性组合物公开于题目为″Amine OrganoboraneComplex Polymerization Initiators and Polymerizable Compositions″，PCT公开No.WO 01/44311A1，U.S.系列No.09/466,321的专利申请中，该文献在此引入作为参考。
高温丙烯酸树脂粘合剂表示其中主要组分是丙烯酸树脂粘合剂的，该丙烯酸树脂当固化时可承受曝露于以上提及的温度的而不分解或从组件脱层。优选的聚氨酯粘合剂可包括与聚氨酯或聚氨酯-硅部分混合的硅(如硅氧烷)。更优选的聚氨酯粘合剂包括甲硅烷基封端的聚氨酯，最优选的粘合剂包括接枝到聚氨酯主链的硅氧烷。优选的聚氨酯粘合剂包括以商品名BETASEALTM由Dow Chemical销售的那些。优选的聚醚粘合剂包括甲硅烷基封端的聚醚，如以商品名Kaneka MS聚合物销售的那些。
在一个实施方案中，粘合剂可以在粘合到第一塑料组件的期间基本上不含溶剂。可以使用基本上不含溶剂的粘合剂。或者，粘合剂可以在施加到第二组件之后基本上不含溶剂。例如，可以使溶剂在环境条件下蒸发或可以使用高温、减压、空气移动、或其组合去除溶剂。此外，可以使粘合剂部分固化(如溶剂损失固化)以脱除可以存在的任何溶剂。溶剂包括用作在其体积内均匀地分散粘合剂的液体。溶剂可以是有机或无机，极性或非极性的，且可以具有任何蒸气压。
优选地，粘合剂基本上不含任何溶剂，该溶剂引起第一塑料组件上的涂料的任何裂纹或脱层。粘合剂还优选没有模糊第一塑料组件的半透明性或透明度的任何溶剂，无论该组件是否涂覆。
优选的基本上不含溶剂的粘合剂包含小于约50wt％溶剂，更优选的粘合剂包含小于约25wt％溶剂，还更优选的粘合剂包含小于约15wt％溶剂，仍然更优选的粘合剂包含小于约10wt％溶剂，而更优选的粘合剂包含小于约5wt％溶剂，最优选的粘合剂包含小于约1wt％溶剂。优选地，溶剂的重量百分比在施加时测量，但也可以在将两个组件粘合在一起时测量。
在一方面，增塑剂可用于降低粘合剂的粘度或另外改进粘合剂的流动性。这有助于粘合剂的施加而不需要使用溶剂。合适的增塑剂包括邻苯二甲酸酯。
在一个实施方案中，在第一组件上不存在底漆的情况下，使用基本上不含溶剂的粘合剂在施加时，将第一涂覆的塑料组件粘合到第二组件。通过消除第一组件上的底漆和明显限制粘合剂中存在的溶剂数量，这样的组合限制与第一塑料组件上涂料接触的溶剂数量。溶剂数量的降低会增加获得的粘合组件的质量，这是由于降低或消除了第一组件上涂料的裂纹和/或脱层。即使不降低或消除脱层，溶剂数量的降低也具有其它优点，如降低溶剂的处理或回收的成本和通过消除溶剂脱除工艺降低生产成本。
可以将粘合剂由任何合适的方法(如喷涂、刷涂、辊涂、浸渍、拭抹及其组合)施加到塑料组件和/或第二组件的匹配表面上。
在一个实施方案中，将粘合剂的珠粒置于(如由泵送)至少一个组件的各自匹配表面上且将相对的匹配表面与其接触。然后固化组合体。在另一个实施方案中，将粘合剂在各自组件的一个或两个匹配表面上预涂覆(如通过喷涂、浸渍、刷涂、拭抹、裱涂等)且然后将组件结合和固化。可同样采用任何合适的结合技术。优选采用的粘合剂数量足以达到组合体的所需性能特性。这样的数量可随应用而变化。还设想它们可用于修理的组合体的再组装或替换组件。
机械紧固件如铆钉、螺母和螺栓、焊接等可以与粘合剂结合以将组件固定在一起。
本发明还涉及由粘合两个或两个以上粘合剂粘合的组件的公开方法制造的制品。在优选的实施方案中，这样的制品包括涂覆的透明或半透明车窗，该车窗粘合到涂覆的金属窗框上。优选地，第二组件是适于接收透明或半透明聚碳酸酯的框架，其中框架由底漆涂覆。制品还包括粘合剂粘合到框架的透镜，粘合剂粘合到框架的结构板，粘合到框架的护罩，其组合等。一旦粘合在一起，组件可形成在窗户、透镜或结构之上、之中、或作为其一部分使用的组合体，更特别地，在车辆中使用的组合体。在车辆中，组合体可包括挡风玻璃，月光顶，窗户等。另外，粘合的组件可形成用于保护用户免受物理，化学，和生物危险的透明或半透明保护屏蔽。特别地，粘合的组件可形成保护头盔或衣服上的屏蔽，工业机器上的屏蔽，屏蔽，反应容器，或进入新反应容器的窗户。在一个实施方案中，由公开的方法制造的制品在塑料基材上完全或基本上没有任何涂料的裂纹或脱层。例如，优选的制品是金属框架中的涂覆的聚碳酸酯窗，该框架在聚碳酸酯窗上基本上没有涂料的裂纹或脱层。
本发明还涉及使用组件的组合体的方法，该组件包括使用在此公开的基本上不含溶剂的粘合剂制备的接合。特别地，方法包括在大于约500psi(约3MPa)，更优选至多约600psi(约4MPa)，最优选大于约700psi(约5MPa)的条件下操作车窗。
实施例
提供如下实施例以更完全说明本发明，实施例不希望限制权利要求的范围。除非另外说明，所有的份和百分比按重量计。
将无底漆聚氨酯粘合剂和与底漆结合使用的粘合剂比较。根据SAE J1529测试方法进行搭接剪切粘合测试和根据SAE J 1720测试方法进行快速刀粘合测试。
对于搭接剪切测试，将大约宽6.3mm高8mm的粘合剂珠粒沿Lexamar聚碳酸酯窗的宽度采用GE AS4700硬涂层(25mm×75mm)且从距末端大约6mm～12mm处施加。将e-涂覆的金属基材放置在粘合剂上且使样品在23℃和50％相对湿度的条件下固化3～7天。在固化之后，将样品进行搭接剪切测试或经受进一步的风化条件。
一种类型的风化是湿循环，该湿循环包括使样品经受88℃下24小时，随后冷凝增湿24小时，随后-29℃下24小时。重复此循环总计5次，其后将样品进行搭接剪切测试。使用Weather-O-Meter(WOM)腔室。除非另外规定，SAEJ1885条件用于测试腔室。
其它类型的风化是干燥循环，该干燥循环包括使样品经受70℃的热水浴7天，其中将样品在原棉中缠绕和密封于聚乙烯袋中。然后，将样品在20℃下置于冷冻16小时，其后将样品在室温下放置2小时。重复此循环总计5次，其后将样品从袋取出并进行搭接剪切测试。
比较五种不同的粘合剂体系；两种使用在聚碳酸酯基材上的底漆和三种无底漆粘合剂。BETASEALTM 57302是不包含硅烷的聚氨酯粘合剂。此粘合剂采用如下形式与两步骤底漆一起使用：BETASEALTM43518(溶剂中的透明底漆)，和BETASEALTM 43520A(溶剂中的黑底漆)。BETASEALTM 57302也以BETAPRIMETM 5500的形式用于两步骤底漆，BETAPRIMETM 5500是溶剂中的单步骤玻璃底漆。BETASEALTM58402是与硅烷共聚的聚氨酯预聚物。BETASEALTM 15625和16000是包含由氨基硅烷接枝的聚氨酯预聚物的聚氨酯粘合剂。BETASEALTM16000也包含热稳定剂，而15625不包含。最后三种粘合剂以无底漆使用和也不含溶剂。
在1英寸/分钟(2.5cm/min)的拉动速率下用lnstron Tester进行搭接剪切测试。每个粘合剂体系的五个样品在每套条件下进行：1)初始固化；2)湿循环；和3)干燥循环。将每个粘合剂体系的五个样品的搭接剪切测试结果平均化且列入表1。
表1：搭接剪切测试
粘合剂 底漆 初始(PSI)   湿循环(PSI)   干燥循环(PSI) 破坏模式
  BETASEALTM57302   BETASEALTM43518/43520A 709 561 672   100CF(5中5个)
  BETASEALTM57302   BETAPRIMETM5500 744 697 618   100CF(5中5个)
  BETASEALTM58402 无 600 590 569   100CF(5中4个)
  BETASEALTM   无   429   613   597   100CF(5
  15625   中4个)
  BETASEALTM16000 无 401 637 444   100CF(5中5个)
无底漆粘合剂显示不存在裂纹且和显示可以与涂底漆粘合剂的搭接剪切强度比较的搭接剪切强度。此外，所有粘合剂显示对于大多数样品形式为内聚破坏的破坏模式。来自无底漆粘合剂BETASEALTM58402和BETASEALTM 15625每种的仅1个样品显示任何基材破坏。
对于快速刀粘合测试，将粘合剂的6.3mm(宽度)×6.3mm(高度)×100mm(长度)珠粒采用GE AS4700硬涂层放置在Lexamar聚碳酸酯窗上和将粘合剂在23℃和50％相对湿度的条件下固化一定时间。然后将固化的珠粒采用剃刀片以45°角度切通到基材，同时以180°角向后拉珠粒的末端。每3mm在基材上切割缺口。粘合的程度评价为内聚破坏(CF)或基材破坏(CF-SB)。在CF的情况下，由于切割和拉动在粘合剂中出现分离，而在CF-SB中，基材出现破坏。用于搭接剪切测试的相同粘合剂/底漆组合和无底漆粘合剂用于快速刀粘合测试，风化条件也相同。将每个粘合剂和风化条件的一个样品进行快速刀粘合测试。结果总结于表2。
表2：快速刀粘合测试
Figure S05837208X20070508D000081
Figure S05837208X20070508D000091
快速刀粘合测试的结果显示对于粘合剂/底漆组合和两种无底漆粘合剂的相似破坏模式，说明无底漆粘合剂表现得如底漆/粘合剂组合一样好。即，两类样品显示达到相似的程度地基材破坏。一种无底漆粘合剂比剩余样品显示明显好的破坏模式。BETASEALTM16000的100％CF结果说明使用此粘合剂在任何风化条件下不存在基材破坏。
总体上，搭接剪切强度测试和快速刀粘合测试显示无底漆粘合剂表现得和底漆/粘合剂组合一样好。这些相似结果是由于避免了溶剂的使用而不劣化性能所带来的改进。
进一步认识到多个组件或步骤的功能可以结合成单一组件或步骤，或一个步骤或组件的功能或结构可以在多个步骤或组件中分解。本发明设想所有这些组合。除非另外说明，在此说明的各种结构的尺寸和几何情况不希望限制本发明，并且其它尺寸和几何情况都是可能的。多个结构组件或步骤可以由单一集成的结构或步骤提供。或者，单一集成的结构或步骤可以分成多个组件或步骤。此外，尽管本发明的特征可在仅一个说明的实施方案的上下文中描述，这样的特征可以与其它实施方案的一个或多个其它特征结合，用于任何给定的应用。也从以上内容认识到此处独特结构的制造和其操作也构成根据本发明的方法。本发明还设想来自此处方法实践所得的中间和最终产物。″包括″或″包含″的使用也设想″基本由″或″由″所述特征组成的实施方案。
此处呈现的解释和说明希望使本领域技术人员熟知本发明，其原理，及其实际应用。本领域技术人员可采用它的许多方式改进和应用本发明，如可最适于特定用途的要求。因此，认为本发明的具体实施方案不希望是穷举或限制本发明。本发明的范围因此应当不参考以上描述而被确定，而应该参考所附的权利要求，以及等同于这样的权利要求的所有范围。包括专利申请和公开文献的所有文章和参考文献的公开内容对于所有目的在此引入作为参考。

Claims (6)

1.一种将聚碳酸酯基材连接到金属框架的方法，包括：
在基材上不存在底漆的情况下，使用聚氨酯粘合剂，将至少部分透明或半透明的涂覆的聚碳酸酯基材连接到框架上，其中粘合剂基本上不含溶剂；固化粘合剂，其中粘合剂是湿固化的，且固化的粘合剂在聚碳酸酯基材和框架之间形成粘合，所述基本上不含溶剂指包含小于50wt％的溶剂且降低或消除聚碳酸酯基材上涂料的裂纹和/或脱层，其中所述聚氨酯粘合剂包括接枝到聚氨酯主链的硅氧烷、由甲硅烷基封端的聚氨酯主链、聚氨酯和硅氧烷的混合物或其组合，其中固化的粘合的搭接剪切强度为至少400psi，根据SAE J1529标准的测量方法测量。
2.根据权利要求1所述的方法，其中金属框架包括车窗框。
3.一种粘合剂粘合的制品，包括：
a.至少部分透明或半透明的硬涂覆的聚碳酸酯基材；
b.金属框架；和
c.湿固化的基本上不含溶剂聚氨酯粘合剂，
其中在基材上不存在底漆的情况下，使用粘合剂将基材粘合到框架上，所述基本上不含溶剂指包含小于50wt％的溶剂且降低或消除聚碳酸酯基材上涂料的裂纹和/或脱层，其中所述粘合剂包括接枝到聚氨酯主链的硅氧烷、由甲硅烷基封端的聚氨酯主链、聚氨酯和硅氧烷的混合物或其组合，其中固化的粘合的搭接剪切强度为400psi，根据SAE J1529标准的测量方法测量。
4.根据权利要求3所述的制品，其中聚碳酸酯基材进一步构成车窗且金属框架进一步包括车窗框。
5.根据权利要求3所述的制品，其中硬涂覆的聚碳酸酯基材基本上没有涂料的裂纹。
6.根据权利要求3所述的制品，其中硬涂覆的聚碳酸酯基材基本上没有涂料的脱层。
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