CN110023367A - 含有醛亚胺的玻璃粘合底漆 - Google Patents

含有醛亚胺的玻璃粘合底漆 Download PDF

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CN110023367A
CN110023367A CN201780074171.0A CN201780074171A CN110023367A CN 110023367 A CN110023367 A CN 110023367A CN 201780074171 A CN201780074171 A CN 201780074171A CN 110023367 A CN110023367 A CN 110023367A
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priming paint
base composition
paint base
aldimine
epoxy resin
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N·马尔瓦德卡
D·P·索菲娅
J·M·维舒恩
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DDP Specialty Electronic Materials US LLC
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Abstract

披露了一种含有醛亚胺和/或环氧树脂的新颖的底漆组合物，一种制造待用于玻璃粘合胶粘剂套件中的此种底漆的方法。

Description

含有醛亚胺的玻璃粘合底漆
本发明涉及一种新的底漆组合物或“底漆”，其在汽车相关应用中、特别是在玻璃粘合应用中具有独特的性能。
典型的玻璃粘合胶粘剂套件包含底漆组合物和湿固化的氨基甲酸乙酯胶粘剂。玻璃粘合底漆典型地含有有机溶剂、有机硅烷中间体、异氰酸酯预聚物、成膜剂、炭黑、催化剂和稳定剂。底漆改性玻璃表面以使其与湿固化的氨基甲酸乙酯胶粘剂良好粘合。底漆中的异氰酸酯经受湿固化以产生交联的热固性网络，这使得底漆足够稳健以在环境条件下具有足够的耐久性。但是，底漆必须具有足够的交联密度以维持高温和高湿度条件。在这些条件下，传统的含有上述组分的底漆易于失去交联密度，从而与玻璃表面分层。因此，希望开发出即使在高温和高湿度条件下也具有足够交联密度的新底漆。
在本发明的一个方面，本发明提供了一种新的底漆，其含有一种或多种醛亚胺，该一种或多种醛亚胺作为潜在的交联剂以产生改善的水解稳定性。在本发明的另一个方面，这些新的底漆不含或基本上不含炭黑，炭黑典型地作为增强剂加入玻璃粘合底漆中以改善其耐久性。然而，在底漆中结合炭黑需要单独的研磨步骤，该步骤是高度时间和能量密集的。因此，消除炭黑简化了制造复杂性并降低了总成本
本发明的底漆典型地含有
A)15wt.％-45wt.％、优选20wt.％-40wt.％并且更优选25wt.％-35wt.％的有机溶剂，如丙酮和/或甲基乙基酮；
B)2wt.％-10wt.％、优选2.5wt.％-8wt.％并且更优选3wt.％-7wt.％的醛亚胺，如二醛亚胺；
C)2wt.％-17wt.％、优选3wt.％-15wt.％并且更优选4wt.％-12wt.％的烷氧基硅烷中间体，在通过引用以其全部内容结合在此的US 5852137中也称为加合物，其为γ-巯基丙基三甲氧基硅烷和六亚甲基二异氰酸酯(HDI)缩二脲的反应产物；在US 5852137中，特别是在第5栏第25行与第7栏第15行之间和实例中详细描述和传授了中间体的化学性质和制备。用于本发明中的烷氧基硅烷中间体也在US 5238993中传授，该专利也通过引用以其全部内容结合在此，并且作为US 5238993的实例1披露；
D)0wt.％-10wt.％、优选4wt.％-8wt.％并且更优选5wt.％-7wt.％的双酚A的二缩水甘油醚，环氧树脂例如D.E.R.TM332；
E)15wt.％-35wt.％、优选20wt.％-33wt.％并且更优选23wt.％-30wt.％的非反应性成膜树脂，例如2301 BU(40wt.％甲基乙基酮中的溶液)；
F)18wt.％-30wt.％、优选20wt.％-28wt.％并且更优选22wt.％-26wt.％的脂族和芳族多异氰酸酯预聚物，例如RFE、HL和PAPITM20；
G)1wt.％-3wt.％、优选1.5wt.％-2.5wt.％并且更优选2wt.％-2.2wt.％的反应性改性剂，例如含有噁唑烷的化合物PARALOIDTMQM-1007；
H)0.1wt.％-0.3wt.％、优选0.15wt.％-0.25wt.％并且更优选0.2wt.％-0.22wt.％的催化剂，例如670；和
I)0.2％-0.5％、优选0.25wt.％-0.4wt.％并且更优选0.3wt.％-0.35wt.％的异氰酸酯稳定剂，例如丙二酸二乙酯。
如上所讨论的，本发明的所有底漆的独特组分是在底漆中使用一种或多种醛亚胺。醛亚胺是通过使醛与伯胺反应形成亚胺官能团而制备的席夫碱。醛亚胺在水分存在下经历水解以释放回醛和胺。然后，从该水解反应中释放的胺可与异氰酸酯基团或环氧基团反应，以增加底漆涂层的交联密度。此外，醛亚胺还有助于稳定底漆并延长底漆的保质期。在优选的实施例中，底漆中使用的醛亚胺是二醛亚胺。
除了醛亚胺之外，还可以将也能够与胺反应的环氧树脂添加到底漆中以提供额外的韧性、耐久性和防潮层。当用胺固化时，环氧树脂如双酚A二缩水甘油醚提供优异的阻隔特性。其结果是，当加入环氧树脂时，底漆的水解稳定性被大大提高。含有环氧树脂的底漆在90℃水中浸泡10天后具有较低的对起泡的敏感性。重要的是要注意，存在羟基的环氧树脂可能引发与底漆组合物中存在的异氰酸酯的反应，导致胶凝。因此，选择不含任何羟基官能团的环氧树脂是重要的。在优选的实施例中，在底漆组合物中使用可从奥林公司(OlinCorporation)商购的环氧树脂DER 332。
底漆中醛亚胺和环氧树脂的存在增加了底漆的玻璃粘合强度，并且还提高了水解稳定性。此外，使用本发明的底漆，与传统上在汽车应用中使用的湿固化的氨基甲酸乙酯胶粘剂的连接速率(link up rate)非常类似于传统的黑色研磨底漆。然而，由于在一些优选的实施例中，这些新的底漆不含炭黑，因此与传统的黑色底漆相比，制造成本显著降低。
实例
通过以下非限制性实例可以进一步说明本发明。
表1展示了在制备说明本发明的实例中使用的各种原料组分及其来源。
表1 本发明中使用的组分
表2总结了为说明本发明制备的各个实例。实例1至6是含有醛亚胺的本发明样品，而实例7至10是不含醛亚胺的对比样品。
表2 制备的各个实例的内容物。
1使用从迈图公司可获得的Fomrez UL28
2使用从金氏工业公司可获得的KKAT 670
另外，还使用两种商业黑色底漆作为对比实例。第一底漆，实例11，是商业两步玻璃粘合底漆，称为BETASEALTM43520A，其可从陶氏化学公司商购，含有炭黑但不含醛亚胺或环氧树脂。底漆必须与BETASEALTM43518(其可从陶氏化学公司商购)结合使用，其是溶剂基硅烷共混物。在玻璃粘合期间，首先将BETASEALTM43518施加在玻璃侧上以调节玻璃表面。然后将BETASEALTM43520A施加在经调节的玻璃表面上。
另一个对比底漆实例，实例12，是商业一步底漆，称为BETAPRIMETM5504G，其也可从陶氏化学公司商购，含有炭黑但不含醛亚胺或环氧树脂。将底漆直接施加在玻璃表面上。
所有样品均按以下方式制备：
使用两步法制备本发明的玻璃粘合用底漆。在第一步中，通过组合N100(基于脂族六亚甲基二异氰酸酯的多异氰酸酯)和A189(γ-巯基丙基三甲氧基硅烷)和甲基乙基酮制备组分C，以得到70％固体溶液。加入N 100和A189以得到3:1当量的异氰酸酯和巯基基团。然后将FASCAT 4202(二月桂酸二丁基锡)催化剂加入到共混物中。使溶液在60℃的反应容器中反应直至所有巯基被消耗。所得反应产物是有机硅烷中间体(表1的组分C)。然后将表1中给出的其余组分加入铝容器中。将有机硅烷中间体连同催化剂(组分H)一起加入。然后使用压舌板搅拌组分。
在不添加醛亚胺的情况下类似地制备对比实例(实例7-10)。
两个种类的实例底漆用于研究底漆在3”x5”玻璃基材上的粘合性能。在施加底漆之前，用丙酮和异丙醇清洁玻璃基材。使用1密耳刮涂棒(drawdown bar)施加底漆。使底漆在环境条件下固化所需的时间量。
使用以下试验方法评估本发明的底漆的性能：
划痕附着力试验：通过将底漆涂覆在玻璃基材上使用1mm直径的半球形不锈钢刮擦头来进行附着力试验。在将底漆固化24小时后，使用该刮擦头在底漆表面上施加划痕。对于每个试验，通过从200g至1000g改变法向载荷来施加一组8个划痕。将从玻璃表面除去底漆所需的最小力报告为底漆与玻璃之间的附着力。
储存稳定性试验：将储存在铝瓶中的新鲜制备的底漆置于54℃的烘箱中3天。3天后，将瓶子从烘箱中取出。凝胶化的底漆没有通过储存稳定性试验，而未凝胶的底漆通过了储存稳定性试验。
水解稳定性试验：使涂覆有底漆的玻璃在环境条件下固化7天。然后将底漆涂覆的玻璃浸入90℃水浴中10天。10天后，将底漆涂覆的玻璃从水浴中取出并空气干燥4小时。最后，对该底漆进行划痕附着力试验，并记录从基材上除去底漆所需的最小附着力。
快刀试验(SAE J1720)：将胶粘剂的6.3mm(宽度)x6.3mm(高度)x 100mm(长度)珠粒放在底漆涂覆的基材上。将胶粘剂在23℃和50％相对湿度的条件下固化24小时。然后用剃刀刀片将固化的珠粒以45°角切通到基材，同时以180°角向后拉珠粒的末端。在基材上每3mm切割缺口。胶粘破坏记为1。内聚破坏(CF)，即在胶粘剂内发生的胶粘破坏；记为2。与底漆胶粘破坏(AFP)，即在底漆胶粘剂界面处破坏；记为3。与玻璃底漆破坏(PFG)，即在底漆玻璃界面处破坏。
搭接剪切试验：将底漆样品涂覆在平板玻璃上并使其干燥1小时。将可从陶氏化学公司商购的BETASEAL Express胶粘剂珠粒施加到干燥的底漆上。然后将电泳涂层(e-coat)试样放置在搭接组件中的珠粒上。在搭接剪切试验之前使胶粘剂固化24小时。通过以5英寸/分钟的速率拉动两个基材来进行搭接剪切。记录拉开两个基材所需的峰值力和胶粘破坏模式。
所有上述性能试验结果总结在表3中。
表3示出了本发明的底漆实例和对比实例的性能。除实例13外，所有底漆在24小时固化后显示出对玻璃表面的良好附着力。这些底漆的附着力值超过仪器的最大可测量值(即1000g)。相比之下，实例13的底漆具有相对低的干附着力值(600g)，这可能归因于底漆的缓慢固化动力学。
在90℃水浸泡10天后进行的划痕附着力试验证明了底漆的水解稳定性。表3中提供了在90℃水浸泡10天后的附着力值。
很明显，本发明的底漆比对比实例表现得更好。需要环氧树脂和醛亚胺二者来增强底漆的水解稳定性。实例1、2、3、4和5的底漆含有环氧树脂和醛亚胺二者，并且导致优异的水解稳定性，如通过将底漆浸入90℃水中10天后进行的划痕试验所看到的。此外，在将组件浸入90℃水中10天后进行的搭接剪切试验也表明，需要存在醛亚胺和环氧树脂二者以具有更好的搭接剪切性能。含有醛亚胺但不含环氧树脂的实例6的底漆在室温下显示出优异的附着力，如从划痕试验中明显的。然而，与实例1至5的底漆相比，该底漆的水解稳定性略低。另外，该底漆相对于实例1至5的底漆也显示出更严重的起泡。在不存在环氧树脂和醛亚胺二者的情况下，底漆具有较低的水解稳定性(实例6、7、10和11)。
此外，醛亚胺有助于稳定底漆并且因此提高了底漆的储存稳定性。储存稳定性还取决于所用的催化剂。在如实例1、2和3中所用的锡催化剂如Fomrez UL28的情况下，底漆没有通过54℃凝胶试验，表明保存期较短。相比之下，如实例4和5中所用的含有非锡催化剂如KKAT 670的底漆更可能通过54℃凝胶试验。然而，即使底漆含有KKAT 670作为催化剂，当组合物中不存在醛亚胺时，它仍然不能通过凝胶试验。这在实例9和10中是明显的。这两种底漆都不含醛亚胺并且因此不能通过凝胶试验。
进行快刀试验以评估与湿固化的氨基甲酸乙酯胶粘剂的连接速率。所有底漆在7天胶粘剂固化后显示出与作为氨基甲酸乙酯胶粘剂的BETASEAL Express的优异的连接时间(100％内聚破坏)。醛亚胺和/或环氧树脂的存在不会损害底漆与胶粘剂的连接速率。
还观察到，在本发明的优选实施例中，底漆含有二醛亚胺，例如Incozel BH(可从Incorez商购)，它是聚醚胺(例如，JEFFAMINE D400，可从亨斯迈公司(Huntsman)商购)和苯甲醛的反应产物。

Claims (10)

1.一种底漆组合物，其基于所述组合物的总重量包含有机溶剂；醛亚胺；烷氧基硅烷；非反应性成膜树脂；多异氰酸酯预聚物；反应性改性剂；催化剂；和异氰酸酯稳定剂。
2.如权利要求1所述的底漆组合物，其进一步包含小于10wt.％的环氧树脂。
3.如权利要求2所述的底漆组合物，其中所述环氧树脂是双酚A的二缩水甘油醚。
4.如权利要求1所述的底漆组合物，其包含基本上不含炭黑。
5.如权利要求1所述的底漆组合物，其不含炭黑。
6.如权利要求1所述的底漆组合物，其中所述有机溶剂包含丙酮、甲基乙基酮和它们的混合物之一；并且其中所述反应性改性剂是含噁唑烷的化合物。
7.如权利要求1所述的底漆组合物，其中所述异氰酸酯稳定剂包括丙二酸二乙酯。
8.如权利要求1所述的底漆组合物，其中所述醛亚胺是二醛亚胺。
9.如权利要求8所述的底漆组合物，其中所述醛亚胺是聚醚胺和苯甲醛的反应。
10.如权利要求1所述的底漆组合物，其中烷氧基硅烷是γ-巯基丙基三甲氧基硅烷和六亚甲基二异氰酸酯(HDI)缩二脲的反应产物。
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