CN1923905B - 聚合物粘合树脂 - Google Patents
聚合物粘合树脂 Download PDFInfo
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- CN1923905B CN1923905B CN2006101285263A CN200610128526A CN1923905B CN 1923905 B CN1923905 B CN 1923905B CN 2006101285263 A CN2006101285263 A CN 2006101285263A CN 200610128526 A CN200610128526 A CN 200610128526A CN 1923905 B CN1923905 B CN 1923905B
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Abstract
提供了一种水性组合物及其固化方法。所述水性组合物包含多羧基聚合物；选自松香基树脂、松香酯、萜基树脂、苯并呋喃基树脂和酚类增粘剂的活性增粘剂；以及多元醇。
Description
技术领域
本发明涉及可固化水性组合物，具体来说涉及用相容性活性增粘剂改性的多羧基聚合物。所述活性增粘剂对胶粘聚合物的流变性质进行了改性，以促进键合的形成，并使键的断裂最小化。
背景技术
由于酚醛粘合剂具有适于在未固化状态下流动的低粘度，而且在固化之后还可形成用于玻璃纤维的刚性热固性聚合物基质，因此已被用来处理玻璃纤维。粘合剂在未固化状态下的低粘度使得涂敷的垫材在离开玻璃纤维成形室的时候可以最大限度地垂直膨胀。在固化后能够形成具有致密交联结构的刚性基质的粘合剂所制得的最终的玻璃纤维绝热或隔音产品，在为了包装和运输而压缩之后，当解除压力并安装在建筑物中之后，能够基本回复其制造之初时的垂直尺寸。
绝缘材料制造商需要用于玻璃纤维产品的替代的聚合物粘合剂体系。但是，使得垫材在离开成形室之后最大可能地垂直膨胀的小分子量、低密度粘合剂通常会在最终产品中固化形成非刚性塑料基质。其结果是，最终的绝缘产品在安装时所能达到的垂直高度回复通常会减小。相反的，那些通常能够在最终产品中固化形成刚性基质的高粘度粘合剂，通常无法使得涂敷的未固化的垫材最大限度地垂直膨胀。因此，绝缘材料制造商需要在未固化时具有低粘度、在固化后具有结构刚性的非酚醛粘合剂。
美国专利第6539152号和第6699945号揭示了替代的聚合物粘合剂体系。具体来说，美国专利第6539152号揭示了用来改进光纤涂料的时间敏感性流变性质(例如粘性和模量)的增粘剂，其中可聚合的原料组合物包含至少一种单体和任选的至少一种低聚物。所述可聚合原料组合物基本不含不饱和的环氧化二烯聚合物。所述增粘剂是非活性的，因此其作为独立的部分保留在可聚合原料组合物中。
美国专利第6699945号揭示了使小分子量多酸单体或低聚物与多元醇预反应，并与聚羧酸混合形成共粘合剂溶液，据称这种溶液在固化前具有低粘度，在固化后具有结构刚性。然而，额外的预反应步骤延长了工艺时间，提高了相关的成本。
用作玻璃纤维粘合剂的聚合物组合物的弹性和粘性必须平衡。其必须具有足够的粘性流动性质，使得粘合剂和玻璃基片充分地紧密接触，以形成胶粘键合。一旦形成了这些键，所述聚合物必须具有弹性强度，将该体系保持在一起。在本发明中，聚羧酸聚合物提供了大部分的弹性性质，活性增粘剂提供了粘性组分。一旦混合，该体系具有粘合剂所需的粘弹性流变性质，即能够形成胶粘键合的粘性流和使其具有强度的弹性。
发明内容
本发明提供一种水性组合物，该组合物可用作粘合剂，这种组合物在固化之前具有低粘度，即粘合剂的粘度使其能够流出并覆盖基材，以抗张强度衡量，该组合物在固化后还具有极佳的刚性。本发明的一个方面涉及一种水性组合物，该组合物包含多羧基聚合物；选自松香基树脂、松香酯、萜基树脂、苯并呋喃基树脂和酚类增粘剂的活性增粘剂；以及多元醇。
具体实施方式
用于本发明水性组合物的多羧基聚合物包含含有一个以上的羧酸侧基的有机聚合物。所述多羧基聚合物可以是由不饱和羧酸制备的均聚物或共聚物，所述不饱和羧酸包括但不限于丙烯酸、甲基丙烯酸、巴豆酸、异巴豆酸、马来酸、肉桂酸、2-甲基马来酸、衣康酸、2-甲基衣康酸以及α-和β-亚甲基戊二酸。或者所述多羧基聚合物可由不饱和酸酐制备，所述不饱和酸酐包括，但不限于马来酸酐、甲基丙烯酸酐及其混合物。这些酸和酸酐的聚合方法是化学领域中众所周知的。
所述多羧基聚合物还可包含一种或多种上述不饱和羧酸或酸酐与一种或多种乙烯基化合物的共聚物，所述乙烯基化合物包括，但不限于苯乙烯、α-甲基苯乙烯、丙烯腈、甲基丙烯腈、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸缩水甘油酯、乙烯基甲基醚和乙酸乙烯酯。所述多羧基聚合物可通过用来聚合烯键式不饱和单体的溶液聚合、乳液聚合或悬浮聚合技术制备，这些技术是本领域众所周知的。在乳液聚合中，可使用阴离子型或非离子型表面活性剂，或它们的混合物。在进行聚合反应的时候，例如可以在聚合反应开始时所有单体全部都在反应釜内，在聚合反应开始时反应釜内包含一部分乳化形式的单体，或者在聚合反应开始时反应釜内包含小粒度的乳液聚合物晶种。
较佳的是，所述多羧基聚合物包括通过自由基加聚反应制备的聚丙烯酸的均聚物和共聚物。所述多羧酸聚合物的分子量约为500-10000000。优选的是分子量约为2000-250000，最优选分子量约为10000-100000。本文中的分子量是重均分子量。以多羧基聚合物的总重量为基准计，当其是包含约5-30重量％的羧酸、酸酐或其盐的碱溶性树脂时，优选分子量约为10000-100000，更高分子量的碱溶性树脂会制得具有过高粘度的可固化组合物。
任何能够对粘度和模量进行所需改性的增粘剂均可用于本发明的水性组合物。增粘剂是能够以一定的方式改进胶粘聚合物的流变性质，以促进键的形成，同时使键更难断裂的树脂。改性的流变性质包括在固化之前，在低剪切下具有低粘度，使其能够良好地流动/上胶，还包括在固化后具有高模量，使其具有结构刚性。通常所述树脂的分子量必须低于被处理的原料聚合物的分子量，而且与原料聚合物具有相当程度的相容性。相容性是两种材料互溶性的度量，取决于两种组分的分子量和Tg，还取决于它们的组成。
更具体来说，在将水性组合物施用到基材之前，所述活性增粘剂可使该水性组合物具有粘性，但是并非必须如此。另外，较佳的是，当所述水性组合物被用作玻璃纤维绝缘体粘合剂时，该水性组合物所包含活性增稠剂的量不足以使得在旋转(引起水分蒸发)之后、以及当涂敷的玻璃纤维在成形室内(在此处除去更多的水)时，施用到热的玻璃纤维上的组合物立刻变得具有显著的粘性。然而，在将涂敷的玻璃纤维从成形室输送出来之后，但是在进入固化室之前，初始水性组合物中活性增粘剂的量优选应足以在涂敷的玻璃纤维到达固化室之前使粘合剂组合物变粘，从而以优于几乎没有粘性的组合物的效果将玻璃纤维垫材保持在一起。换而言之，当使用术语“活性增粘剂”的时候，并不表示其在任何时间都使得组合物具有粘性，但是优选的是，该增粘剂在上述玻璃纤维生产阶段使组合物至少具有一定的粘性。换而言之，用于本发明的活性增粘剂还可以使粘合剂组合物具有粘性以外的其他所需性质。
活性增粘剂是具有能够与所述水性组合物的多羧基聚合物和/或多元醇组分反应的官能团的增粘剂。在本发明中，所述官能团包括羧酸基团、羟基和酯基。优选的活性增粘剂是被分成以下种类的增粘剂：松香基树脂、萜基树脂、苯并呋喃基树脂和酚类增粘剂。
松香基树脂是包含松香或松香衍生物作为原料的树脂。松香基树脂可以根据它们的松香酸进行分类，可以是枞酸或海松酸。优选枞酸类松香。松香衍生物包括聚合松香、歧化松香、氢化松香和酯化松香。这些松香(rosin)衍生物的代表性的例子包括松浆油的季戊四醇酯、脂松香(gum rosin)、木松香或其混合物。
萜基树脂包括以下物质的萜聚合物：α-蒎烯、β-蒎烯、双戊烯(dipentel)、苎烯、月桂烯、冰片烯和莰烯，以及通过用一种或多种酚对这些萜基树脂改性制得的酚改性的萜基树脂。优选的是酚改性的萜。示例性的酚改性的萜是购自Arakawa Chemical Inc.(美国伊利诺斯州，芝加哥)的TAMANOL 803L。苯并呋喃基树脂包括例如苯并呋喃、苯并呋喃-茚树脂和酚改性的苯并呋喃-茚树脂。优选的是酚改性的苯并呋喃-茚树脂。示例性的酚改性的苯并呋喃-茚树脂是购自Rütgers Chemicals(德国)的
CA80。
适用于本发明的酚类增粘剂是C1-12烷基酚、C1-12芳基酚和C1-12芳烷基酚，以及这些酚与醛(例如甲醛、乙醛和糠醛)的缩合产物，这些缩合产物的分子量(Mn)小于1500，优选小于500。“酚”表示其中一个或多个羟基与苯环直接相连的一类芳族有机化合物(例如苯酚(benzophenol)、甲酚、二甲苯酚、间苯二酚和萘酚)。示例性的酚类增粘剂包括购自Akrokem Corporation(美国俄亥俄州，Akron)的P-133RESIN，购自Shedenectady International Inc.(美国纽约州，Schenectady)的HRJ-10420，和购自Arakawa Chemical Inc.(美国伊利诺伊州，芝加哥)的TAMANOL 500系列树脂。
在合适的活性增粘剂中，优选的是松香衍生物。在松香衍生物中，最优选酯化松香，特别是酯化枞酸松香。酯化松香优选由乙二醇、甘油和季戊四醇之类的多元醇酯化。通常使用多元醇酯化以制得具有较高软化点且本身具有更高聚合度的产物。示例性的枞酸酯是购自Arizona Chemical(美国佛罗里达州，Hacksonville)的
RE40，以前被称为购自Union Camp Corp.(美国新泽西州，Wayne)的
R-40。
较佳的是，出于改进组合物的应力依赖性流变性质的目的，在本发明的水性组合物中使用有效量的活性增粘剂。有效量是所述多羧基聚合物的0.1-30重量％，较优选1-20重量％，更优选2-10重量％。
所述活性增粘剂作为“固溶剂”促进了粘合剂组合物在固化形成基质之前的粘性流动，降低了所述多羧基聚合物的平均分子量，从而使处理的难度最小化(包括流动性较差)，改进了最终产品的上胶。在固化过程中，活性增粘剂与多羧基聚合物和/或多元醇(优选前者)反应，成为形成的聚合物基质的永久性部分，从而增大了组合物的平均分子量和强度。
由活性增粘剂改性的水性组合物的流变性质决定了所述组合物在特定的应力强度(stress rate)下是否会发挥所需的功能；也即是说，在低应力强度下具有低粘度，在高应力强度下具有高模量。对于玻璃纤维涂料，预期水性组合物在固化前和固化后都会经历低应力强度条件和高应力强度条件。高应力强度条件是指约等于或大于100Hz的条件，低应力强度条件是指约等于或小于1Hz的条件。通常，根据所施加的应力强度与其中任一极值的接近程度，预期介于这两个极值之间的应力强度会使得组合物或多或少地表现出玻璃状产品的性质，或者或多或少地表现出橡胶状产品的性质。由于水性组合物的性质是由温度决定的，接近用活性增粘剂改性的多羧基聚合物的Tg的温度，对水分基本除去、但是尚未固化时(即在制造中对成形的玻璃纤维施加应力作用的时候)的组合物是否具有类似玻璃或橡胶的性质产生显著影响。
所述水性组合物的多元醇优选包含至少三个羟基。所述多元醇必须具有足够的非挥发性，使得在加热和固化操作过程中，其能够基本保留在组合物中，与组合物中的多羧基聚合物反应。所述多元醇可以是包含至少两个羟基的分子量约小于1000的化合物，例如乙二酸、甘油、季戊四醇、三羟甲基丙烷、山梨醇、蔗糖、葡萄糖、间苯二酚、邻苯二酚、焦棓酚、乙醇酸化的脲、1，4-环己二醇、二乙醇胺、三乙醇胺和某些活性多元醇，例如β-羟烷基酰胺，例如双[N，N-二(β-羟乙基)]己二酰胺。多元醇可根据美国专利第4076917号所述制备，或者可以是包含至少两个羟基的加聚物，例如聚乙烯醇、部分水解的聚乙酸乙烯酯、以及(甲基)丙烯酸羟乙酯和(甲基)丙烯酸羟丙酯的均聚物或共聚物。最优选的多元醇是三乙醇胺(TEA)。
所述多羧基聚合物的羧基、酸酐或其盐与多元醇中羟基的当量比约为1/0.01至1/3。优选的是多羧基聚合物中的羧基、酸酐或其盐相对于多元醇中羟基的当量比是过量的。更优选该比例约为1/0.1至1/0.7，最优选该比例为1/0.25至1/0.6。
所述水性组合物优选pH值很低，例如不大于3.5。更优选该水性组合物的pH值等于或小于2.5，最优选等于或小于2。发现当使用这种低pH值的组合物时，可获得极佳的操作优势，所得的产品在压缩后能够回复其初始厚度，具有能够抵抗由于暴露于水分或湿气而造成的下陷或厚度损失的刚性。这些操作优势表现在收集箱中累积纤维的减少，以及固化温度的降低。固化温度的降低使得固化粘合剂所需能量减少，从而如果需要的话，可以在粘合剂中使用更多的水以获得许多操作优势。
本发明的水性组合物还可包含促进剂。优选该促进剂是含磷化合物，该化合物的分子量可约小于1000。其例子包括碱金属次磷酸盐、次磷酸、碱金属亚磷酸盐、碱金属多磷酸盐、碱金属磷酸二氢盐、多磷酸和烷基次膦酸，或者可以是包含含磷基团的低聚物或聚合物，例如在次磷酸钠存在下形成的丙烯酸和/或马来酸的加聚物，在磷盐链转移剂或终止剂的存在下由烯键式不饱和单体制备的加聚物，以及包含酸官能单体残基的加聚物例如共聚的甲基丙烯酸磷酸乙酯和其他膦酸酯，以及共聚的乙烯基磺酸单体及其盐。
为了改进在水性介质中的溶解性，可以用一种或多种固定碱或挥发性碱对所述一种或多种多羧基聚合物的羧酸基团、酸酐基或其盐进行中和。挥发性碱表示在用所述组合物处理基材的条件下具有显著的挥发性的一种或多种碱。固定碱表示在用所述组合物处理基材的条件下基本为非挥发性的碱。
在可能的时候，使用挥发性碱可以使得水性组合物在不需要强酸促进剂的情况下固化。合适的挥发性碱包括例如氨和挥发性低级烷胺。合适的固定碱包括例如氢氧化钠、氢氧化钾、碳酸钠和氢氧化叔丁基铵。所述固定碱具有足够的非挥发性，使得在加热和固化操作的过程中其能够基本保留在水性组合物中。可以在使用固定碱的同时，另外使用挥发性碱。如果所用的共聚物组分是水分散体的形式，碳酸钙之类的多价固定碱会使水性组合物不稳定；然而，可少量使用这些多价固定碱。
在本发明一个实施方式中，所述水性组合物还包含分子量等于或小于1000、优选等于或小于500、最优选等于或小于200的至少一种小分子量多元羧酸、酸酐或其盐。“多元”表示包含至少两个活性酸官能团或酸酐官能团。合适的小分子量多元羧酸和酸酐的例子包括例如马来酸、马来酸酐、富马酸、琥珀酸、琥珀酸酐、癸二酸、壬二酸、己二酸、柠檬酸、戊二酸、酒石酸、衣康酸、苯偏三酸、苯连三酸、苯均三酸、丙三羧酸、1，2，3，4-丁烷四甲酸、苯均四酸、和羧酸的低聚物。所述小分子量多元羧酸、酸酐或其盐可任选在与多羧基聚合物混合之前，在活性条件下与多元醇混合。
在另一实施方式中，所述水性组合物还包含强酸，即至少一个pKa不大于3的非羧酸。在此实施方式中，相对于全部羧酸当量，所述水性组合物优选包含0.01-0.2当量的强酸，更优选为0.01-0.18当量。“全部羧酸”表示水性组合物中羧酸的总含量。所述强酸可以是硫酸之类的无机酸，或者磺酸之类的有机酸。优选无机酸。
在其中所述多羧基加聚物的羧酸基团、酸酐基或其盐被碱(挥发性碱或固定碱)中和的实施方式中，所述水性组合物的pH值可等于或小于9.5。优选pH值等于或小于8.5，较优选等于或小于7.5，更优选等于或小于6.5。在其中所述水性组合物包含强酸的实施方式中，所述粘合剂组合物的pH值优选等于或小于4.5，较优选等于或小于3.5，更优选等于或小于2.5。
在本发明一个实施方式中，所述水性组合物还与包含至少一种共聚的烯键式不饱和非离子型丙烯酸类单体作为聚合单元的乳液聚合物相混合。“主要为丙烯酸类的”表示聚合物中包含大于50重量％、优选大于60重量％的源自(甲基)丙烯酸类单体的共聚单元，例如(甲基)丙烯酸酯、(甲基)丙烯酰胺、(甲基)丙烯腈和(甲基)丙烯酸。非离子型单体表示共聚单体残基在pH值为1-14的范围内不带离子电荷。
烯键式不饱和非离子型丙烯酸类单体包括例如：(甲基)丙烯酸酯单体，其包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸癸酯、丙烯酸月桂酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异癸酯、甲基丙烯酸月桂酯；(甲基)丙烯酸羟烷酯单体，例如甲基丙烯酸-2-羟乙酯、丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯、甲基丙烯酸-1-甲基-2-羟乙酯、丙烯酸-2-羟基丙酯、丙烯酸-1-甲基-2-羟乙酯、甲基丙烯酸-2-羟丁酯和丙烯酸-2-羟丁酯。其他可以结合入所述乳液聚合物中的烯键式不饱和非离子型单体包括乙烯基芳香族化合物，例如苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙基乙烯基苯、乙烯基萘、乙烯基二甲苯和乙烯基甲苯；乙酸乙烯酯、丁酸乙烯酯和其他乙烯酯；乙烯基单体，例如氯乙烯、乙烯基甲苯、乙烯基二苯甲酮和偏二氯乙烯。
其他烯键式不饱和非离子型丙烯酸类单体包括丙烯酰胺；烷基取代的丙烯酰胺，例如丙烯酰胺，甲基丙烯酰胺，N-叔丁基丙烯酰胺和N-甲基(甲基)丙烯酰胺；以及羟基取代的丙烯酰胺，例如羟甲基丙烯酰胺和β-羟烷基酰胺。
所述乳液聚合物可包含单烯键式不饱和酸单体，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、马来酸酐、2-丙烯酰氨基-2-甲基丙磺酸、乙烯基磺酸、苯乙烯磺酸、1-烯丙氧基-2-羟基丙磺酸、烷基烯丙基磺基琥珀酸、(甲基)丙烯酸磺乙酯；(甲基)丙烯酸磷酸烷基酯，例如(甲基)丙烯酸磷酸乙酯、(甲基)丙烯酸磷酸丙酯和(甲基)丙烯酸磷酸丁酯；巴豆酸磷酸烷基酯、马来酸磷酸烷基酯、富马酸磷酸烷基酯、(甲基)丙烯酸磷酸二烷基酯、巴豆酸磷酸二烷基酯和磷酸烯丙酯。
本发明所用的乳液聚合物可包含共聚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、二甲基丙烯酸-1，4-丁二醇酯、二甲基丙烯酸-1，2-乙二醇酯、二丙烯酸-1，6-己二醇酯、丁二烯和二乙烯基苯。
另外，所述水性组合物还可包含常规的处理组分，例如乳化剂、颜料、填料、防迁移助剂、固化剂、聚结剂、润湿剂、疏水剂、生物杀伤剂、增塑剂、有机硅烷、防沫剂、着色剂、蜡和抗氧化剂。
可使用常规混合技术混合所述多羧基聚合物、活性增粘剂和多元醇来制备本发明的水性组合物。或者含羧基或酸酐的聚合物和多元醇可存在于同一聚合物中，所述聚合物可同时包含羧酸、酸酐或其盐的官能团和羟基官能团。在另一实施方式中，所述羧基的盐是具有至少两个羟基的官能化链烷醇胺的盐，所述链烷醇胺是例如二乙醇胺、三乙醇胺，二丙醇胺和二异丙醇胺。在另一实施方式中，多元醇和含磷促进剂可存在于同一聚合物中，该聚合物可与多羧基聚合物混合。在另一实施方式中，所述含羧基或含酸酐的聚合物、多元醇和含磷促进剂可存在于同一聚合物中。其他实施方式对本领域技术人员是显而易见的。
在将所述水性组合物施用在涂敷的垫材之类的基材上之后，对其进行加热使其干燥和固化。加热的持续时间和温度将影响干燥速率、加工性能、操作性能；以及处理后基材所显示的性质。可以在约120-400℃进行约3秒至15分钟的热处理。如果需要的话，干燥和固化可在两个或更多个独立的步骤中进行。例如，可以首先在一定温度下对所述水性组合物加热一段足够长的时间，使组合物基本干燥但是基本不发生固化，然后进行第二次加热，在更高的温度下进行加热以及/或者加热更长的时间以进行固化。
所述水性组合物形成之后，可以立刻用作玻璃纤维之类的材料的粘合剂。在制备玻璃纤维隔绝产品的时候，可使用已知的常规技术。众所周知的是，可以通过对熔融玻璃进行纤维化处理，然后立刻在移动的传送机上形成玻璃纤维垫材，从而制得玻璃纤维多孔垫材。然后将膨胀的垫材传送通过固化炉，在此炉内，加热的空气通过该垫材而使树脂固化。对该垫材进行轻微的挤压，使制得的最终产品具有预定的厚度和表面精整度。通常固化炉的操作温度约为150-325℃。较佳的是，该温度约为180-250℃。通常垫材在炉内停留约1/2分钟至3分钟。在制造常规的绝热或隔音产品时，停留时间约为1分钟至2又1/2分钟。包括固化的刚性粘合剂基质的玻璃纤维以页层(bat)的形式离开固化炉，可以压缩该页层进行包装和运输，当不受限制时，该页层会基本回复其垂直尺寸。
本发明的水性组合物还可用作耐热性非织造织物的粘合剂，所述耐热性非织造织物是例如包含以下耐热性纤维的非织造织物，例如芳族聚酰胺纤维、陶瓷纤维、金属纤维、碳纤维、聚酰亚胺纤维、某些聚酯纤维、人造丝纤维、石棉和玻璃纤维。“耐热性纤维”表示暴露于125℃以上的温度时基本不会受影响的纤维。耐热性非织造织物还可包括本身并非耐热性的纤维，例如某些聚酯纤维、人造丝纤维、尼龙纤维和高吸水性纤维，只要它们不会对基材的性能造成显著的不利影响(例如在足够高的温度下分解)即可。
非织造织物由能够在该织物形成之前、形成过程中和之后通过以下方法固结的纤维制成：纯机械法，例如通过针刺造成的缠结，气流铺置法，以及湿法成网法；化学法，例如用聚合物粘合剂处理；或者机械法和化学法的组合。一些非织造织物在显著高于环境温度的温度下使用，例如用热沥青组合物浸润含玻璃纤维的非织造织物，用来制造屋顶板或屋面卷材材料。当非织造织物与150-250℃温度的热沥青组合物接触时，该非织造织物会发生凹陷、收缩或变形。因此，结合了共聚物组合物的非织造织物应基本保持由固化的水性组合物提供的性能，例如拉伸强度。另外，固化的组合物应当基本不会降低非织造织物的主要性质，例如固化的组合物在加工条件下不能过硬或过脆或变粘。
所述耐热性非织造织物可用于例如绝缘细毛毡或卷材，作为屋顶或地板的增强垫，作为粗纱，作为用于印刷电路板或蓄电池隔板的微型玻璃基材，作为过滤器基质(filter stock)，作为带材基座(tape stock)，以及作为以下材料中的强化纱状织物(scrim)：用于砖石结构的水泥和非水泥涂料，屋顶瓦，纤维质屋顶瓦，窗饰用品，墙面涂层，模塑部件，用来对浆液进行皱状纹理改性，用于粉末涂料等。
Claims (13)
1.一种水性组合物，该组合物包含：
多羧基聚合物，选自：不饱和羧酸的均聚物、或不饱和羧酸或酸酐与一种或多种乙烯基化合物的共聚物；
选自松香基树脂、萜基树脂、苯并呋喃基树脂和酚类增粘剂的活性增粘剂；多元醇。
2.如权利要求1所述的水性组合物，其特征在于，所述组合物的pH值不大于3.5。
3.如权利要求1所述的水性组合物，所述组合物还包含以下的至少一种：含磷促进剂、分子量等于或小于1000的多元酸、和乳液聚合物；
其中所述的含磷促进剂选自：碱金属次磷酸盐、次磷酸、碱金属亚磷酸盐、碱金属多磷酸盐、碱金属磷酸二氢盐、多磷酸、在次磷酸钠存在下形成的丙烯酸和/或马来酸的加聚物、在磷盐链转移剂或终止剂的存在下由烯键式不饱和单体制备的加聚物、包含含磷基团和酸官能单体残基的加聚物、或包含含磷基团的共聚的乙烯基磺酸单体和/或其盐；
其中所述的乳液聚合物是包含至少一种共聚的烯键式不饱和非离子型丙烯酸类单体作为聚合单元的乳液聚合物。
4.如权利要求3所述的水性组合物，其中所述的包含含磷基团和酸官能单体残基的加聚物是包含含磷基团的共聚的甲基丙烯酸磷酸乙酯和其他膦酸酯。
5.如权利要求1所述的水性组合物，其特征在于，所述酚类增粘剂选自：C1-12烷基酚、C1-12芳基酚和C1-12芳烷基酚，以及这些酚与醛的缩合产物。
6.如权利要求1所述的水性组合物，所述组合物还包含选自次磷酸钠、亚磷酸钠及其混合物的促进剂。
7.如权利要求1所述的水性组合物，其特征在于，所述粘合剂中多羧基聚合物和多元醇的量使得羧基与羟基的当量比为1/0.25至1/0.6。
8.如权利要求1所述的水性组合物，其特征在于，所述活性增粘剂是含有以下物质的松香基树脂：聚合松香、歧化松香、氢化松香和酯化松香。
9.如权利要求1所述的水性组合物，其特征在于，所述多元醇是三乙醇胺。
10.如权利要求1所述的水性组合物，其特征在于，所述多羧基聚合物中活性增粘剂的含量占0.1重量％-30重量％。
11.如权利要求1所述的水性组合物，其中所述的不饱和羧酸的均聚物或共聚物是通过自由基加聚反应制备的聚丙烯酸的均聚物或共聚物。
12.一种垫材，包含：玻璃纤维和权利要求1所述的水性组合物，所述的水性组合物用作玻璃纤维的粘合剂。
13.一种耐热性非织造织物，包含：耐热性纤维和权利要求1所述的水性组合物，所述的水性组合物用作耐热性纤维的粘合剂。
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| EP1942119A1 (en) * | 2006-12-22 | 2008-07-09 | Rohm and Haas France SAS | Curable aqueous composition |
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| CN107075257B (zh) * | 2014-10-31 | 2020-10-20 | 陶氏环球技术有限责任公司 | 增粘剂及其连续过程 |
| CN110325596B (zh) * | 2017-07-11 | 2022-03-15 | 盛势达技研株式会社 | 热交联性组合物 |
| CN107502154A (zh) * | 2017-09-14 | 2017-12-22 | 无锡市永兴金属软管有限公司 | 一种适于高压开关柜内金属软管喷涂的耐击穿涂料 |
| US11028214B2 (en) | 2018-01-22 | 2021-06-08 | Corning Incorporated | Synthesis of oligomer for optical fiber coating |
| US11822117B2 (en) * | 2019-10-08 | 2023-11-21 | Corning Incorporated | Primary coating compositions with improved microbending performance |
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