CN106459369A - 无铬酸盐的预处理底漆 - Google Patents
无铬酸盐的预处理底漆 Download PDFInfo
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- CN106459369A CN106459369A CN201580030230.5A CN201580030230A CN106459369A CN 106459369 A CN106459369 A CN 106459369A CN 201580030230 A CN201580030230 A CN 201580030230A CN 106459369 A CN106459369 A CN 106459369A
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Abstract
公开了一种包含环氧官能树脂，耐腐蚀颗粒和多官能交联剂的涂料，还同开了使用这样的涂料来涂覆基材的至少一部分的方法和由此涂覆的基材。
Description
发明领域
本发明涉及涂料组合物，其包含环氧官能树脂，耐腐蚀颗粒和交联剂，该交联剂具有第一官能团(functionality)(其将与环氧官能团交联)和第二官能团(其是自交联的)。本发明还涉及至少部分地涂覆有由这样的组合物沉积的涂层的基材，和多组分复合涂层，其中至少一个涂层是由这样的涂料组合物沉积的。
发明背景
涂料出于多种原因而施涂到器具，汽车，飞机等上，典型地用于腐蚀保护和/或增强的性能。为了改进金属基材的耐腐蚀性，缓蚀剂通常用于施涂到基材的涂料中。常用的缓蚀剂是铬酸锶，其为金属基材(特别是铝基材)提供了优异的耐腐蚀性。但是，缓蚀剂例如铬酸锶是高毒性的和致癌的，并且它们的使用导致产生了废物流，其引起了环境关注和处置问题。
因此，令人期望的是提供一种耐腐蚀涂料，其基本上没有铬酸盐颜料。
发明内容
本发明涉及一种涂料，其包含：(a)第一组分，其包含：(i)环氧官能树脂；和(ii)耐腐蚀颗粒；和(b)第二组分，其包含交联剂，该交联剂具有与第一组分的环氧官能团交联的第一官能团，和自交联的第二官能团。
具体实施方式
本发明涉及一种多组分涂料组合物，其包含在第一组分中的环氧官能树脂和耐腐蚀颗粒和在第二组分中的交联剂。该交联剂具有官能团，其提供了经由两种机理的交联。第一，该交联剂包含官能团，其与环氧树脂上的环氧官能团反应；该交联剂还包含第二官能团，其可以经历自交联。除了自交联之外，在某些实施方案中，该第二官能团还可以充当附着力促进剂。
任何环氧官能树脂可以根据本发明使用。作为此处使用的，“环氧树脂”或者“环氧官能树脂”是具有未反应的环氧官能团的树脂。未反应的环氧官能团能够与涂料上所用的其他化合物上存在的官能团反应。环氧树脂合适的例子包括双酚A，双酚F的二缩水甘油醚，甘油，酚醛清漆等，包括描述在美国专利No.4681811的第5栏第33-58行的那些环氧树脂，其引用部分在此通过引用并入。其他合适的环氧树脂包括聚氨酯环氧树脂(urethaneepoxy)，环氧官能聚硫醚和环氧官能聚硫化物。环氧树脂是广泛市售的，例如在它们的EPON和EPIKOTE种类(line)下市售自Momentive。环氧树脂的混合物也处于本发明的范围内。
任何耐腐蚀颗粒可以根据本发明使用。作为此处使用的，术语“耐腐蚀颗粒”指的是这样的颗粒，其当包括在沉积于基材上的涂料组合物中时，用于提供这样的涂层，其耐受或者在一些情况中甚至防止基材例如由于化学或者电化学氧化过程而导致的改变(alteration)或者降解，包括含铁基材的生锈和铝基材的降解性氧化物。
在某些实施方案中，本发明涉及涂料组合物，其包含含有无机氧化物的耐腐蚀颗粒，在一些实施方案是多种无机氧化物，例如诸如氧化锌(ZnO)，氧化镁(MgO)，氧化铈(CeO2)，氧化钼(MoO3)，氧化镨和/或二氧化硅(SiO2)等。作为此处使用的，术语“多种”表示两种或者更多种。所以，本发明涂料组合物的某些实施方案包含耐腐蚀颗粒，其包含两种，三种，四种或者大于四种的无机氧化物。在某些实施方案中，这些无机氧化物存在于这样的颗粒中，例如以多种氧化物的均匀混合物或者固态溶液的形式存在。
在本发明的某些实施方案中，该耐腐蚀颗粒包含锌，铈，钇，锰，镁，钼，锂，铝，镁，锡或者钙的氧化物。在某些实施方案中，该颗粒包含镁，锌，铈或者钙的氧化物。在某些实施方案中，该颗粒还包含硼，磷，硅，锆，铁或者钛的氧化物。在某些实施方案中，该颗粒包含二氧化硅(“氧化硅”)。
在某些实施方案中，根据本发明使用的耐腐蚀颗粒包含多种无机氧化物，其选自(i)包含铈，锌和硅的氧化物的颗粒；(ii)包含钙，锌和硅的氧化物的颗粒；(iii)包含磷，锌和硅的氧化物的颗粒；(iv)包含钇，锌和硅的氧化物的颗粒；(v)包含钼，锌，和硅的氧化物的颗粒；(vi)包含硼，锌和硅的氧化物的颗粒；(vii)包含铈，铝和硅的氧化物的颗粒，(viii)包含镁或者锡和硅的氧化物的颗粒，和(ix)包含铈，硼和硅的氧化物的颗粒，或者颗粒(i)-(ix)中两种或更多种的混合物。MgO(单独地或者与其他无机氧化物相组合)是特别合适的。
任何平均粒度的任何耐腐蚀颗粒例如MgO可以根据本发明使用。在某些实施方案中，该耐腐蚀颗粒是微米级的，例如0.5-50微米或者1-15微米，并且该尺寸基于平均粒度。在某些实施方案中，该耐腐蚀颗粒是纳米级的，例如10-499纳米，或者10-100纳米，并且该尺寸基于平均粒度。应理解这些粒度指的是在引入至涂料中时耐腐蚀颗粒的粒度。不同的涂料制备方法可导致耐腐蚀颗粒聚集，其将增加平均粒度，或者剪切或者其他作用，其可降低平均粒度。耐腐蚀颗粒市售自许多来源，例如在实施例部分所列的那些。
例如本发明涂料组合物的某些实施方案包含超细耐腐蚀颗粒。作为此处使用的，术语“超细”指的是这样的颗粒，其的B.E.T.比表面积是至少10平方米/克，例如30-500平方米/克，或者在一些情况中是80-250平方米/克。作为此处使用的，术语“B.E.T.比表面积”指的是通过氮气吸附，根据ASTMD3663-78标准，基于描述在期刊“TheJournal of theAmerican Chemical Society”，60，309(1938)中的Brunauer-Emmett-Teller方法所测定的比表面积。
在某些实施方案中，本发明的涂料组合物包含耐腐蚀颗粒例如MgO颗粒，其所计算的当量球直径(equivalent spherical diameter)不大于200nm，例如不大于100nm，或者在某些实施方案中是5-50nm。如本领域技术人员会理解的，所计算的等价球直径可以由B.E.T.比表面积，根据下面的等式来测定：直径(nm)＝6000/[BET(m2/g)*.ρ.(g/cm3)]。
本发明涂料组合物的某些实施方案包含耐腐蚀颗粒例如MgO颗粒，其的平均初级粒度(primary particle size)不大于100nm，例如不大于50nm，或者在某些实施方案中不大于25nm，其是如下来测定的：通过目视检查透射电子显微镜(“TEM”)图像的显微图，测量图像中颗粒的直径，并且计算所测量颗粒的平均初级粒度(基于TEM图像的放大倍率)。本领域技术人员会理解如何准备这样的TEM图像和测定初级粒度(基于放大倍率)。颗粒的初级粒度指的是完全包纳该颗粒的最小球直径。作为此处使用的，术语“初级粒度”指的是单个颗粒的尺寸，这不同于两个或更多个的单个颗粒的聚集体。
在某些实施方案中，该耐腐蚀颗粒具有对组合物介质的亲合力，该亲合力足以将该颗粒保持悬浮于其中。在这些实施方案中，颗粒对于介质的亲合力大于该颗粒对于彼此的亲合力，由此降低或者消除该颗粒在介质内的聚集。
耐腐蚀颗粒例如MgO颗粒的形状(或者形态)可以改变。例如可以使用大体球形的形态，以及立方体的，扁平状的，多面体的或者针状(延长的或者纤维的)的颗粒。在其他具体实施方案中，该颗粒可以完全覆盖于聚合物凝胶中，根本不覆盖于聚合物凝胶中，或者被聚合物凝胶部分地覆盖。“被聚合物凝胶部分地覆盖”表示颗粒的至少某些部分在其上具有沉积的聚合物凝胶，其例如可以共价键合到所述颗粒或者仅仅与所述颗粒相连。
用于本发明涂料中的耐腐蚀颗粒例如MgO的量可以根据用户需要而变化。例如本发明的涂料可以包含1-75重量％的颗粒，例如5-50或者10-50，该重量％基于共混涂料的总固体，包括颜料。“共混涂料”表示施用到基材上的涂料；即，由混合在一起的两种组分所形成的涂料。
在某些实施方案中，该耐腐蚀颗粒明确排除镨。仍然的其他实施方案明确排除全部的稀土元素。稀土表示周期表17个化学元素的整体(collection)，具体地是15个镧系元素(原子数57-71的15个元素，从镧到镥)加上钪和钇。其他具体实施方案排除铬或者其衍生物，例如含铬材料。作为此处使用的，术语“含铬材料”指的是包括三氧化铬基团CrO3的材料。这样的材料非限定性例子包括铬酸，三氧化铬，铬酸酐，重铬酸盐例如重铬酸铵，重铬酸钠，重铬酸钾和重铬酸的钙、钡、镁、锌、镉和锶盐。当本发明的涂料基本上没有或者完全没有铬时，这包括任何形式的铬，包括含铬材料。
因此在某些实施方案中，本发明的涂料基本上没有一种或多种任何形式的稀土金属，包括但不限于氧化镨，和/或任何形式的铬。在其他实施方案中，本发明的涂料组合物完全没有任何或者全部的这些化合物或者材料。作为此处使用的，术语“基本上没有”表示组合物中的特定材料或者化合物(如果有的话)作为附带的杂质存在。换言之，材料的量是如此地小，以至于它不影响组合物的性能；在铬酸盐或者铬的情况中，这可以进一步包括材料不以这样的水平(即，它们造成了环境负担)存在于涂料中。这意味着在本发明的某些实施方案中，该涂料组合物包含小于2重量％的任何或者全部上述化合物或者材料，或者在一些情况中小于0.05重量％的任何或者全部上述化合物或者材料，其中这样的重量百分比是基于组合物的总重量。作为此处使用的，术语“完全没有”表示材料根本不存在于组合物中。
本发明的涂料可以进一步包含氨基酸。当存在时，该氨基酸可以处于第一组分、第二组分或者二者中。氨基酸被本领域技术人员理解为具有酸和胺官能团二者的化合物，其具有对于每个氨基酸来说特定的侧链。该氨基酸可以是单体型或者低聚型，包括二聚物。在某些实施方案中，当使用低聚型氨基酸时，该低聚物通过GPC测定的分子量小于1000。
虽然任何氨基酸可以根据本发明使用，但是特别合适的是组氨酸，精氨酸，赖氨酸，半胱氨酸，胱氨酸，色氨酸，蛋氨酸，苯丙氨酸和酪氨酸。进一步会理解氨基酸可以是L-或者D-对映体，其是彼此的镜像，和L-构型典型地存在于蛋白质和自然界中，并且因此是广泛市售的。作为此处使用的，术语“氨基酸”因此指的是D-和L-构型二者；在某些实施方案中，可以包括仅仅L-或者仅仅D-构型。氨基酸可以例如购自SigmaAldrich，Thermo FisherScientific，Hawkins Pharmaceutical，或者Ajinomato。本发明的某些实施方案明确排除了氨基酸甘氨酸，精氨酸，脯氨酸，半胱氨酸和/或蛋氨酸。
氨基酸可以以任何量存在，其改进了涂料的耐腐蚀性。例如该氨基酸的存在量可以是0.1-20重量％，例如2-4重量％，并且重量百分比基于共混涂料的树脂固体。氨基酸的量和耐腐蚀颗粒的量可以一起经选择来赋予涂料优化的耐腐蚀性。
如上所述，本发明的涂料组合物包含第二组分，该第二组分包含交联剂或者固化剂。该交联剂具有与环氧树脂的环氧官能团反应的官能团。这样的官能团的例子包括例如胺基团，酰胺基团和硫醇基团。该交联剂还包含会自交联的官能团；即，它会与自身交联。这样的官能团的例子包括烷氧基-硅烷，烷氧基-钛酸酯和烷氧基-锆酸酯。虽然该交联剂已经在此描述为具有两种不同类型的官能团，但是它也可以具有大于两种类型。
特别合适的交联剂包括氨基硅烷。在某些实施方案中，该交联剂包含双足(dipodal)硅烷。“双足硅烷”应理解为指的是具有两个明显分开的硅原子的交联剂，其包含烷氧基-硅烷官能团。市售的双足硅烷的例子包括来自于Momentive的SILQUEST A1170(双(三甲氧基甲硅烷基丙基)胺)，来自于Gelest的SIB1834(双[(三甲氧基甲硅烷基)丙基]-亚乙基二胺)和同样来自于Gelest的SIB1620(双(甲基二乙氧基甲硅烷基丙基)胺)。
本发明的涂料组合物是多组分涂料组合物。虽然在此描述为包含第一和第二组分，但是会理解任何数目的另外的也组分可以用于配制所述涂料。该组分将在施用之前混合。
该环氧树脂和交联剂包含成膜树脂。作为此处使用的，术语“成膜树脂”指的是这样的树脂，其可以在除去组合物中存在的任何稀释剂或载体后或者在环境温度或升高的温度固化后，以在基材的至少水平表面上形成自支撑连续膜。本发明的涂料可以在环境条件下固化。环境条件表示该涂料不借助于热或者其他能量(例如不在烘箱中焙烤，不使用强制通风等)而经历热固化反应。
如上所述，本发明的组合物通过两种机理固化。在第一机理中，交联剂上的环氧反应性官能团例如胺官能团与环氧树脂上的环氧官能团反应。在第二机理中，交联剂上的硅烷自缩合。可以进行甚至另外的固化机理，这取决于该第一组分或者第二组分中的其他官能团。
还可以在涂料中使用一种或多种另外的成膜树脂。可以使用的另外的成膜树脂包括但不限于用于航空航天涂料组合物，汽车OEM涂料组合物，汽车整修(refinish)涂料组合物，工业涂料组合物，建筑涂料组合物和卷材涂料组合物等的那些。适用于本发明涂料组合物的成膜树脂包括例如基于丙烯酸类，饱和或者不饱和聚酯，醇酸，聚氨酯或者聚醚，聚乙烯基，纤维素，硅基聚合物，其共聚物的树脂，该树脂可以包含反应性基团例如环氧，羧酸，羟基，异氰酸酯，酰胺，氨基甲酸酯，胺和羧酸酯基团等，包括其混合物。可以使用成膜树脂的组合。在某些实施方案中，包括在本发明的涂料组合物中的另外的成膜树脂包含具有会与上述交联剂固化的官能团的树脂，而在其他实施方案中，可以使用一种或多种另外的交联剂。合适的交联剂可以由本领域技术人员基于所选择的树脂来确定。
在本发明的某些实施方案中，环氧树脂在本发明的涂料组合物中的存在量大于10重量％，例如20-90重量％，或者在一些情况中是20-60重量％，并且重量百分比基于共混涂料组合物的总固体重量。交联剂在这些实施方案中的总量可以以至多70重量％，例如10-70或者10-40重量％的量存在；这个重量百分比也基于共混涂料组合物的总固体重量。应理解根据本发明的某些实施方案所用的氨基硅烷被用作成膜树脂中的交联剂，并且不以硅烷用作添加剂来例如改进附着性时典型的用量加入。在某些实施方案中，环氧与胺的当量比是2：1-1：2，例如1.5：1-1：1.5或者1.2：1.0。
根据本发明的实施方案，该涂料组合物处于液体涂料组合物的形式，其例子包括水性(WB)和溶剂性(SB)涂料组合物和可电沉积涂料组合物。本发明的涂料组合物也可以处于微粒形式的可共反应(co-reactable)固体形式(即，粉末涂料组合物)。
当水用作主稀释剂(即大于50％)时，涂料组合物可以是水性涂料组合物。在其他实施方案中，当溶剂用作主稀释剂(即大于50％)时，该涂料组合物可以是溶剂性涂料组合物。例如在某些实施方案中，本发明可以包含溶剂例如酮，乙酸酯，二醇，醇和/或芳族溶剂。示例性的合适的溶剂描述在美国专利No.6774168第3栏第28-41行中，其引用部分在此通过引用并入。
如上所述，该水性或者溶剂性涂料组合物是多组分体系，其包括基础组分例如环氧官能聚合物，活化剂或者交联剂组分，例如胺官能硅烷，和任选的第三组分，例如稀释剂组分，例如水或者水溶液。其他成分可以任选地包含在任何所述组分中。该混合物的三种组分可以在即将施用到基材之前合并。例如该环氧官能聚合物基础组分和胺官能硅烷活化剂组分，和任何其他另外的组分(若使用)，可以分别储存和在即将使用之前混合。
本发明的涂料组合物还可以包含涂料制造领域的任何常规添加剂，包括着色剂，增塑剂，耐磨颗粒，膜增强颗粒，流动控制剂，触变剂，流变改性剂，催化剂，抗氧化剂，生物杀灭剂，消泡剂，表面活性剂，润湿剂，分散助剂，附着力促进剂，粘土，受阻胺光稳定剂，UV光吸收剂和稳定剂，稳定剂，填料，有机助溶剂，反应性稀释剂，研磨载体和其他常规助剂或者其组合。作为此处使用的，术语“着色剂”是美国专利公开No.2012/0149820第29-38段所定义的，其引用部分在此通过引用并入。
“耐磨颗粒”是这样的颗粒，其当用于涂料时，与没有该颗粒的相同涂料相比，将赋予涂料一些水平的耐磨性。合适的耐磨颗粒包括有机和/或无机颗粒。合适的有机颗粒的例子包括但不限于金刚石颗粒，例如金刚石粉末(diamond dust)颗粒，和由碳化物材料形成的颗粒；碳化物颗粒的例子包括但不限于碳化钛，碳化硅和碳化硼。合适的无机颗粒的例子包括但不限于二氧化硅；氧化铝；氧化铝硅酸盐；二氧化硅氧化铝；碱性铝硅酸盐；硼硅酸盐玻璃；氮化物，包括氮化硼和氮化硅；氧化物，包括二氧化钛和氧化锌；石英；霞石正长岩；锆石例如处于氧化锆的形式；buddeluyite；和异性石。可以使用任何尺寸的颗粒，如可以使用不同的颗粒和/或不同尺寸的颗粒的混合物。例如该颗粒可以是微粒，平均粒度是0.1-50，0.1-20，1-12，1-10，或者3-6微米，或者处于这些范围的任何的任意组合。所述颗粒可以是纳米颗粒，平均粒度小于0.1微米例如0.8-500，10-100，或者100-500nm，或者这些范围内的任意组合。
作为此处使用的，术语“附着力促进剂”和“附着力促进性组分”指的是任何这样的材料，其当包括在组合物中时，增强了涂料组合物到金属基材的附着力。在本发明的某些实施方案中，这样的附着力促进性“组分”是交联剂本身。这据信是通过与基材表面形成共价键而发生的，虽然本发明人不希望受限于这种机理。
在某些实施方案中，本发明的涂料组合物除了任何前述耐腐蚀颗粒之外，还可以包括另外的常规非铬耐腐蚀颗粒。合适的常规非铬耐腐蚀颗粒包括但不限于磷酸铁，磷酸锌，钙离子交换的二氧化硅，胶体二氧化硅，合成非晶二氧化硅和钼酸盐例如钼酸钙，钼酸锌，钼酸钡，钼酸锶及其混合物。合适的钙离子交换的二氧化硅作为SHIELDEX.AC3和/或SHIELDEX.C303市售自W.R.Grace&Co.。合适的非晶二氧化硅作为SYLOID获自W.R.Grace&Co.。合适的羟基磷酸锌作为NALZIN.2市售自Elementis Specialties，Inc.。这些常规的非铬耐腐蚀颜料典型地包含粒度是大约1微米或者更大的颗粒。在某些实施方案中，这些颗粒在本发明的涂料组合物中的存在量是5-40重量％，例如10-25重量％，并且该重量百分比基于组合物的总固体重量。
本发明的涂料还可以包含一种或多种有机抑制剂。这样的抑制剂的例子包括但不限于含硫和/或含氮的杂环化合物，其例子包括唑类，噻吩，肼和衍生物，吡咯和衍生物。这样的有机抑制剂描述在美国公开No.2013/0065985第52段，其在此通过引用并入。当使用时，有机抑制剂在涂料组合物中的存在量是0.1-20重量％，例如0.5-10重量％，并且重量百分比是基于共混的组合物的总固体重量。
本发明的涂料还可以包含一种或多种催化剂。虽然任何适当的催化剂可以根据本领域技术人员的决定来使用，但是胺催化剂是特别合适的。例子包括叔胺催化剂例如2，4，6-三(二甲基氨基甲基)苯酚，其作为ANCAMINE K54市售自Air Products。其他合适的催化剂包括但不限于咪唑，路易斯酸和间苯二酚。
如上所述，本发明的涂料组合物可以是液体涂料组合物，其例子包括含水或者水基和溶剂基涂料组合物和可电沉积涂料组合物，或者处于可共反应固体(处于微粒形式)的形式，即，粉末涂料组合物。不管形式如何，本发明的涂料组合物可以是着色的或者是透明的，并且可以单独使用或者组合使用，用作底漆，底涂层或者面漆。如下面更详细讨论的，本发明的某些实施方案涉及耐腐蚀底漆和/或预处理涂料组合物。如所述的，本发明的某些实施方案涉及金属基材底漆涂料组合物，例如“洗涤底漆(wash primer)”和/或金属基材预处理涂料组合物。作为此处使用的，术语“底漆涂料组合物”指的是这样的涂料组合物，底涂层(undercoating)可以由其沉积到基材上。在一些工业或者基材中，施涂底漆来制备表面，以用于施用保护性或者装饰性涂层系统。在其他工业或者基材中，另一涂层不施涂到底漆的顶上。例如，基材表面(其具有有限的或者没有外部曝露)可以具有顶上不具有其他层的底漆。作为此处使用的，术语“洗涤底漆”指的是这样的底漆涂料组合物，其包括附着力促进性组分例如烷氧基硅烷，如上面更详细描述的。作为此处使用的，术语“预处理涂料组合物”指的是这样的涂料组合物，其可以以非常低的膜厚施用到裸基材上，来改进耐腐蚀性或者增加随后施涂的涂层的附着力。
当本发明的涂料组合物用作底漆时，在一些实施方案中，保护性和/或装饰性涂层系统可以施用到底漆的至少一部分上，例如单涂层面漆或者着色的底涂料组合物和透明涂料组合物的组合，即，彩色加透明体系。因此，本发明还涉及多组分复合涂料，其包含由本发明的涂料组合物沉积的至少一个涂层。在某些实施方案中，本发明的多组分复合涂料组合物包含底涂层成膜组合物，其充当了底涂层(经常是着色的有色涂层)，和施用到该底涂层上的成膜组合物，其充当了面漆(经常是透明涂层)。
在本发明的这些实施方案中，涂料组合物(由其来沉积底涂层和/或面漆)可以包含例如在例如配制汽车OEM涂料组合物，汽车整修涂料组合物，工业涂料组合物，建筑涂料组合物，卷材涂料组合物和航空航天涂料组合物的领域的本领域技术人员已知的任何的常规底涂层或者面漆涂料组合物。这样的组合物典型地包括成膜树脂，其可以包括例如丙烯酸类聚合物，聚酯和/或聚氨酯。示例性的成膜树脂公开在美国专利No.4220679第2栏第24行到第4栏第40行；以及美国专利No.4403003，美国专利No.4147679和美国专利No.5071904，其整个内容在此通过引用并入。
可以用这样的组合物涂覆的金属基材包括例如包含如下的基材，钢(包括电镀锌钢，冷轧钢，热浸镀锌钢等)，铝，铝合金，锌-铝合金，包层铝(clad aluminum)和镀铝钢。可以用这样的组合物涂覆的基材还可以包含大于一种金属或者金属合金，这在于该基材可以是组装在一起的两种或者更多种金属基材的组合，例如与铝基材组装的热浸镀锌钢。该基材可以是这样的基材，其已经以一些方式处理，例如来赋予视觉和/或颜色效果，或者一些性能增强例如耐腐蚀性。
因此，本发明进一步涉及一种基材，其至少部分地涂覆有本发明的涂料。该基材可以包含运载工具的一部分。“运载工具”在此是以它最宽的含义来使用的，并且包括全部类型的运载工具，例如但不限于飞机，直升飞机，汽车，卡车，巴士，货车，高尔夫球车，摩托车，自行车，有轨电车，坦克等。会理解该运载工具的根据本发明涂覆的部分可以取决于为什么涂料被使用而变化。
本发明的涂料组合物(其可以例如是金属基材底漆涂料组合物和/或金属基材预处理涂料组合物)可施用到裸的金属上。“裸”表示纯净材料，其没有用任何预处理组合物处理，例如诸如常规的磷化浴(phosphating bath)，重金属冲洗等。另外，用本发明的涂料组合物涂覆的裸金属基材可以是基材的切割边缘，该基材是在它的其余表面上以其他方式处理和/或涂覆的。在某些实施方案中，所述基材可以在施用涂料和/或预处理之前研磨。“研磨”表示通过机械作用部分地研磨掉基材表面。这可以通过手或者机器，使用研磨性材料例如砂纸，SCOTCHBRITE垫，或者研磨性材料的浆体例如摩擦化合物或者抛光化合物来进行。
在将本发明的涂料组合物作为底漆和/或金属预处理施用之前，待涂覆的金属基材可以首先经清洁来除去油脂、脏物或者其他异物。可以使用常规的清洁程序和材料。这些材料可以包括例如中等或者强碱性清洁剂，例如是市售的那些。例子包括BASE Phase Non-Phos和BASE Phase#6，二者都获自PPG Industries，Pretreatment and SpecialtyProducts。其他例子包括ALK-660和ED-500，二者都获自PPG Industries，AerospaceCoatings Products。这样的清洁剂的施用经常在水冲洗之前和/或之后。
在用碱性清洁剂清洁之后和在与本发明的涂料组合物接触之前，该金属表面然后可以用酸性水溶液冲洗。合适的冲洗溶液的例子包括中等或者强酸性清洁剂，例如市售的稀硝酸溶液。例子包括AC-5，AC-12和EAC-8，其全部获自PPG Industries，AerospaceCoatings Products。还可以使用组合的清洁/研磨溶液。
本发明的涂料组合物可以通过任何多种方法来制备。例如在某些实施方案中，耐腐蚀颗粒可以在配制包含环氧官能树脂的涂料组合物过程中的任何时间加入，只要它们形成在环氧官能树脂中的稳定的分散体就行。本发明的涂料组合物可以如下来制备：首先将环氧官能树脂，耐腐蚀颗粒，颜料，填料和稀释剂例如有机溶剂和/或水进行混合，将该混合物用高速分散机以1000-2000RPM分散10-30分钟，然后将该分散体送过油漆磨机来实现5+的研磨细度(其是用研磨规(grinding gauge)检测的)。
本发明的涂料组合物可以通过已知的施涂技术施涂到基材上，例如浸涂或者浸没，喷涂，间歇喷涂，浸涂随后喷涂，喷涂随后浸涂，刷涂或者通过辊涂。可以使用通常的喷涂技术和用于空气喷涂和静电喷涂(手动或者自动方法)的装置。虽然本发明的涂料组合物可以施涂到不同的基材，例如木材，玻璃，布，塑料，泡沫，包括弹性体基材等，但是在许多情况中，该基材包含金属，例如上述的那些。
在本发明的涂料组合物的某些实施方案中，在将所述组合物施涂到基材之后，通过加热或者通过空气干燥期来将溶剂(即，有机溶剂和/或水)逐出所述膜，以在基材表面上形成膜。合适的干燥条件将取决于具体组成和/或应用，但是在一些情况中在大约70-250°F(27-121℃)的温度大约1-5分钟的干燥时间将是足够的。如果期望，可以施用本发明组合物的大于一个涂层。在某些实施方案中，两个或更多个涂层是“湿碰湿”施涂的，其中所述涂层的至少一个包括本发明的涂层。通常在涂覆之间，闪蒸在先施用的涂层；即，曝露于环境条件持续期望的时间量。在某些实施方案中，涂层厚度是0.1-3密耳(2.5-75微米)，例如0.2-2.0密耳(5.0-50微米)。该涂料组合物然后可经加热。在固化操作过程，将溶剂驱除，并且所述组合物的可交联组分(如果有的话)经交联。该加热和固化操作有时候在70-250°F(27-121℃)的温度进行，但是如果需要，可以使用更低或者更高的温度。如前所述，本发明的涂料也可以固化，而无需加入加热或者干燥步骤，即，在“环境条件”固化。在环境条件下固化的能力是本发明涂料的优点。
卷材涂料(其在许多工业中具有广泛应用)也处于本发明范围内。
作为此处使用的，除非另有明确规定，否则全部的数字例如表达值，范围，量或者百分比的那些可以解读为是用措词“大约”作为前缀的，即使该术语没有明确出现也是如此。同样，此处所引用的任何数字范围目的是包括其中所含的全部子范围。复数包括了单数，并且反之亦然。例如，虽然此处提及了“一种”环氧官能树脂，“一种”耐腐蚀颗粒和“一种”交联剂，但是可以使用此处所述的这些和任何其他组分的每个中的一种或多种。作为此处使用的，术语“聚合物”指的是低聚物以及均聚物和共聚物二者，和前缀“聚”指的是两种或更多种。包括和类似术语表示包括但不限于。当给定范围时，那些范围的任何端点和/或处于那些范围内的数字可以在本发明范围内组合。
实施例
下面的实施例旨在说明本发明，并且不应当解释以任何方式限制本发明。
表1提供了对于实施例制备中所用材料的描述。
表1
对于全部实施例，每个材料的给定量是以克计(重量)的。
一种涂料是如下所述，使用表2所示材料来制备的。
表2
涂料实施例的基础组分是通过将组合物的材料使用高速分散共混在一起，随后在水平珠磨机上研磨来制备的。最终的基础组分的研磨细度低于10微米，其是通过研磨规，根据ISO1524测量的。涂料实施例的活化剂组分是通过将组合物的材料使用温和搅拌共混在一起来制备的。将两种组分放置最少1天，然后施用到试件(test piece)上。
该基础和活化剂组分是以2单位的基础比2单位的活化剂的体积比来混合在一起的。将所述组分手工混合直到均匀。在混合产物施用之前，无需诱导时间。
测试面板的制备
将该混合的涂料实施例施用到包层和未包层的2024-T3铝合金面板上，该面板已经使用来自于3M的绿色进行研磨。该制备程序包括溶剂脱脂所述面板，随后使用浸泡在碱性脱脂溶液中的Scotchbrite研磨。该面板然后在自来水下冲洗，并且在用溶剂擦拭之前使其干燥，然后施用该混合的涂料实施例。
该混合的涂料实施例使用重力供料空气雾化喷枪来施涂到所制备的测试面板上，来实现最终(干膜)膜厚是10+/-2微米。
所进行的测试
所进行的测试包括根据测试方法ISO 2409进行干和湿粘附和根据测试方法ISO3665进行丝状腐蚀测试。
结果评价
典型的结果显示在下表中；数值评价是在用于干和湿粘附测试的ISO 2409中定义的。丝状腐蚀等级是作为存在于每个面板上的最长的细丝来记录的，并且以毫米为单位测量。一式三份进行每个测试，并且每个单个测试面板的结果在下表中通过短划线隔开。
| 基材 | 粘附 | 水 | 丝状1000H |
| 包层 | 0-0-0 | 1-1-1 | 0.8-1.1-0.8 |
| 裸 | 1.2-1.9-1.4 |
要注意的是本发明的涂料表现出对于包层铝合金良好的粘附特性，初始时是100％粘附，和在曝露于水之后是95％或更大的粘附。此外，本发明的涂料对于包层和裸的铝合金二者表现出良好的腐蚀丝状腐蚀结果，其中不存在长度大于1.9mm的腐蚀细丝。
制备测试面板II
将混合的涂料实施例施用到包层和未包层的2024-T3铝合金面板上，其具有如AMS-3095A第4.3.2节所述制备的表面。将该混合的涂料实施例使用重力供料空气雾化喷枪施用到所制备的测试面板上，以实现最终(干膜)膜厚10+/-2微米。使得含有该涂料实施例的测试面板在环境条件干燥4-24小时，然后将获自PPG Industries，Inc.的DESOPRIMECF7065无铬底漆施用到所述面板，并且根据制造商的说明书进行干燥。在合适的干燥之后，将获自PPG Industries，Inc.的DESOTHANE HS Topcoat Grey CA8800B00707施用到所述面板，并且根据制造商的说明书进行干燥。
所进行的测试II
在多层涂层面板上的测试是根据AMS 3095A进行的，并且包括干和湿粘附，反向冲击，锥形心轴挠性，圆柱形心轴挠性，耐流体性(fluid resistance)，丝状腐蚀和盐雾腐蚀。
测试结果II的评价
典型的结果显示于下表中。所述测试方法和参数的进一步说明可以在AMS 3095A中获得。全部结果是针对2024T3包层，除非另有指示
要注意的是当用于具有市售底漆和面漆的多层涂层体系中时，本发明的涂料表现出良好的性能特性，其与AMS 3095A航空航天性能规格所概述的这些测试是一致的。
Claims (22)
1.一种涂料，包含：
(a)第一组分，其包含：
(i)环氧官能树脂；和
(ii)耐腐蚀颗粒；和
(b)第二组分，其包含交联剂，该交联剂具有与第一组分的环氧官能团交联的第一官能团，和自交联的第二官能团。
2.权利要求1的涂料，其中该环氧官能树脂包含双酚-A的残基。
3.权利要求1的涂料，其中该环氧树脂包括聚氨酯环氧树脂。
4.权利要求1的涂料，其中缓蚀剂包括MgO。
5.权利要求4的涂料，其中该MgO的表面积是至少10平方米/克。
6.权利要求1的涂料，其中该涂料进一步包含氨基酸。
7.权利要求1的涂料，其中该交联剂包括硅烷。
8.权利要求7的涂料，其中该硅烷包括双足硅烷。
9.权利要求7的涂料，其中该硅烷主要由双足硅烷组成。
10.权利要求8的涂料，其中该硅烷包括双(三甲氧基甲硅烷基丙基)胺。
11.权利要求9的涂料，其中该硅烷包括双(三甲氧基甲硅烷基丙基)胺。
12.权利要求1的涂料，其中该第二组分进一步包含胺催化剂。
13.权利要求12的涂料，其中该胺催化剂包括叔胺。
14.权利要求7的涂料，其中该与环氧树脂反应的官能团是胺。
15.权利要求1的涂料，其中所述涂料基本上没有铬。
16.权利要求1的涂料，其中所述涂料基本上没有氧化镨。
17.一种涂覆基材的方法，其包括向该基材的至少一部分上施涂权利要求1的涂料。
18.根据权利要求17涂覆的基材。
19.权利要求18的基材，其中该基材包括铝。
20.权利要求18的基材，其中该基材包括钢。
21.权利要求1的涂料，其中该涂料基本上没有稀土元素。
22.权利要求1的涂料，其中该涂料在环境条件固化。
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| CN114806322A (zh) * | 2021-01-29 | 2022-07-29 | 海洋化工研究院有限公司 | 一种生物基柔性环氧防火涂料及其制备方法和应用 |
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| US20210363358A1 (en) * | 2017-12-20 | 2021-11-25 | Ppg Industries Ohio, Inc. | Coating Compositions Having Improved Corrosion Resistance |
| CN115279842A (zh) * | 2020-03-30 | 2022-11-01 | 阿克佐诺贝尔国际涂料股份有限公司 | 可高温固化的涂料组合物 |
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2014
- 2014-05-09 US US14/273,567 patent/US20150322271A1/en not_active Abandoned
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114806322A (zh) * | 2021-01-29 | 2022-07-29 | 海洋化工研究院有限公司 | 一种生物基柔性环氧防火涂料及其制备方法和应用 |
| CN114806322B (zh) * | 2021-01-29 | 2022-12-20 | 海洋化工研究院有限公司 | 一种生物基柔性环氧防火涂料及其制备方法和应用 |
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| US11739222B2 (en) | 2023-08-29 |
| EP3140356A1 (en) | 2017-03-15 |
| JP6594341B2 (ja) | 2019-10-23 |
| RU2016148289A3 (zh) | 2018-06-09 |
| ES2708585T3 (es) | 2019-04-10 |
| AU2015255918B2 (en) | 2017-07-27 |
| KR20170007364A (ko) | 2017-01-18 |
| US20150322271A1 (en) | 2015-11-12 |
| RU2664103C2 (ru) | 2018-08-15 |
| US20230407103A1 (en) | 2023-12-21 |
| JP2017517599A (ja) | 2017-06-29 |
| JP2018059123A (ja) | 2018-04-12 |
| US12024645B2 (en) | 2024-07-02 |
| US20200224038A1 (en) | 2020-07-16 |
| KR101980953B1 (ko) | 2019-05-21 |
| CN114106657A (zh) | 2022-03-01 |
| RU2016148289A (ru) | 2018-06-09 |
| CA2948350A1 (en) | 2015-11-12 |
| AU2015255918A1 (en) | 2016-12-15 |
| EP3140356B1 (en) | 2018-11-14 |
| CA2948350C (en) | 2019-09-17 |
| WO2015171891A1 (en) | 2015-11-12 |
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