CN102325949A - 表面组合物及应用方法 - Google Patents

表面组合物及应用方法 Download PDF

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Publication number
CN102325949A
CN102325949A CN2009801573510A CN200980157351A CN102325949A CN 102325949 A CN102325949 A CN 102325949A CN 2009801573510 A CN2009801573510 A CN 2009801573510A CN 200980157351 A CN200980157351 A CN 200980157351A CN 102325949 A CN102325949 A CN 102325949A
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China
Prior art keywords
surface composition
layer
transparent
gel layer
lower floor
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CN2009801573510A
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CN102325949B (zh
Inventor
卢·贝亚勒
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Hydrawall Pty Ltd
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Hydrawall Pty Ltd
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Priority claimed from AU2009900767A external-priority patent/AU2009900767A0/en
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Abstract

在此提供了用于减小这些经受了在水性液体中的长期浸没的表面的降解和褪色的一种表面组合物。这种表面组合物包括至少一个透明阻挡层以及至少一个下层，其中该透明阻挡层在使用中被布置在该下层之上并且与该水性液体相接触，由此该透明阻挡层保护了该下层的结构和外观。该表面组合物在以下应用中是特别有用的：在其中该表面经受了在包含水解或氧化性试剂的液体中的长期浸没、在紫外辐射中的暴露或两者的组合，由此该透明阻挡层提供了结构性保护以对抗来自化学侵蚀的降解和由于UV暴露造成的褪色。还提供了一种用于制造游泳池的表面组合物的方法。进一步提供了一种表面组合物在制造游泳池或温泉池中的用途。还提供了由本发明的表面组合物所制造的游泳池或温泉池。

Description

表面组合物及应用方法
技术领域
本发明涉及一种用于保护经受长期浸没的表面免于降解和褪色的表面组合物，例如保护游泳池和温泉池的表面层饰面(finish)。本发明还涉及一种表面组合物的应用方法并且涉及由其制造的产品。
发明背景
可以安装游泳池以及温泉池用于私人或公共用途并且用于多种不同的用途，例如比赛、锻炼、娱乐、休闲或疗养。用于水池的构造方法可以不相同，但如果该水池作为一个永久的固定设施来保留，埋地式的形式是最流行的。埋地式水池的主要类型是混凝土、玻璃纤维增强的塑料(FRP)以及乙烯基衬里的池。
典型地，玻璃纤维池对于私人设施是最流行的，例如在私人住宅中安装的那些。玻璃纤维水池是由玻璃纤维增强的塑料制成的，该塑料被模制成一个盆的形状，这是该水池的最终形状。该水池的形状以及构型取决于该模具的形状。典型地，任何一个水池制造厂商将具有一组模具选择，消费者可以从中选择他们的水池设计。
选择玻璃纤维水池的形状和尺寸是当消费者选择其水池时必须做出的重要决定。可以认为，另一个最重要的决定是选择该水池的表面饰面，该表面饰面决定了该水池在充满水时将具有的外观。表面饰面的选择可以包括颜色、闪耀或闪烁的选择，其组合可以使水池的外观与其周围环境相匹配并且给予这个外观颜色深度和亮度，并且获得大理石或花岗岩效果。
不论所选择的水池形状或表面饰面如何，对于所有玻璃纤维水池的共同之处是一旦安装，该表面就完全浸没在水中并且无限地保持为这样。也就是说，水从不会完全排出并且一直保持在该水池结构中。这不可避免地产生了两个方面的问题。第一个是，水本身(典型地具有12℃至41℃之间的温度)是能够溶解任何水溶性材料(WSM)并且水解在水池制造中所使用的任何水溶性组分的一种严苛的溶剂。
第二个问题是，水必须是卫生的以杀死藻类和病原体如细菌和原生动物，因为不进行消毒，这些病原体则将在水中茁壮成长，从而创造一个让微生物从一个人传递给下一个的完美场所。水池过滤器系统可以辅助保持水的清洁；然而，为了适当地关注水病原体，必要的是向水中引入一种消毒剂。
最普遍的水池消毒剂是氯，它能以不同形式引入，例如次氯酸钙或次氯酸钠。氯也通过盐的水解而产生，通常称为“盐水加氯器(salt waterchlorinator)”。当这些化合物加入到水中时，氯组分发生反应而形成不同的化学物，包括起到杀死病原体作用的次氯酸。替代的卫生消毒剂如溴化物、臭氧或过氧化氢发挥了基本上相同的消毒作用。
因为次氯酸不是一种特别稳定的化合物，所以通常必须要向池水中加入另外的化学物，包括稳定剂，如氰尿酸。此外，令人希望地将池水的pH水平保持在基本上中性的水平(7与7.8之间的pH)，因为太酸性亦或太碱性的水将引起所不希望的化学反应。典型地向池水中加入另外的化学物以维持该pH，如提高pH的碳酸钠或碳酸氢钠，以及硫酸氢钠或液体酸，如盐酸或硫酸。
这种化学鸡尾酒(chemical cocktail)在水性环境中的组合最终造成了水池表面的漂白以及降解。随着时间过去，通常存在清晰的池表面褪色和退化的标志，这将显著地减损水池的美学外观。褪色和退化问题由于许多其他因素而增加，例如：
a)暴露于UV光中，特别是当该水池位于户外时；
b)对水池的疏忽和管理不善，包括消费者不正确地施加化学物；
c)由于温泉池的加热和应用而导致的水温升高，这恶化了水和化学物的降解过程；以及
d)使用自动消毒剂、盐水加氯器以及pH控制剂，它们会导致水池的酸、碱以及氧化剂在产品的有效操作参数之外的过量投加。
e)连续暴露于水中以及水的水解作用。
尽管存在这些问题，但消费者的期望是要求如下一种产品，它可以经受住降解并且重要地是长期保持初始颜色而不必需昂贵且耗时的对水池表面的剥离和翻新或甚至更换池本身(这些是一旦发生水池表面的降解时唯一永久的且消费者可接受的补救方法)。类似地，一般对水池提供某种程度的保证的水池制造商不希望在水池表面不能经受住规定时期的降解时对修补或更换负责。
由于表面降解问题(包括褪色)是这样一种普遍的问题，所以已经进行了不同尝试来补救或至少减轻这种问题。此种补救包括优先于有机颜料而使用无机彩色颜料，如金属的盐和氧化物，因为这种有机颜料尽管一般更明亮，但是是较不稳定的。另一种补救方法是以诸如白色、奶油色或非常浅的蓝色来生产水池，这些颜色只显示最小的褪色作用。此种补救方法的不幸结果是然后颜色以及饰面的选择会严格地受限制。
通过在聚酯凝胶层(该凝胶层具有某些耐UV的特性)中施加颜色和装饰性表面饰面已经实现了某种成功。然而，尽管已知的凝胶层能够提供某种程度的对水池外观而言的耐受性以及长寿命，但在大约6至10年之后，这种表面饰面颜料不可避免地开始褪色并且水池外观变得消弱并且看上去被冲洗掉。
此外，尽管施加一个另外的保护层或阻挡层起先看上去是保护美学(特别是颜色)品质的一种可行方案，但迄今为止，此种施加没有一种在独特的水池环境中(其中水池表面经受长期的浸没)是成功的。
因此对于如下一种产品存在着需要，该产品可以阻止水池表面饰面的褪色和降解而不损害对颜色和饰面选择的可得性。
发明概述
根据本发明的一个第一方面，提供了用于减小这些经受在水性液体中的长期浸没的表面的降解和褪色的一种表面组合物，这种表面组合物包括至少一个透明阻挡层以及至少一个下层，其中该透明阻挡层在使用中被布置在该下层之上并且与该水性液体相接触，由此该透明阻挡层保护了该下层的结构和外观。
该表面组合物在以下应用中是特别有用的：在其中该表面经受了在包含水解或氧化性试剂的液体中的长期浸没、在紫外辐射中的暴露或两者的组合，由此该透明阻挡层提供了结构性保护以对抗来自化学侵蚀的降解和由UV暴露所造成的褪色。
在本发明的一个特别优选的实施方案中，该下层是一个装饰层，包含一种或多种装饰性或观赏性试剂，这些试剂被提供来给予一种所希望的视觉或美学外观。这种装饰性或观赏性试剂可以包括但不限于颜料、颗粒以及碎屑。
这种表面组合物特别地应用于对游泳池和温泉池创造一个表面饰面，特别是对纤维增强的塑料(FRP)池。
这种表面组合物提供了在阻挡层与下层之间强力的层间结合。照这样，本发明的表面组合物有利地最小化了分层作用并且阻止了渗透性起泡。
在一个实施方案中，该组合物包括一种或多种UV抑制剂、吸收剂和/或稳定剂。优选地，该透明阻挡层包括一种或多种UV抑制剂、吸收剂和/或稳定剂。
在另一个实施方案中，该透明阻挡层是一个透明的聚酯凝胶层。优选地，该透明的聚酯凝胶层包括一种或多种含邻苯二甲酸酯的聚酯、含乙烯基的聚酯或含甲基丙烯酸甲酯的聚酯。更优选地，该透明的聚酯凝胶层包括一种含邻苯二甲酸酯的聚酯，特别是衍生自间苯二甲酸新戊二醇(iso-NPG)的一种含邻苯二甲酸酯的聚酯。
有利地将这种iso-NPG与添加剂进行组合，这些添加剂包括促进剂以及UV抑制剂/吸收剂、是在将该iso-NPG施加到一个水池模具中之前加入。
在一个实施方案中，该阻挡层包括一种基于三嗪的UV吸收剂。此外或替代地，该阻挡层包括一种受阻胺光稳定剂。
在又一个实施方案中，该阻挡层包括一种或多种金属促进剂，优选是一种或多种选自下组的金属促进剂，该组由以下各项组成：辛酸锌、辛酸钾或辛酸钴。特别优选的促进剂是辛酸锌与辛酸钾的一种混合物。
该下层包括一种或多种基于聚酯、乙烯基酯或对苯二酸酯的树脂。优选地，该下层包括一种或多种环氧乙烯基酯、溴化的环氧乙烯基酯、线性酚醛环氧乙烯基酯树脂或弹性体改性的乙烯基酯树脂。一种特别优选的下层是包括双酚-A环氧乙烯基酯树脂的一种环氧乙烯基酯树脂。
在一个实施方案中，该下层包括一种或多种金属促进剂。
该下层配备有多种装饰性添加剂如颜料(这些颜料可以包括有机或无机颜料)以及任选地其他装饰性要素如小碎屑或颗粒，以给予一种花岗岩、大理石、晶状的或石英的外观。
根据本发明的另一个方面，提供了一种制造水池表面组合物的方法，该方法包括：将一种透明的凝胶层液体施加到一个水池模具中、允许该凝胶层固化并且随后将一个有色的或装饰性乙烯基酯层施加到该固化的凝胶层上。
根据本发明的又一个方面，提供了根据以上所述的实施方案中任一项所述的表面组合物在游泳池或温泉池的制造中的用途。
根据本发明的又一个方面，提供了一种游泳池或温泉池，该池包括由至少一个透明阻挡层以及至少一个下层构成的一种表面组合物，其中该透明阻挡层在使用中被布置在该下层之上并且与该池中的液体相接触，由此该透明阻挡层保护了该下层免于降解。
贯穿本说明书，术语“包括了”或“包括”或其之上的语法变体的使用应理解为指明所指特征、整数、步骤或组分的存在而不是排除未确切提及的一种或多种其他特征、整数、步骤、组分或其群体的存在或加入。
附图说明
现在参照以下附图对本发明进行描述，其中：
图1是根据本发明的一种表面组合物的多个层的简图；并且
图2是对一种已知的表面组合物与本发明的表面组合物在一个FRP面板上的浸没以及化学暴露效果进行比较的一张照片。
图3至14是比较耐候性的一系列试验面板的照片。
具体实施方式
如以下描述的本发明是本发明的优选实施方案的一种说明并且应理解为是为了展示本发明的可能的实施方案的非限制性实例的目的而进行的说明。所描述的实施方案和实例并不限定本发明的总体更宽的范围。
本发明的表面组合物特别地应用于在FRP游泳池以及温泉池中创造一个表面饰面或层，其中该表面长时期地浸没在水中并且与水直接接触，特别是包含水解和/或氧化性试剂(如来自水池消毒化合物)的水。这种表面组合物具有的主要目的是不仅保持FRP产品在浸没于水中时的结构整体性而且还保护装饰性要素(如着色物)免于由长期暴露于水、化学物以及UV辐射中所引起的损害或褪色。
该表面组合物包括一个透明的阻挡物凝胶层表面层，该表面层在使用中与水以及水中可能包含的任何化学物直接接触。该透明阻挡层的目的是保护该第二凝胶层(该第二层或者装饰层包含装饰性组分或添加剂，如着色物以及碎屑或颗粒)免于由水、化学物以及UV光造成的降解。也就是，在施加该第二、装饰性或有色的凝胶层之前施加到水池或温泉池上的透明阻挡层具有的目的是保护该第二层内的装饰品质，该品质的维护对于保护该池的观赏或美学品质是必要的。
迄今为止，还没有成功地施加一个透明阻挡层来保护一个装饰性下层在独特的环境中的品质，在该环境中该表面经受长期的浸没并且还经常经受长期的UV辐射暴露。为何没有在施加一个第二有色凝胶层之前成功地施加一个透明的凝胶层的主要原因之一是当完全浸没在水中并且经受水解和渗透压力时在彼此之上施加两种类似的凝胶层物质最终会失败。结合这个问题，所要求的颜料以及物理试剂的大量使用阻止了两个表面之间的充分结合。在早先的尝试中，在这两个层的界面处发生了渗透起泡，这不仅减损了水池的美学品质而且还折损了结构整体性。迄今为止，在另一个有色的或装饰性聚酯凝胶层上施加一个透明的聚酯凝胶层在对任何水池表面的涂敷中都失败了。
在寻求使用不同材料的其他尝试中，所选择材料的固有品质(尽管具有对用于水池表面组合物而言适当且必须的结构品质)已经部分地造成了这些失败。用来制造凝胶层的基础树脂经常本身并不是透明的，因为制造过程给予了该树脂一种棕色的品质。此外，对于在室温下固化树脂所必须的促进剂或加速剂总体上是基于钴的，它们是紫色的并且因此也改变了最终树脂的颜色。而且，树脂的催化以及固化的实际过程同样地改变了颜色。简言之，一旦针对喷雾而对树脂进行加工，它们将不再是透明的。一般不希望制造出具有此类颜色的表面的水池。在任何情况下，使用变成棕色或紫色的树脂阻止了消费者可用的并且所希望的各种各样颜色以及观赏效果的使用。
针对在有色层上提供透明的保护层的一些其他尝试已经失败，因为该透明层一旦暴露于UV光中就变得不透明或浑浊并且保护层的澄清度将永远消失。
本发明的组合物已经通过在该透明阻挡层和位于其下的有色的装饰层的每个中都利用特定的组分和添加剂而解决了这些问题。
在本发明的目前描述的实施方案中，本发明的表面组合物的透明阻挡层是作为一种透明的聚酯凝胶层如透明的间苯二甲酸新戊二醇(iso-NPG)而提供的。优选地，该iso-NPG是一种高品质、高分子量的iso-NPG。适当的iso-NPG的一个非限制的例子是可商购的Cray Valley(Cray ValleyKorea Co.Ltd)配制的凝胶层，Polycor GPLY 9107-011，这是一种苯乙烯单体的不饱和的聚酯树脂。
尽管这是用于该透明阻挡层的一种优选组合物，但在此考虑了还可以使用其他适当的产品选择，例如但不限于：透明的基于邻苯二甲酸NPG的凝胶层，透明的邻苯二甲酸的凝胶层、透明的乙烯基酯凝胶层或透明的甲基丙烯酸甲酯改性的凝胶层。
将特定的添加剂加入到未促进的iso-NPG中以给予保护该第二装饰层所需要的品质。在这个实施方案中，这些添加剂包括特定的促进剂以及UV抑制剂和/或UV吸收剂。
所加入的促进剂(加速剂)的特定选择是施加该透明的阻挡物凝胶层并且其包括在本表面组合物中成功的主要因素之一。通常在FRP池制造的技术中，选择的促进剂是基于钴的，即辛酸钴，它是紫色的。这种组分的单独加入足以改变树脂的颜色，从而使之不够透明。
在本发明中，将混合的金属促进剂加入到该iso-NPG中。优选的金属促进剂是辛酸锌(6％)和辛酸钾(12％)，它们在加入iso-NPG中时不会改变其颜色。此外，甚至是在催化和固化时，它们也不会改变该凝胶层的澄清度。
尽管辛酸锌以及辛酸钾是优选的促进剂，但很可能其他的也是适当的。可以在该过程中合适地使用的其他产品包括但不限于：SHEN催化剂PC-6、EFKA-2020消泡剂、二甲基苯胺以及某些少量的辛酸钴(6％)。
所加入的促进剂的选择也是重要的，因为混合的金属促进剂的具体选择已经解决了与施加iso-NPG有关的固化问题。iso-NPG尽管具有对于本应用而言理想的物理品质、已知是比其他树脂如邻苯二甲酸类树脂更加水解稳定的，但是是更难以施加并且更难以处理的。至少由于这个原因，iso-NPG已经被认为是不适合用于提供一个透明的阻挡物凝胶层的目的，或的确甚至不适合用于在FPR池的生产中的普遍推广的应用。高分子量的iso-NPG是更加反应性的并且如果施加太厚的话易于从模具中收缩、或在欠理想的条件下被过度地催化或促进或喷雾。然而，混合的金属促进剂如辛酸锌和辛酸钾的选择克服了固化问题并且允许生产一个具有强力积极固化的透明层。
这样该透明的阻挡物凝胶层有利地具有将保护该有色凝胶层免于UV褪色的品质，也向该iso-NPG中加入至少一种UV抑制剂和/或吸收剂或一种光稳定剂。在这个具体实施方案中，加入了两种UV吸收剂，它们在各自是由CibaTM Specialty Chemicals Inc.生产的商标TinuvinTM和ChimasorbTM下是商业上已知的，。优选的共混物是TinuvinTM 384-2和ChimasorbTM 119FL。特别优选的共混物是TinuvinTM 400和TinuvinTM123。这些UV吸收剂和稳定剂起作用来改进该透明的阻挡物凝胶层对UV暴露失效(如脱色、开裂和褪色)的耐受性。
按照要求可以向iso-NPG中加入另外的添加剂，例如触变剂。触变剂的选择本身对于本发明的表面组合物的工作不是关键的，仅是使得未固化的组分是适当地可喷雾的，这对于本领域中已知的在生产FRP池中施加iso-NPG的方法而言是必须的。然而，这种触变剂应该是疏水的以排斥水分。水分的消除对于保持该透明的阻挡物凝胶层的澄清度是必须的，因为水分将导致该凝胶层变得模糊并且减损美学品质。
如以上描述的特定组分的组合有利地提供了一种透明的阻挡物凝胶层，该层可以在施加该第二有色凝胶层之前被喷雾到该水池模具上。这些组分的组合在施加之前是透明的并且在施加以及固化之后保持是透明的。然而，作为一种水池表面组合物来成功创造该透明的阻挡物凝胶层在所打算的应用中不可能是成功的，除非它还有助于施加该第二有色凝胶层而不使该透明的涂层起皱。还必须的是在第一与第二凝胶层之间产生强力的层间结合从而消除相邻的凝胶层之间的层离可能性。
为了实现这些优点并且得到本发明的表面组合物，第二有色凝胶层的组成是关键的。在本发明的实施方案中，该第二彩色凝胶层主要包含一种乙烯基酯树脂。
乙烯基酯树脂具有许多特性(这为本应用增添了它们)，因为它们是极其强的、具有大的水解稳定性、提供了优异的拉伸以及挠曲强度并且具有高的热变形温度并且因此能够对抗渗透起泡。此外，它们具有优异的粘合以及粘结特性并且是非常耐化学性的。然而，尽管具有这些品质，乙烯基酯从未在水池表面组合物或在表面长期暴露于水中的任何应用中用作装饰剂(如颜料以及质地化试剂)的载体。已知乙烯基酯在经受不变的水浸没以及连续的UV辐射时会降解。这样，由乙烯基酯制造的并且施加到一个水池表面上的任何凝胶层在制造、施加时并且特别是在老化和暴露于水及UV光中之后将改变颜色。
此外，乙烯基酯已经被认为是固有地不适合应用在水池表面中，这是由于当用作凝胶层时，它们会特有地比聚酯树脂固化得更软这个事实。也就是，使用一个Barber Coleman刻迹物来测试巴科尔氏硬度，可以测试出一种乙烯基树脂是比基于iso-NPG或ortho-NPG的凝胶层的硬度低25％。这样，尽管具有许多正面的属性，乙烯基酯凝胶层总体上不能经受水池使用的严苛条件，特别是来自清洁性产品、清洁方法和自动的水池清洁机的磨损。
然而，本发明的构思(其中通过该透明的阻挡物凝胶层保护了被着色的乙烯基酯免于暴露于此类要素中)解决了这些困难并且允许乙烯基酯的这些有利品质被用于本应用中。
对于本发明所选择的乙烯基酯树脂是一种被配制为是透明的并且重要的是不表现出常规的乙烯基酯树脂的区别性棕色色调的一种树脂。标准的乙烯基酯树脂是棕色的并且因此并不对可得到的各种不同着色物的应用提供良好基础。因为本发明的目的之一是允许不仅在水池中使用标准颜色、而且还使用扩展的种类的颜色、以及通过加入小碎屑或颗粒而进行颜色的培育和质地化，所以希望的是所选择的乙烯基酯甚至在施加和固化之后也可以保持尽可能的透明。因此，虽然不必须要乙烯基酯树脂保持如透明的阻挡物凝胶层那样透明，但一种暗的乙烯基酯具有的效果会压倒某些颜色还以及碎屑和颗粒的效果并且因此是不希望的。这种基础乙烯基酯因此优选地维持是尽可能透明的，甚至在施加以及固化之后。
已发现适合应用于本发明中的乙烯基酯的一个非限制性的例子是双酚-A环氧乙烯基酯树脂，如Cray Valley Epovia KayakTM KRF-1001MV，这是一种清澈的透明性液体树脂。可以使用任何合适的乙烯基酯，只要它能够提供该乙烯基酯凝胶层的优异固化并且可以使得该高度耐水和耐化学性的乙烯基酯树脂在该透明的阻挡物凝胶层后面能共存。
类似于用于该透明的阻挡物凝胶层的组成的选择，在此考虑到其他产品可能也适合用于该有色的凝胶层中。可能的非限制性例子是基于聚酯、乙烯基酯或对苯二甲酸酯的树脂或凝胶层的选集，它们可以结合颜料和/或质地化组分，包括任何双酚-A环氧乙烯基酯树脂、溴化的环氧乙烯基酯树脂、线性酚醛环氧乙烯基酯树脂或弹性体改性的乙烯基酯树脂。
如与iso-NPG一起，加入该乙烯基酯中的添加剂的选择对于给予总的表面组合物所希望的品质而言是重要的。为了保持该乙烯基酯的接近于透明的品质，再次希望避免使用辛酸钴作为促进剂。再次优选的是使用混合的金属促进剂，例如辛酸锌以及辛酸钾。然而，适当的添加剂的另外例子包括Shen催化剂PC-6、二甲基苯胺、EFKA-2020消泡剂以及苯乙烯单体。在有色层的最终颜色较暗的应用中，可以适当地加入辛酸钴(6％和8％)。
还加入了一种适当的触变剂来获得可喷雾性。
本发明还包括一种用于制造表面组合物和制造FRP产品如游泳池或温泉池的方法。该方法实质上包括向一个模具的表面施加一种透明的聚酯凝胶层液体，在此情况下是该透明的高分子量的iso-NPG。将这种包含以上描述的添加剂的iso-NPG以本领域已知的方式均匀地喷涂到该模具上，实现0.65mm的最小湿厚度。这种固化的凝胶层优选地在24小时的施加内实现了35的最小巴科尔氏硬度。这样，该透明阻挡层能够提供耐久性以及耐磨损性以经受住游泳池的正常每日使用，包括自动水池清洁机的使用，并且尤其在温泉池的情况下经受住高达41℃的水温。
一旦该iso-NPG适当地固化而形成透明阻挡层，就将乙烯基酯(在此情况下是双酚-A环氧乙烯基酯树脂)与以上描述的添加剂喷雾到该凝胶涂覆的模具上以给予该产品其彩色的并且任选地质地化的外观。然后还允许该乙烯基酯按照要求进行固化。
如所要求的并且如产品的具体预期用途所指出的，加入另外的结构层以及化学和/或腐蚀阻挡层。例如，在游泳池或温泉池的制造中，另外的层可以包括一个另外的乙烯基酯腐蚀阻挡层来改进抗冲击性以及绝热性、一个间苯二甲酸类腐蚀和结构层、玻璃纤维叠层片还以及另外的增强层。将固化的最终产品从该膜中脱出、进行修整并且运输到其使用位置。
使用本发明的表面组合物来生产一种产品如游泳池给与了该产品在现有技术中尚未实现的品质和弹性。本发明的表面组合物提供了在有害的UV辐射作用下不会变色或失效的一个透明阻挡层或凝胶层，这些作用是在该水池位于户外并且因此暴露于长期的日光或水与化学物的组合中时所经历的。此外，这个透明阻挡层提供了这样一种程度提高的保护，使得布置在其下的第二有色的或装饰性的层可以比之前可能的持续更长的时期而没有着色物的褪色或脱色。重要的是，该透明阻挡层所给予的保护程度是使得可以在该有色层中使用更宽范围内的颜料。也就是，在该有色的凝胶层中可以包括如下的有机颜料，它们在特别暴露于UV以及氧化剂中时会被破坏或损害。
在此提出在游泳池以及类似物中施加本发明的表面组合物将允许制造商为消费者提供更长的产品保证而不使自己遭受对于水池翻新和更换进行赔偿的风险。也就是，这些产品看上去更好并且在长得多的时期内保持了它们的新的并且明亮的外观。
本发明的表面组合物的耐久性和弹性由实验数据来证明，这些实验数据测试了该表面组合物对化学降解的耐受性，如以下提出的：
实例
实例1
氯的脱色试验
在使用适用于FRP池制造的已知制造技术、程序和配制品所制造的玻璃纤维增强的塑料(FRP)面板上进行了一系列的试验，以比较一种已知远超过工业标准的表面组合物与根据本发明的实施方案的表面组合物的效能。
从具有一种已知的表面组合物的两个FRP变体上(对照面板)、还从在其上施加有本发明的实施方案的表面组合物的两个FRP变体上切割了一系列的正方形面板，尺寸为约200mm×200mm。这些变体在下表1中列出：
Figure BPA00001423517100111
将每个面板置于一个单独的水槽中并且将三氯异氰尿酸酯游泳池消毒片剂放置为与每个面板的表面直接接触，其中两个面板和片剂完全浸没在水中。将片剂直接地置于每个面板上以模拟多年的水和消毒剂造成的游泳池降解和漂白的作用。将每个槽中的片剂压低以阻止该片剂由于气体的释放和表面的相互作用而跨过该面板的表面进行迁移。
将每个槽中的水每天排空并且用干净的新鲜自来水代替以确保在试验水中氯残余量不过高并且不促成面板的过早褪色。在排出该水时，对每个面板进行洗涤、拍照并且对颜色或表面降解的迹象进行检查。更换每个槽中的水以及面板之后，将相同的片剂置于该面板表面上精确相同的位置处。两个小时后对每个面板进行检查以确保该片剂没有从其位置移动。
每天重复这个过程，持续7天。观察到的每个面板的外观描述在下表2中：
Figure BPA00001423517100121
将面板PBC和PD在暴露两天之后从试验程序中移出，因为面板PD(不具有本发明的表面组合物)已经褪色并且恶化到无法修复。
第五天的暴露之后，将面板PAC移出、进行清洁并且通过对表面的温和的温柔摩擦进行精细砂磨(湿的和干的，600目)。这种几乎不费力的作用造成了变色的立即消除。然后将该面板抛光并且返回到试验过程中。
使另一个PAC面板经受该试验过程而不进行任何的中间抛光或清洁。
在试验过程的结尾处，对面板PC进行检查，其中确定了该表面被严重降解，显示了与片剂接触的表面的极度点蚀和氧化。对表面造成的损害程度是使得它是不能修补的并且不可逆的。
相比之下，面板PAC显示除来自于氯的轻微染色(游离有效氯的绿色)以及极轻微的表面点蚀之外对该表面的极小改变。没有观察到面板本身中实际着色物的退化。使用湿的和干的600目砂砾温和摩擦之后，表面点蚀以及大部分氯变色被消除。
以上结果证明了本发明的表面组合物保护该总体结构的整体性和颜色免于水和化学物的降解的能力。
实例2
高级加速的80℃试验
使如实例1描述的面板PAC以及PBC按照“AS/NZS 1838-1994Swimming pools-premoulded fibre-reinforced plastics-design andfabrication[AS/NZS 1838-1994游泳池-预模制的纤维增强的塑料-设计与制造]”标准经受耐水性试验。这个标准要求这些面板能够根据规定的退化分级在80℃下经过30天(来自该标准的表E1)。这两个面板经受了所要求的条件并且以异常的结果通过了该试验。不存在表面的降解和渗透起泡。75天之后，仍然没有可见的渗透起泡并且内表面降解是可忽略的。
因此清楚的是本发明的表面组合物有利地使能制造如下的FRP游泳池以及温泉池：这些池是实质上完全耐褪色的，超过了目前的工业标准，并且就耐起泡、耐化学性以及水解稳定性而言符合AS/NZS 1838-1994。
实例3
耐候性以及耐紫外线的产品试验
制造了十二个单独的面板并且使用ASTM G154-06“Standardpractice for operating fluorescent light apparatus for UV exposure ofnon-metallic materials[非金属材料UV暴露用荧光灯装置操作的标准惯例]”进行测试。出于对比的目的还提供了作为相同样品的一部分而制造的对照面板。
试验由澳大利亚Dandenong Victoria 3175的Chisholm Institute的聚合物测试实验室进行，该实验室是一个NATA认证的试验室。
将每个面板暴露于4小时的在50℃下的冷凝作用中，接着是60℃下8小时的UV-A暴露。将这个模式重复2000小时的试验持续时间。
对每个面板给予不同的识别字母，是面板G、H、I、J、K、L、M、N、O、P、Q和R。
每个面板在本质上是不同的。十个面板是使用根据本发明的一个实施方案的表面组合物制造的而两个面板是由可以被认为是工业上最好惯例的物质制造的。
所有的十二个面板都具有变化的量和/或利用了不同的紫外抑制剂以及吸收剂。
进行该测试的这个具体方面以解决：相对于以下方面而言，哪些添加剂将给予该表面组合物有益的效果：
a)能够在橡胶基质中使用并且是可喷雾的并且不影响该凝胶层的流变学。
b)不抑制该固化过程。
c)不给予该透明的凝胶层任何特征性色调或变色。
d)不增加凝胶层的充气，因为充分增生的微小的或微观的空气气泡将引起凝胶层中的浑浊或乳状。
e)不抑制该凝胶层的巴氏硬度而由此减小产品的耐磨性以及总的耐久性。
f)提供了基于ASTM G 154-06在2000小时之后最佳的耐候性以及UVA耐受性。
g)确立最佳的添加剂浓度。
h)确立凝胶层的UV光吸收剂与稳定剂的最合适比率。
将以下添加剂加入每个面板上所施加的透明的凝胶层阻挡层中：
CIBA TINUVINTM 400
一种液体羟苯基-三嗪(HPT)UV吸收剂。
CIBA TINUVINTM 384-2
羟苯基-苯并三唑类别的一种液体UV吸收剂。
CIBA TINUVINTM 123
一种基于受阻氨基醚官能度的液体HALS稳定剂。
设置这些面板并且根据ASTM G 154-06进行试验，并在500小时、1000小时、1500小时以及2000小时之后进行评估。
表3总结了这十二个面板上的颜色、涂层、添加剂以及试验结果。
Figure BPA00001423517100161
面板M和N的颜色是几乎相同的
具有地中海银色的面板R在颜色上与Sterling面板几乎相同。描述“没有变化”表示在面板的外观上在与其初始状态或与先前的检查结果之间不存在变化
iso-NPG＝间苯二甲酸新戊二醇
VE＝双酚-A环氧乙烯基酯
如在图3至14中展示的，具有本发明的组合物的十个面板表现得清楚地且显著地优于对比试验面板M以及R。可以得出以下结论：
1.面板M和R在试验过程中显示了表面外观和质地的显著退化。
2.表现最好的面板是面板G、H、J以及K。全都仅显示出些微的光泽损失以及浅的黄色色彩。所有面板上的表面摩擦的初始变化是明显的，然而面板G、H、J以及K均没有显示与先前试验之间的变化，表明在更长的稳定时期之后非常轻微的初始变化并且没有进一步的变化。
3.具有更高浓度TINUVINTM添加剂的面板表现得不如具有更低添加剂浓度的那些。因此，具有1.5％添加剂的面板比具有2.0％添加剂的面板表现更好。
4.具有2％添加剂比率的面板显示出了模糊/浑浊的外观。
5.具有该两部分吸收剂与一部分稳定剂之比的面板与具有一部分吸收剂比一部分稳定剂的面板相比表现更好。
6.在面板G、H和K之间存在可忽略的差异。
7.面板G比面板J表现更好，表明TINUVINTM 400提供了优于TINUVINTM 384-2的性能。
与具有1％添加剂的面板G相比，面板H包含1.5％的添加剂。因为2000小时之后对面板H没有任何减损作用，可以得出结论：面板H将在ASTM G154-06条件下在大于2000小时的时期内在所有可能性中比面板G表现更好。
总体上，总结出本发明的组合物提供了优于标准涂层的以下主要改进和益处，特别是当与TINUVINTM 400以及TINUVINTM 123吸收剂和稳定剂的有利特征相结合时。
这些集体的结果表明以下改进和优点可能是来自于本发明的表面组合物的使用。
1.在许多年都不褪色并且保持其生动明亮的颜色的一种游泳池。
2.没有漂白标记、变黄或白垩化。
3.通过施加该阻挡层，水池颜色与氯、溴或其他氧化剂的漂白作用相分离。
4.抗海藻、染色并且更易清洁的的明亮且持久的光泽饰面，从而导致了水池的更少维护。
5.完全保护了这些美学以及结构性的叠层免于水的侵蚀性质。
6.优异的层间附着，从而确保了本发明的涂层组合物及游泳池叠层材料的所有特定涂覆都在结构上、机械上和化学上结合在一起，从而给予游泳池更大的强度、耐久性以及耐起泡性。
7.改善的水解稳定性。
8.“渗透起泡”的机会被显著地最小化。
9.抵抗了UV光辐射造成的降解并且消除了UV暴露造成的开裂倾向。具有高的热稳定性并且适合于极端的环境条件。
尽管本发明的表面组合物特别地用于制造游泳池和温泉池，但是它同等地适用于并且可用于任何产品，特别是FRP产品，这些产品将显著的时间段用在浸没于水中和/或经受UV辐射。

Claims (22)

1.一种表面组合物，用于减小经受了在水性液体中的长期浸没的表面的降解和褪色，该表面组合物包括至少一个透明阻挡层以及至少一个下层，其中该透明阻挡层在使用中被布置在该下层之上并且与该水性液体相接触，由此该透明阻挡层保护了该下层的结构和外观。
2.根据权利要求1所述的表面组合物，其中该下层是包含一种或多种装饰性或观赏性试剂的一个装饰层。
3.根据权利要求1或2所述的表面组合物，其中该组合物包括一种或多种UV抑制剂、吸收剂和/或稳定剂。
4.根据权利要求1至3中任一项所述的表面组合物，其中该透明阻挡层包括一种或多种UV抑制剂、吸收剂和/或稳定剂。
5.根据权利要求1至4中任一项所述的表面组合物，其中该透明阻挡层是一个透明的聚酯凝胶层。
6.根据权利要求5所述的表面组合物，其中该透明的聚酯凝胶层包括一种或多种含邻苯二甲酸酯的聚酯、含乙烯基的聚酯或含甲基丙烯酸酯的聚酯。
7.根据权利要求6所述的表面组合物，其中该透明的聚酯凝胶层包括一种含邻苯二甲酸酯的聚酯。
8.根据权利要求7所述的表面组合物，其中该透明的聚酯凝胶层是衍生自一种间苯二甲酸新戊二醇。
9.根据权利要求8所述的表面组合物，其中该透明的聚酯凝胶层是衍生自基于该聚酯中二羟基化合物的总摩尔％而大于70摩尔％的新戊二醇。
10.根据权利要求3至9中任一项所述的表面组合物，其中该阻挡层包括一种基于三嗪的UV吸收剂。
11.根据权利要求3至10中任一项所述的表面组合物，其中该阻挡层包括一种受阻胺光稳定剂。
12.根据权利要求1至11中任一项所述的表面组合物，其中该阻挡层包括一种或多种金属促进剂。
13.根据权利要求1至12中任一项所述的表面组合物，其中该一种或多种金属促进剂是选自下组，该组由以下各项组成：辛酸锌、辛酸钾或辛酸钴。
14.根据权利要求1至13中任一项所述的表面组合物，其中该下层包括一种或多种聚酯、乙烯基酯或基于对苯二酸酯的树脂。
15.根据权利要求14所述的表面组合物，其中该下层包括一种或多种环氧乙烯基酯、溴化的环氧乙烯基酯、线性酚醛环氧乙烯基酯树脂或弹性体改性的乙烯基酯树脂。
16.根据权利要求15中所述的表面组合物，其中该环氧乙烯基酯树脂包括一种双酚-A环氧乙烯基酯树脂。
17.根据权利要求1至16中任一项所述的表面组合物，其中该下层包括一种或多种金属促进剂。
18.一种用于制造表面组合物的方法，该方法包括将一个透明的凝胶层液体施加到一个模具中，允许该凝胶层固化并且随后将一个有色的或装饰性的乙烯基酯层施加到该固化的凝胶层上。
19.根据权利要求18所述的方法，其中该透明的凝胶层是衍生自一种间苯二甲酸新戊二醇。
20.根据权利要求18或19所述的方法，其中该乙烯基酯层包括一种双酚-A环氧乙烯基酯树脂。
21.根据权利要求1至17中任一项所述的表面组合物在制造游泳池或温泉池中的用途。
22.一种游泳池或温泉池，该池具有由至少一个透明阻挡层以及至少一个下层构成的一种表面组合物，其中该透明阻挡层在使用中被布置在该下层之上并且与该池中的液体相接触，由此该透明阻挡层保护该下层免于降解。
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