CN101679806A - 可剥临时涂层 - Google Patents

可剥临时涂层 Download PDF

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CN101679806A
CN101679806A CN200880018768A CN200880018768A CN101679806A CN 101679806 A CN101679806 A CN 101679806A CN 200880018768 A CN200880018768 A CN 200880018768A CN 200880018768 A CN200880018768 A CN 200880018768A CN 101679806 A CN101679806 A CN 101679806A
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M·J·M·范金内肯
E·马里纳斯
P·H·德布鲁因
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Abstract

本发明涉及一种用于在基材上形成可剥临时涂层的水性涂料组合物,所述水性涂料组合物包含至少一种水基成膜聚合物,其特征在于所述组合物额外包含氨基树脂基聚合物固体颗粒。

Description

可剥临时涂层
本发明涉及一种用于在基材上形成可剥临时涂层的水性涂料组合物,一种在基材上形成可剥临时涂层的方法以及一种涂覆基材。
上述类型的涂料组合物由德国专利申请DE 19921885 A已知。该已知的组合物包含聚合物分散体和无机矿物填料颗粒。当施加至无孔基材时,所述组合物形成内聚力高于其与基材粘合力的膜。由所述组合物制备的临时涂层用于保护各种产品和组件的暴露表面是有效的并且可通过剥离去除。
这类涂层适合用于汽车及其组件的临时保护和/或装饰。新车的表面涂层在装配工艺和从装配工厂运输到零售地点的过程中均要经受各种破坏。一般的破坏源包括酸雨、鸟粪和“轨道粉尘”,当火车经过轨道时由轨道床产生或者由架空电力线上电传感器摩擦产生的硬研磨颗粒尘。轨道粉尘对于汽车制造商来说是尤其麻烦的问题,因为许多汽车通过轨道从装配工厂或造船厂运输到零售市场。除了新车以外,其它产品在运输过程以及制造和装配成其它产品过程中也经受磨损和有害的条件。例如,必须特殊保护防雨窗和其它玻璃产品以避免在公路和铁路运输过程中擦刮和损坏。仓面货也易遭受海水和其它因素引起的表面破坏。类似地,在制造或下游生产商装配过程中必须保护许多产品。例如,在运输以及安装或装配成其它产品的过程中必须保护具有高光泽面漆的塑料层压材料和其它材料如浴室设备和镀铬或黄铜表面。
当前需要改进临时涂层的性能,尤其是在改进导致涂层去除时更好剥离的机械性能方面以及临时涂层在户外暴露时的耐久性,尤其是防水性方面。因此,本发明试图提供一种用于形成符合这些需要的可剥临时涂层的涂料组合物。
本发明当前提供一种用于在基材上形成可剥临时涂层的水性涂料组合物,所述水性涂料组合物包含至少一种水基成膜聚合物,并且所述组合物额外包含氨基树脂基聚合物固体颗粒。
已发现氨基树脂基聚合物固体颗粒作为水性涂料组合物中的添加剂改进了临时涂层的可剥性。在许多情况下,额外改进了防水性。
本发明涂料组合物使得临时保护涂层不再需要时易于通过剥离去除临时涂层。通常,所述涂层也具有良好的防水性。
水基成膜聚合物的选择至少部分地决定了临时涂层易于通过剥离去除。通常优选具有低玻璃化转变温度(Tg)的成膜聚合物。合适的成膜聚合物的Tg可以为19℃或更低,或者13℃或更低,或者9℃或更低。通常,成膜聚合物的Tg可以为-30℃或更高,或者-25℃或更高。
临时涂层的柔韧性对其可剥性同样具有有利影响。为此优选使用干燥后产生弹性模量为80MPa或更低,或者50MPa或更低的油漆涂层的油漆组合物。当油漆涂层的弹性模量为至多20MPa时,也获得良好结果。油漆涂层的弹性模量通常为至少9MPa,或者至少10MPa。临时涂层的断裂伸长与良好可剥性同样有关。临时涂层的断裂伸长通常为至少400%,或者至少500%,或者甚至至少600%,从而防止从基材上剥离涂层时而过早断裂。断裂伸长太高对可剥性不利。合适的断裂伸长不超过1,000%,优选不超过900%。到目前为止,当弹性模量为5-12MPa时已实现非常好的结果,断裂伸长为500-800%。
合适的水基成膜聚合物的实例为聚氨酯、聚酯、聚碳酸酯和通过使烯属不饱和单体聚合而制备的聚合物如聚(甲基)丙烯酸酯或乙酸乙烯酯的共聚物。还可以使用这类成膜聚合物的混合物和/或杂化物。水基成膜聚合物的制备通过常规技术进行。可以在不存在水的情况下制备所述聚合物,然后在水中分散。或者,可例如通过乳液聚合而在水性环境中制备所述聚合物。在一个实施方案中,本发明涂料组合物包含至少两种不同的水基成膜聚合物。
合适的水基成膜聚合物可市购,例如来自Synthomer的丙烯酸酯-丙烯腈共聚物的水分散体
Figure G2008800187684D00021
274、来自Synthomer的乙酸乙烯酯-丙烯酸丁酯共聚物的水分散体
Figure G2008800187684D00022
AC 430、来自Polymer Latex的甲基丙烯酸酯-丙烯酸酯共聚物的水分散体
Figure G2008800187684D00023
B 500或来自DSM Neoresins的聚氨酯水分散体
Figure G2008800187684D00031
R987。
氨基树脂基聚合物固体颗粒在所述涂料组合物中以所述组合物的总重计通常为至少1重量%,或至少2重量%,或甚至至少4重量%的量存在。所述颗粒的量的上限以所述组合物的总重计适当地为25重量%,或20重量%,或14重量%。平均粒度通常为1-150μm。所用颗粒通常具有粒度分布。例如,全部颗粒中90%可能小于14μm并且全部颗粒中50%可能小于6.5μm。
在一个实施方案中,颗粒的横向尺寸和纵向尺寸可为相似数量级。所述颗粒例如可基本为球形。然而,所述颗粒还可以具有其它形状如片状或针状。
氨基树脂基聚合物可适当地通过使氨基树脂或氨基树脂前体与甲醛缩合或者通过胺的其它缩合和/或加成反应而制备。合适的氨基树脂基聚合物的实例为胍基聚合物、蜜胺基聚合物、尿烷基聚合物、酰胺基聚合物和脲基聚合物,尤其是甲基脲基聚合物。氨基树脂基聚合物适当地为交联的,即所述聚合物为硬塑料。可在氨基树脂与甲醛的缩合反应中进行交联。然而,也可通过额外的交联剂产生交联。合适的氨基树脂基聚合物固体颗粒例如可以由德国Deuteron GmbH以商标
Figure G2008800187684D00032
MK市购。
Figure G2008800187684D00033
MK颗粒基于甲基脲聚合物。
本发明还涉及氨基树脂基聚合物固体颗粒在用于在基材上形成可剥临时涂层的水性涂料组合物中作为添加剂以改进临时涂层可剥性的用途。
本发明涂料组合物的大部分挥发物含量由水组成。然而,所述涂料组合物可含有一种或多种有机溶剂,条件是现用涂料组合物的有机挥发物含量(VOC)不超过420g/l。优选不超过210g/l。这种有机溶剂的存在可有利于分散的聚合物颗粒聚结形成均匀膜。因此,这类溶剂通常称为聚结剂。作为合适的聚结剂,可提及二甲基二丙二醇、双丙酮醇的甲基醚、乙酸乙酯、乙酸丁酯、乙基乙二醇乙酸酯、丁基乙二醇乙酸酯、乙酸1-甲氧基-2-丙酯、丙酸丁酯、丙酸乙氧基乙酯、甲苯、二甲苯、甲基乙基酮、甲基异丁基酮、甲基异戊基酮、乙基戊基酮、二氧戊环、N-甲基-2-吡咯烷酮、碳酸二甲酯、2,2,4-三甲基-1,3-戊二醇单异丁酸酯、碳酸亚丙酯、丁内酯、己内酯及其混合物。
本发明涂料组合物可进一步包含涂料组合物中通常存在的其它组分和添加剂如颜料、增量剂、着色剂、颜料分散剂、乳化剂(表面活性剂)、流变控制剂、均化剂、平光剂、湿润剂、防缩孔剂、消泡剂、生物杀伤剂、增塑剂、UV吸收剂、光稳定剂和气味遮盖剂。
为了实现所需颜色,涂料组合物可含有一种或多种颜料。所述颜料可为有机或无机的。颜料含量以成膜聚合物的重量计通常为1-20重量%。替代或者额外地,所述涂料组合物可含有一种或多种可全部或部分溶于所述组合物的染料。
本发明还涉及一种在基材上形成临时涂层的方法,其中将本发明涂料组合物施加至基材并使其在所述基材上形成可剥临时涂层。在一个实施方案中,所述方法额外包含通过剥离去除临时涂层。
将涂料组合物施加至基材的任何已知方法均可用于施加所述涂料组合物。这类施加方法的实例为刮涂(例如通过搓漆或刮刀刷涂、滚涂),喷涂(例如供气喷涂、无空气喷涂、热喷涂和静电喷涂),流涂(例如浸涂、幕涂、辊涂和逆向辊涂)和电沉积。
由本发明组合物制备的涂层可在0-160℃,或5-80℃,或10-60℃,例如环境温度下干燥。可在烘箱中在升温下进行干燥。或者,可借助红外和/或近红外辐射干燥。
所述涂料组合物非常适合用于在基材上形成临时保护涂层。然而,替代或额外地,所述涂料组合物也可用于临时装饰目的,尤其是在所述组合物额外包含颜料时。为了形成临时涂层,将所述组合物施加至基材并使其形成可剥临时涂层。如上文进一步描述,在装配工艺过程中和/或之间或运输过程中可能需要临时保护涂层用于临时保护基材。在节日活动的过程中,可能需要临时装饰用于使汽车具有特定外观和颜色。当基材上不再需要存在临时保护和/或装饰时,可通过剥掉基材上的涂层而去除临时涂层。
基材合适地为非孔基材。合适非孔基材的实例为已预处理或未预处理的金属、预处理的木材、合成聚合物材料和玻璃。其它合适的基材为其它油漆涂层,例如在运输工具和汽车或其部件,例如客车、自行车、火车、卡车、公共汽车和飞机上存在。
实施例
所用原料
AC 430            来自Synthomer的
Figure G2008800187684D00051
AC 430,乙酸乙烯酯-
                  丙烯酸丁酯共聚物的水分散体
R 274             来自Synthomer的
Figure G2008800187684D00052
274,丙烯酸酯-丙烯腈
                  共聚物的水分散体,
P B500            来自Polymer Latex的
Figure G2008800187684D00053
B 500,甲基丙烯酸酯
                  -丙烯酸酯共聚物的水分散体
R987              来自DSM Neoresins的R987,聚氨酯水分
                  散体
D MK              来自Deuteron的
Figure G2008800187684D00055
MK,氨基树脂基聚合
                  物颗粒
Figure G2008800187684D00056
2,2,4-三甲基-1,3-戊二醇单异丁酸酯
333               来自BYK Chemie的表面活性添加剂
着色剂            包含颜料的市购调色组合物
实施例1-3和对比例A-C的涂料组合物通过将各组分以表1所示的重量比例混合而制备。
表1:
Figure G2008800187684D00058
本发明涂料组合物1-3含有氨基树脂基聚合物固体颗粒。对比组合物A-C不含这类颗粒。将液体涂料组合物施加至用包含底漆和面漆的汽车涂料预涂覆的金属板。用Devilbiss喷枪通过空气助喷进行施加。当通过辊涂或刷涂进行施加时,可适当地添加增稠剂和任选消泡剂。使涂层在室温下干燥2小时或在60℃下干燥30分钟。干层厚度为50-90μm。1天后,通过手动剥离去除施加的涂层。通过其中多人手动剥离膜的试验测定可剥性。发现实施例1-3的涂层相比于实施例A-C分别显示出改进的可剥性。因此,证实了氨基树脂基聚合物固体颗粒的添加导致去除临时涂层时更好的可剥性。由表1还可以推出通过添加氨基树脂基聚合物固体颗粒而使弹性模量显著增加。
通过浸水7天测定所述临时涂层的水敏性。发现实施例1和3的涂层相比于实施例A和C分别显示出改进的防水性。因此,证实了氨基树脂基聚合物固体颗粒的添加可改进临时涂层的防水性。

Claims (12)

1.一种用于在基材上形成可剥临时涂层的水性涂料组合物,所述水性涂料组合物包含至少一种水基成膜聚合物,其特征在于所述组合物额外包含氨基树脂基聚合物固体颗粒。
2.根据权利要求1的水性涂料组合物,其特征在于所述氨基树脂基聚合物为甲基脲基聚合物。
3.根据权利要求1的水性涂料组合物,其特征在于所述氨基树脂基聚合物为交联聚合物。
4.根据上述权利要求中任一项的水性涂料组合物,其特征在于所述氨基树脂基聚合物固体颗粒以基于全部组合物的重量为1-25重量%的量存在。
5.根据上述权利要求中任一项的水性涂料组合物,其特征在于所述组合物额外包含聚结剂。
6.根据上述权利要求中任一项的水性涂料组合物,其特征在于所述水基成膜聚合物为(甲基)丙烯酸酯基共聚物。
7.根据上述权利要求中任一项的水性涂料组合物,其特征在于所述组合物包含至少两种不同的水基成膜聚合物。
8.一种在基材上形成临时涂层的方法,其特征在于将上述权利要求中任一项的涂料组合物施加至所述基材并使其在所述基材上形成可剥临时涂层。
9.根据权利要求8的方法,其特征在于所述方法额外包括通过剥离去除临时涂层。
10.一种用可剥临时涂层涂覆的基材,其特征在于所述可剥临时涂层由权利要求1-7中任一项的涂料组合物获得。
11.根据权利要求10的基材,其特征在于所述基材为汽车或其部件。
12.氨基树脂基聚合物固体颗粒在用于在基材上形成可剥临时涂层的水性涂料组合物中作为添加剂以改进临时涂层可剥性的用途。
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