CN103788748B - 具有消泡剂的制剂 - Google Patents
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Abstract
本发明涉及具有消泡剂的制剂。本发明涉及一种组合物,该组合物包含粘合剂的水性分散体和0.01‑2重量%的消泡剂(以粘合剂的重量计),所述消泡剂用如下结构进行表征:其中,R1、R2、x、y、m和n如本文所定义。本发明的组合物特别适用于降低低VOC漆制剂中的泡沫的形成。
Description
背景技术
本发明涉及含消泡剂的组合物,更具体地,本发明涉及含有特定类型的消泡剂的一类具体的漆制剂。
监管压力使得市场引入低VOC漆的需求增加,对于此类低VOC漆所产生的挑战变得更为明显。例如,部分地从高VOC聚结剂的去除和低VOC表面活性剂的使用增加产生过多的泡沫,这促进了稳定泡沫的形成。此外,在不存在聚结剂和溶剂的情况下,漆制备工艺涉及将那些有助于带走空气的材料混合在一起,这也是形成不合乎希望水平的稳定泡沫的另一来源。
泡沫问题并不是低VOC漆所独有的,例如,具有含磷酸单体的重复单元的粘合剂,如甲基丙烯酸磷酸乙酯倾向于发生形成过多泡沫,这可能是由于粘合剂负载的较高电荷密度所导致的泡沫稳定化的增加所引起的。
因此,希望找到一种能够在各种粘合剂体系中使得泡沫失稳的消泡剂。
发明内容
本发明通过提供一种包含粘合剂的水性分散体和0.01-2重量%的消泡剂(以粘合剂的重量计)的组合物来解决上述需求,所述消泡剂的用如下结构进行表征:
其中R1是-(CH2)3O(C3H6O)pCH3;
R2是-(CH2)3O(C2H4O)qCH3;
x为0至240;
y为0至240;
m+n=10至30;
x+y+m+n=150至250;
p是15至25;以及
q是10至40;
其中,所述粘合剂的Tg小于20℃,和/或所述粘合剂含有含磷酸单体的结构单元。
本发明通过提供一种不会形成过多泡沫的组合物来解决本领域的需求。
发明详述
本发明是一种组合物,该组合物包含粘合剂的水性分散体和0.01-2重量%的消泡剂(以粘合剂的重量计),所述消泡剂的用如下结构进行表征:
其中R1是-(CH2)3O(C3H6O)pCH3;
R2是-(CH2)3O(C2H4O)qCH3;
x为0至240;
y为0至240;
m+n=10至30;
x+y+m+n=150至250;
p是5至40;以及
q是5至50;
其中,所述粘合剂的Tg小于20℃,和/或所述粘合剂含有含磷酸单体的结构单元。
优选地,x+y+m+n=175至225;优选地,m+n=15至25;优选地,p=10至40,更优选为15至25;并且优选地,q=30至40。优选地,消泡剂的浓度为0.05-1重量%,以粘合剂的重量计。
粘合剂是聚合物颗粒的稳定水性分散体,所述聚合物颗粒的Tg优选为-60℃至60℃,更优选为-60℃至20℃,最优选为-60℃至15℃的范围内,并且所述粘合剂可以是适合于涂料组合物的任意粘合剂,包括以下聚合物颗粒的水性分散体:丙烯酸类、苯乙烯-丙烯酸类、乙烯基酯-丙烯酸类、乙烯基酯-乙烯、硅酮、氨基甲酸酯、偏二卤乙烯和乙烯基卤化物。
所述粘合剂可包括含磷酸的单体的结构单元,优选为0.2-4重量%,以粘合剂的重量计。合适的含磷酸的单体的例子包括醇的膦酸酯和磷酸二氢酯,其中所述醇含有可聚合乙烯基或烯烃基团或者被可聚合乙烯基或烯烃基团取代。优选的磷酸二氢酯是(甲基)丙烯酸羟烷基酯的磷酸酯,包括甲基丙烯酸磷酸乙酯和甲基丙烯酸磷酸丙酯,特别优选的是甲基丙烯酸磷酸乙酯。本文所述的“甲基丙烯酸磷酸乙酯”(PEM)指的是以下结构:
其中R是H或者
本文所用术语“结构单元”指的是指定单体的残留部分。PEM的结构单元如下所示:
其中,虚线表示连接到聚合物主链的位置。市售可得的含PEM粘合剂的例子包括EVOQUETM2350预复合体聚合物(陶氏化学公司或其附属公司的商标)和EVOQUETM1140预复合体聚合物。
本发明的组合物可用于低VOC漆制剂和/或包含具有含磷酸单体的结构单元的粘合剂的漆制剂。漆组合物中的粘合剂的量取决于所需的光泽度。例如,对于高光泽度装饰漆,粘合剂的重量百分比通常在30-40重量%的范围内,以制剂的重量计;对于半光泽度,粘合剂的重量百分比通常在15-25重量%的范围内,以制剂的重量计;对于缎光和平面漆,通常为5-10重量%的范围内,以制剂的重量计。
本发明的组合物还可包括附加材料,例如:颜料,如未包封、部分包封或完全包封的TiO2;填料;表面活性剂;分散剂;增稠剂;着色剂;防腐剂;流动剂;流平剂;延展剂,包括不透明聚合物;以及中和剂。虽然也可以包括溶剂和聚结剂,但是对于低VOC制剂而言,这些物质应该最小化,也就是说,制剂含有不超过50g/L的这些物质。
实施例
下面的实施例仅是为了阐述,而不是用来限制本发明的范围。
在以下实施例中,粘合剂1指的是EVOQUETM1140预复合体聚合物(低VOC,Tg=3-5℃);粘合剂2指的是RHOPLEXTMVSR1050丙烯酸类乳液(低VOC,Tg=5-10℃)。DF1指的是DC71消泡剂,这是用于本发明的实施例的组合物的消泡剂。DC71的特征如下:
其中,R1是-(CH2)3O(C3H6O)pCH3;R2是-(CH2)3O(C2H4O)qCH3;p是19至21;q是33至35;n+m是18至20;x+y+n+m是195至205。
DF2、DF3和DF4是用于比较例的消泡剂。DF2指的是道康宁添加剂DC74消泡剂(DowCorning Additive DC74Defoamer);DF3是Byk 022消泡剂;DF4是DrewPlus L475消泡剂。DC74是具有环氧乙烷和环氧丙烷基团的侧链嵌段共聚物的聚硅氧烷聚醚消泡剂;这些基团主要被OH基团封端,没有被甲基基团封端的。Byk 022是具有侧链环氧乙烷和环氧丙烷基团的聚硅氧烷聚醚消泡剂;这些基团主要被OH基团封端,没有被甲基基团封端的。DrewPlusL475是矿物油中的含疏水性聚合物的非硅消泡剂。
表1显示漆1的配方,所述漆1是低VOC漆,VOC浓度为33g/L。
表1-漆1的配方
表2显示漆2的配方,所述漆2是低VOC漆,VOC浓度为33g/L。
方案1:乳胶制剂的消泡测试
在具有Tite密封(TiteSeal)罩的小瓶(通常称作PPR小瓶,平行压力反应器小瓶)中,将已知体积(0.5-2mL)的粘合剂1和粘合剂2独立地与消泡剂混合。粘合剂中的消泡剂浓度见表3。含有制剂的小瓶放置过夜。然后用机械“腕振荡器”以2-5次振荡/秒的频率振荡小瓶3分钟。产生的剪切导致制剂中已知体积的空气以微气泡/大气泡的形式被夹带走。然后将制剂置于麦拉(Mylar)膜上,下拉至润湿厚度为12密耳。然后将拉制涂层置于显微镜下,初始化时间间隔图像采集,以测量涂层中含有的气泡的程度。微气泡/大气泡的数量结果(微气泡定义为直径<70微米的任意气泡,大气泡定义为直径>70微米的任意气泡)见表3所示。基于微气泡和大气泡的数量,限定了阈值,基于该阈值来判断消泡剂是合格或者不合格的,结果见表3。
方案2:乳胶-TiO2制剂的消泡测试
在500mL塑料容器中装载粘合剂(225g)和已知浓度的消泡剂(湿润粘合剂上的活性消泡剂)来制备样品。将容器放置在水平台顶振荡器上,以180次振荡/分钟持续30分钟。在从振荡器取出后用密度杯测量并记录混合物的密度。然后将一部分经搅动的混合物用于制备粘合剂/TiO2复合样品。
通过将粘合剂与消泡剂的预搅动混合物(201g)装载到1夸脱金属罐中,然后加入水(60.59g)来制备样品。然后将混合物放置在具有船用螺旋桨叶片的悬臂式搅拌器上;然后向以450rpm搅拌的所述混合物中加入TiO2浆液(193g)。在完成加入浆液之后,完整的复合混合物再搅拌15分钟。采用密度杯测量最终混合物的密度。最终密度与理论计算密度的比值用于评价不同消泡剂的性能。结果示于表4中。
方案3:漆制剂的消泡
如方案1所述混合粘合剂和消泡剂。粘合剂中的消泡剂浓度见表5。含有制剂的小瓶放置过夜。向小瓶中加入Zirconox陶瓷珠(0.5g,1.0-1.2mm)以增加涂料物质的剪切。然后用机械腕振荡器以2-5次振荡/秒的频率振荡小瓶3分钟,用于消泡测试。产生的剪切导致制剂中已知体积的空气以微气泡/大气泡的形式被夹带走。然后将制剂置于麦拉(Mylar)膜上,下拉至润湿厚度为12密耳。然后将拉制涂层置于显微镜下,初始化时间间隔图像采集,以测量涂层中含有的气泡的程度。微气泡/大气泡的数量结果(微气泡定义为直径<70微米的任意气泡,大气泡定义为直径>70微米的任意气泡)见表3所示。基于微气泡和大气泡的数量,限定了阈值,基于该阈值来判断消泡剂是合格或者不合格的,结果见表5。
表3-方案1的泡沫结果
如表4所示,DF-1是仅有的在所有的测试的制剂中合格的消泡剂。
表4-方案2的泡沫结果
表5-方案3的泡沫结果
结果表明对于所有的3个方案,粘合剂、粘合剂+TiO2复合制剂以及漆制剂研究,DF1其降低微泡沫和大泡沫的量的能力是通用的。
Claims (9)
1.一种组合物,该组合物包含粘合剂的水性分散体和0.01-2重量%的消泡剂,以粘合剂的重量计,所述消泡剂用如下结构进行表征:
其中R1是-(CH2)3O(C3H6O)pCH3;
R2是-(CH2)3O(C2H4O)qCH3;
x为0至240;
y为0至240;
m+n=15至25;
x+y+m+n=175至225;
p是10至40;以及
q是30至40;
其中,所述粘合剂的Tg小于20℃,和/或所述粘合剂含有含磷酸单体的结构单元。
2.如权利要求1所述的组合物,其特征在于,所述消泡剂的浓度为0.05-1重量%,以粘合剂的重量计。
3.如权利要求1或2所述的组合物,其特征在于,所述粘合剂是丙烯酸类、苯乙烯-丙烯酸类或者乙烯基酯丙烯酸类聚合物颗粒的水性分散体。
4.如权利要求1或2所述的组合物,其特征在于,R1是-(CH2)3O(C3H6O)19-21CH3;R2是-(CH2)3O(C2H4O)33-35CH3;
并且n+m是18至20;x+y+n+m是195至205。
5.如权利要求1或2所述的组合物,其特征在于,所述粘合剂的Tg小于15℃。
6.如权利要求1或2所述的组合物,其特征在于,所述粘合剂包含0.2-4重量%的甲基丙烯酸磷酸乙酯的结构单元,以粘合剂的重量计。
7.如权利要求1或2所述的组合物,其特征在于,所述组合物还包含一种或多种选自下组的材料:TiO2、中和试剂、分散剂、表面活性剂、填料、增稠剂、聚结剂、防腐剂、流动剂以及流平剂。
8.如权利要求7所述的组合物,该组合物还包含增量剂。
9.如权利要求7所述的组合物,该组合物的VOC不大于50g/L。
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