CN104893399A - 含有三胺官能化的分散剂的涂料组合物 - Google Patents

含有三胺官能化的分散剂的涂料组合物 Download PDF

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CN104893399A
CN104893399A CN201510064371.0A CN201510064371A CN104893399A CN 104893399 A CN104893399 A CN 104893399A CN 201510064371 A CN201510064371 A CN 201510064371A CN 104893399 A CN104893399 A CN 104893399A
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S·巴利杰帕里
L·圣米凯尔里弗拉
S·H·耐赫
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Abstract

本发明涉及一种组合物，所述组合物包含聚合物颗粒的稳定水性分散体和吸附在TiO2颗粒表面上的分散剂，其中所述分散剂是用羧酸酯和三(羟甲基)氨基甲烷的结构单元官能化的水溶性聚合物。本发明的组合物特别适用于使含缔合性增稠剂的油漆实现高遮盖性。

Description

含有三胺官能化的分散剂的涂料组合物
背景技术
本发明涉及一种涂料组合物，该组合物包含三胺官能化的分散剂。所述分散剂可用于促进油漆制剂的遮盖性。
含有缔合性流变改性剂(例如疏水改性的环氧乙烷氨基甲酸酯(HEUR)、疏水改性的碱溶性乳液(HASE)和疏水改性羟乙基纤维素(HMHEC)增稠剂)的油漆可以使胶乳颗粒自缔合，致使TiO2颗粒自缔合(聚集)，因而使得与使用非缔合性增稠剂增稠的组合物相比，前者的遮盖效率降低。发生这种聚集效应是由于缔合性流变改性剂与油漆体系中的粘合剂形成网络，从而迫使TiO2颗粒更加靠近。因此，需要探索一种方式来改进使用缔合性流变改性剂配制的涂料的遮盖效率。
发明内容
本发明通过提供一种组合物解决了本领域中存在的需求，所述组合物包含聚合物颗粒的稳定水性分散体和吸附在TiO2颗粒表面上的分散剂，其中所述分散剂是用羧酸酯单体和三(羟甲基)氨基甲烷的结构单元官能化的水溶性聚合物。本发明通过提供一种方式用来改进用缔合性增稠剂增稠的油漆制剂的遮盖性，从而解决了本领域的需求。
具体实施方式
本发明通过提供一种组合物解决了本领域中存在的需求，所述组合物包含聚合物颗粒的稳定水性分散体和吸附在TiO2颗粒表面上的分散剂，其中所述分散剂是用羧酸酯单体和三(羟甲基)氨基甲烷的结构单元官能化的水溶性聚合物。
羧酸酯单体的结构单元如下所示：
其中，R是H或甲基，R1是C1-C20烷基，虚线表示该单元与聚合物主链的连接位点。
三(羟甲基)甲烷的结构单元由酰氨基转移单元和/或酯基转移单元表示：
所述分散剂可以在以下条件下通过使三(羟甲基)胺与用羧酸酯单体的结构单元官能化的聚合物接触，优选与甲基丙烯酸甲酯的均聚物接触来制备：在升高的温度下，优选在150-200℃的范围内，在存在高沸点溶剂例如N-甲基吡咯烷酮的条件下，在存在合适的催化剂例如二丁基氧化锡的条件下。所述分散剂还可通过使三(羟甲基)丙烯酰胺与羧酸酯单体，例如甲基丙烯酸甲酯发生共聚来制备。
所得的聚合物优选包含酰氨基转移单元和酯基转移单元，优选以2:1至10:1的摩尔:摩尔比包含更多的酰氨基转移；所述聚合物还优选包含未反应的羧酸酯(优选甲基丙烯酸甲酯)结构单元。
较好的是，三(羟甲基)甲烷的结构单元与羧酸酯单体(优选甲基丙烯酸甲酯)的结构单元的摩尔:摩尔比为40:60至90:10。所述分散剂的优选Mw为1000-25,000克/摩尔。
本发明的组合物可以通过使所述分散剂、聚合物颗粒的稳定水性分散体与TiO2一起接触来制备。所述组合物还可包含以下材料中的一种或多种：流变改性剂；不透明聚合物；填料；着色剂，其它颜料，包括包封或部分包封的颜料和不透明颜料；分散剂；润湿助剂；分散助剂；分散剂佐剂；表面活性剂；助溶剂；聚结剂和增塑剂；消泡剂；防腐剂；抗划痕添加剂；流动剂；流平剂；增滑添加剂；和中和剂。
在以下实施例中，聚甲基丙烯酸甲酯购自奥德里奇公司(Aldrich)，据报道其具有～15,000g/mol(实施例1)和～5300g/mol(实施例2)的Mw。
实施例
实施例1-聚(甲基丙烯酸甲酯)-g-三(羟甲基)氨基甲烷的制备
在装配有回流冷凝器的反应烧瓶中，将聚甲基丙烯酸甲酯(20g,Mw＝15,000g/mol，由奥德里奇公司提供),三(羟甲基)氨基甲烷(70g),N-甲基-2-吡咯烷酮(NMP,40mL)和二丁基氧化锡(500mg)混合并加热至190–200℃，加热2小时。将产物冷却并在***中沉淀，然后在真空60℃下干燥。通过溶解在NMP并在***中沉淀，使该聚合物重新沉淀，然后在真空中在60℃下重新干燥。
实施例2-聚(甲基丙烯酸甲酯)-g-三(羟甲基)氨基甲烷的制备
基本上按照实施例1所述的步骤进行制备，不同之处在于，使用Mw为5,300g/mol的聚甲基丙烯酸甲酯。
油漆制剂
使用实施例1和2制备油漆制剂，以及使用TAMOLTM2002分散剂(一种疏水性多酸共聚物)制备比较例制剂。在下表1中，TiO2表示Ti-纯R-706TiO2,SG-10M表示RHOPLEXTMSG-10M丙烯酸类共聚物，Texanol表示Texanol聚结剂,RM-2020表示ACRYSOLTMRM-2020NPR流变改性剂,RM-825表示ACRYSOLTMRM-825流变改性剂,15-S-9表示TERGITOLTM15-S-9表面活性剂。(TAMPOLTM,RHOPLEXTM,ACRYSOLTM和TERGITOLTM均为陶氏化学公司(The Dow Chemical Company)或其附属公司的商标)。
表1-使用实施例1或实施例2分散剂的油漆制剂
磨料 重量(g)
分散剂(干) 0.07
水 1.68
TiO2 4.69
磨料小计 6.44
调漆料
SG-10M 13.94
Texanol 0.56
水 3.55
RM-2020 0.56
RM-825 0.015
15-S-9 0.1
调漆料小计 18.72
总计 25.16
将油漆涂覆在Leneta卡片上，并使用库贝尔卡-蒙克(Kubelka-Munk)S/密耳测试方法来测定遮盖性(S/密耳)。
库贝尔卡-蒙克S/密耳测试方法
对于每一种漆，使用1.5密耳博德下拉棒(Bird draw down bar)在黑色脱模卡片(Leneta Form RC-BC)上制备两个下拉样，卡片自然干燥过夜。用X-ACTO刀使用模板在每一个卡片上切割出3.25”x 4”的矩形。使用BYK Gardner光谱导向(Spectro-guide)45/0光泽色彩分光光度计(Gloss Color spectrophotometer)在每一刻划区域对Y-反射率测量五次，在起始于矩形顶部的对角线上进行测量，并记录平均Y-反射率。对于每一种漆，使用3”25密耳块下拉棒(block draw downbar)在黑色乙烯基卡片(Leneta Form P121-10N)上制备厚膜下拉样，使得卡片自然干燥过夜。在下拉样的五个不同区域测量Y-反射率，并记录平均Y-反射率。库贝尔卡-蒙克遮盖值S由以下等式1得出：
等式1
S = R X × ( 1 - R 2 ) × ln 1 - ( R B × R ) 1 - R B R
其中X是平均膜厚度，R是厚膜的平均反射率，RB是薄膜在黑色上的平均反射率。可由油漆膜的重量(Wpf),干膜的密度(D)以及膜面积(A)计算X。3.25”x4”模板的膜面积是13英寸2。
在表2中，显示了配制的漆的遮盖数值。
实施例编号 油漆制剂中的分散剂 S/密耳
实施例1 PMMA-Tris Mw＝15K 6.54
实施例2 PMMA-Tris Mw＝5.2K 6.52
比较例1 TAMOL 2002分散剂 5.64
结果表明，使用本发明的PMMA-Tris分散剂、包含缔合性增稠剂(在这些实施例中，HEUR增稠剂)的油漆制剂可实现极好的遮盖性。

Claims (5)

1.一种组合物，所述组合物包含聚合物颗粒的稳定水性分散体和吸附在TiO2颗粒表面上的分散剂，其中所述分散剂是用羧酸酯和三(羟甲基)氨基甲烷的结构单元官能化的水溶性聚合物。
2.如权利要求1所述的组合物，其特征在于，所述羧酸酯是甲基丙烯酸甲酯。
3.如权利要求2所述的组合物，其特征在于，三(羟甲基)氨基甲烷的结构单元与甲基丙烯酸甲酯的结构单元的摩尔:摩尔比为40:60至90:10。
4.如权利要求1-3中任一项所述的组合物，其特征在于，所述组合物还包含缔合性增稠剂。
5.如权利要求1-3中任一项所述的组合物，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：流变改性剂；不透明聚合物；填料；着色剂，其它颜料，其包括包封或部分包封的颜料和不透明颜料；分散剂；润湿助剂；分散助剂；分散剂佐剂；表面活性剂；助溶剂；聚结剂和增塑剂；消泡剂；防腐剂；抗划痕添加剂；流动剂；流平剂；增滑添加剂；和中和剂。
CN201510064371.0A 2014-03-07 2015-02-06 含有三胺官能化的分散剂的涂料组合物 Pending CN104893399A (zh)

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