CN112739734B - 聚合物颗粒、微球和聚硅氧烷颗粒的水性分散体 - Google Patents
聚合物颗粒、微球和聚硅氧烷颗粒的水性分散体 Download PDFInfo
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- CN112739734B CN112739734B CN201980062251.3A CN201980062251A CN112739734B CN 112739734 B CN112739734 B CN 112739734B CN 201980062251 A CN201980062251 A CN 201980062251A CN 112739734 B CN112739734 B CN 112739734B
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Abstract
本发明涉及一种漆组合物，其包含以下的水性分散体：a)平均粒径在80nm到500nm的范围内的聚合物颗粒；b)粒径在1μm到20μm的范围内的聚合有机交联微球；c)粒径在1μm到30μm的范围内的聚硅氧烷颗粒；d)流变改性剂；e)折射率>1.9的不透明白色颜料；和f)小于10重量％的低Tg聚氨酯。本发明的组合物给予涂层优异的耐磨光性。
Description
背景技术
本发明涉及一种漆组合物，其包含聚合物颗粒(胶乳)、微球和聚硅氧烷颗粒的水性分散体；所述漆组合物适用于制备具有改善的耐磨光性的涂层。
实现具有传统哑光涂层光泽的半光泽涂层的性能属性是一个远大目标，并且迄今尚未实现。哑光涂层因其遮蔽基材的表面缺陷的能力而合乎期望。控制光泽(其在这些低光泽装饰漆的设计中至关重要)用消光剂(也被称为增量剂或失光剂)完成，所述消光剂为碳酸钙、二氧化硅、粘土、滑石等的无机颗粒。
消光剂通过增加膜的表面粗糙度来降低光泽；不利的是，传统的消光剂损害了所得膜的耐久性和性能。因此，由于耐磨光性差(摩擦或研磨引起的光泽/光泽度不必要的增加)，高流量区域不使用哑光涂料。因此，设计形成具有改善的耐磨光性的涂层的哑光涂料组合物将是有利的。
发明内容
本发明通过提供包含以下的水性分散体的漆组合物解决所属领域的需求：
a)z平均粒径在80nm到500nm的范围内的聚合物颗粒；
b)平均粒径在1μm到20μm的范围内的聚合有机交联微球；
c)平均粒径在1μm到30μm的范围内的聚硅氧烷颗粒；
d)流变改性剂；
e)颜料体积浓度在1到30的范围内的折射率>1.9的不透明白色颜料，其条件是当不透明白色颜料的颜料体积浓度小于10时，以漆组合物的重量计，漆组合物包含在5重量％到20重量％固体的范围内的非白色着色剂；和
f)以聚合物颗粒的重量计，小于10重量％的Tg<0℃的聚氨酯；
其中以漆组合物的重量计，聚合物颗粒和交联微球的浓度在10重量％到65重量％的范围内；
其中聚合物颗粒与交联微球的重量:重量比在1.1:1到20:1的范围内；以漆组合物的重量计，聚硅氧烷颗粒的浓度在0.05重量％到5重量％的范围内；并且以漆组合物的重量计，流变改性剂的浓度在0.1重量％到5重量％的范围内。
本发明通过提供给予哑光面漆半光泽涂漆基材的耐磨光性的组合物来解决所属领域中的需要。
具体实施方式
本发明为包含以下的水性分散体的漆组合物：
a)z平均粒径在80nm到500nm的范围内的聚合物颗粒；
b)平均粒径在1μm到20μm的范围内的聚合有机交联微球；
c)平均粒径在1μm到30μm的范围内的聚硅氧烷颗粒；
d)流变改性剂；
e)颜料体积浓度在1到30的范围内的折射率>1.9的不透明白色颜料，其条件是当不透明白色颜料的颜料体积浓度小于10时，以漆组合物的重量计，所述漆组合物包含在5重量％到20重量％固体的范围内的非白色着色剂；和
f)以述聚合物颗粒的重量计，小于10重量％的Tg<0℃的聚氨酯。
其中以漆组合物的重量计，聚合物颗粒和交联微球的浓度在10重量％到65重量％的范围内；
其中聚合物颗粒与交联微球的重量:重量比在1.1:1到20:1的范围内；以漆组合物的重量计，聚硅氧烷颗粒的浓度在0.05重量％到5重量％的范围内；并且以漆组合物的重量计，流变改性剂的浓度在0.1重量％到5重量％的范围内。
聚合物颗粒优选地为丙烯酸类，这意指以聚合物颗粒的重量计，这些聚合物颗粒包含至少30重量％一种或多种甲基丙烯酸酯单体(如甲基丙烯酸甲酯)和甲基丙烯酸乙酯，和/或一种或多种丙烯酸酯单体(如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯)的结构单元。丙烯酸类聚合物还可包括烯键式不饱和羧酸单体(如甲基丙烯酸、丙烯酸和衣康酸)的结构单元或其盐，以及磷酸单体(如甲基丙烯酸磷酸乙酯)的结构单元或其盐。
聚合物颗粒还可包括其它非丙烯酸酯或甲基丙烯酸酯单体的结构单元，如苯乙烯和乙酸乙烯酯。聚合物颗粒优选地在低于室温下成膜；并且优选地通过福克斯方程计算的Tg<20℃，更优选地<15℃。
优选地，以聚合物颗粒和聚合有机微球的重量计，聚合物颗粒还包含0.05重量％，更优选地0.5重量％到12重量％更优选到5重量％具有酮官能团的单体的结构单元，包括甲基丙烯酸乙酰乙酰氧基乙酯(AAEM)或二丙酮丙烯酰胺(DAAM)。
如果聚合物颗粒被官能化为具有酮官能团的单体的结构单元，那么以聚合物颗粒和微球的重量计，漆组合物有利地包括0.1重量％，优选地0.2重量％，并且更优选地0.5重量％到10重量％，并且优选地到5重量％的二酰肼或聚胺交联剂。聚胺交联剂的实例包括二胺，如3,3'-(乙烷-1,2-二基双(氧基))双(丙-1-胺)；4,9-二氧十二烷-1,12-二胺；4,9-二氧十二烷-1,12-二胺；4,7-二氧十二烷-1,10-二胺；和4,7,10-三氧十三烷-1,13-二胺。聚胺的商业实例是聚醚胺，如JEFFAMINE D-230、JEFFAMINE D-400、JEFFAMINE D-2000、JEFFAMINE M-600、JEFFAMINE M-1000、JEFFAMINE ED-600、JEFFAMINE ED-900、T-403以及JEFFAMINE T-3000聚醚胺。当具有酮官能团的单体为DAAM时，组合物优选地包括二酰肼交联剂，如己二酸二酰肼(ADH)、碳二酰肼(CDH)、癸二酸二酰肼(SDH)、缬氨酸二酰肼(VDH)、间苯二甲酸二酰肼(ISODH)和二十碳二酰肼(ICODH)。优选地，用于DAAM官能化的聚合物颗粒的交联剂为二酰肼，更优选地ADH。
术语“结构单元”在本文中用于描述聚合之后的所述单体的残余。举例来说，甲基丙烯酸甲酯的结构单元如下所示：
其中虚线表示结构单元与聚合物主链的连接点。
以漆组合物的重量计，聚合物颗粒的浓度优选地在10重量％，更优选地15重量％到35重量％，更优选地到30重量％，并且最优选地到25重量％的范围内。优选地，聚合物颗粒的z均粒径在100nm到300nm，更优选地到250nm的范围内如使用Brookhaven BI90粒子分析仪或类似的动态光散射仪进行测量。
聚合有机交联微球优选地包含低Tg第一级(≤20℃，优选地<10℃，并且更优选地<0℃，如通过福克斯方程计算)聚合物，其交联以提供回弹性并且不扩散到基材；和高Tg第二级(≥30℃，优选地大于50℃，如通过福克斯方程计算)以提供在室温下不成膜的微球。优选地，至少50重量％，更优选地至少70重量％，并且最优选地至少90重量％的交联第一级包含I)丙烯酸甲酯、丙烯酸丁酯或丙烯酸乙酯或其组合；和II)下文例示的多烯键式不饱和非离子单体的结构单元，I:II w/w比在99.5:0.5到90:10的范围内；优选地，甲基丙烯酸甲酯包含至少60重量％，更优选地至少80重量％，并且最优选地至少90重量％的第二级。
聚合有机交联微球的平均粒径(技术上，中值重均粒径，D50)在2μm，优选地4μm到20μm，优选地15μm的范围内，如使用如下文所描述的圆盘式离心机光测沉淀计所测量。交联微球的含水分散体可通过多种方式制备，包括描述于美国专利公开2013/0052454；US 4,403,003；US 7,768,602；和US7,829,626中的那些。
在制备聚合有机交联多级微球的水性分散体的优选方法(优选方法A)中，包含第一单烯键式不饱和非离子单体的结构单元的第一微球的水性分散体在聚合条件下与以第一级单体的重量计包含以下的第一级单体接触：a)0.05重量％到5重量％的可聚合有机磷酸酯或其盐；和b)70重量％到99.95重量％的第二单烯键式不饱和非离子单体，以生长出第一微球以形成有机磷酸酯官能化第二微球的水性分散体，其中第一微球的粒径在1μm到15μm的范围内，并且第二微球的粒径在1.1μm和20μm的范围内；并且其中可聚合有机磷酸酯由式I的结构或其盐表示：
或其盐；其中R为H或CH3，其中R1和R2各自独立地为H或CH3，其条件是没有两个相邻的CR2CR1基团各自被甲基取代；每个R3独立地为直链或支链C2-C6亚烷基；m为1到10并且n为0到5，其条件是当m为1时，n为1到5；x为1或2；并且y为1或2；并且x+y＝3。通过此方法制备的所得微球优选地用以微球的重量计0.05重量％到5重量％的式I的结构单元或其盐官能化。
当n为0，x为1且y为2时，可聚合的有机磷酸酯或其盐由式II的结构表示：
优选地，R1和R2中的一个为H，并且R1和R2中的另一个为CH3；更优选地，每个R2为H并且每个R1为CH3；m优选地为3，并且更优选地4；到优选地到8，并且更优选地到7。SipomerPAM-100、Sipomer PAM-200和Sipomer PAM到600磷酸酯为在式II化合物的范围内可商购的化合物的实例。
在另一个方面，其中n为1；m为1；R为CH3；R1和R2各自为H；R3-(CH2)5-；x为1或2；y为1或2；并且x+y＝3，可聚合有机磷酸酯或其盐由式III的结构表示：
在式III的范围内的可商购化合物为Kayamer PM-21磷酸酯。
在此方法中，第一微球优选地包含90重量％到99.9重量％单烯键式不饱和非离子单体的结构单元，其实例包括丙烯酸酯，如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯；甲基丙烯酸酯，如甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸乙酰乙酰氧基乙酯和甲基丙烯酸脲酯；丙烯腈；丙烯酰胺，如丙烯酰胺和二丙酮丙烯酰胺；苯乙烯；和乙烯基酯，如乙酸乙烯酯。尽管有可能第一微球包括羧酸单体(如甲基丙烯酸或丙烯酸)的结构单元，但是优选地，以微球的重量计，第一微球包含小于5重量％，更优选地小于3，并且最优选地小于1重量％羧酸单体的结构单元。第一微球更优选地包含丙烯酸酯或甲基丙烯酸酯或丙烯酸酯和甲基丙烯酸酯的组合的结构单元。
如本文所描述的，第一微球有利地由重均分子量(Mw)在800g/mol，优选地1000g/mol到20,000g/mol，优选地到10,000g/mol并且最优选地到5000g/mol的范围内的低聚种子的水性分散体制备，所述重均分子量如使用聚苯乙烯标准物通过尺寸排阻色谱法确定的。如本文所描述的，低聚种子的平均直径在200nm，更优选地400nm，并且最优选地600nm到8000nm，优选地到5000nm，更优选地到1500nm，并且最优选地到1000nm，如通过盘式离心DCP确定的。低聚种子含有如烷基硫醇的链转移剂的结构，其实例包括正十二烷基硫醇、1-己硫醇、1-辛硫醇和2-丁硫醇。
低聚种子和疏水性引发剂的水性分散体有利地与第一单烯键式不饱和单体接触；替代地，单体可溶胀成低聚种子，随后添加疏水性引发剂。疏水性引发剂优选地以水性分散体的形式添加。如本文所使用的，疏水性引发剂是指水溶解度在5ppm，优选地10ppm到10,000ppm，优选地到1000ppm且更优选地到100ppm范围内的引发剂。合适的疏水性引发剂的实例包括如过氧基-2-乙基己酸叔戊酯(在20℃下水溶解度＝17.6mg/L)或过氧基-2-乙基己酸叔丁酯(在20℃下水溶解度＝46mg/L)。溶胀程度(种子生长)可通过单体与种子的比来控制。合适的单烯键式不饱和非离子单体的实例包括丙烯酸酯，如丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯；甲基丙烯酸酯，如甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸乙酰乙酰氧基乙酯和甲基丙烯酸脲酯；丙烯腈；丙烯酰胺，如丙烯酰胺和双丙酮丙烯酰胺；苯乙烯和乙烯基酯，如乙酸乙烯酯。
由低聚种子形成微球提供了控制微球粒径分布的有效方式。优选地，如通过DCP确定的第一和第二微球的变异系数小于25％，更优选地小于20％，更优选地小于15％且最优选地小于10％。优选地，以水性分散体的重量计，在制备第二微球的水性分散体的过程中形成的凝胶的浓度优选地小于0.5重量％，更优选地小于0.2重量％，更优地选小于0.1重量％且最优选地小于0.05重量％。具有低变异系数的微球的分散体最终导致涂料在最终用途应用中具有可靠且可再现的性能。相比之下，变异系数大于30％的微球给予涂料不可靠且不可预测的特性。
优选地，第一微球的D50粒径为2.5μm，更优选地3.0μm，优选地到12μm，更优选地到10μm，并且最优选地到8.5μm。
在优选的制备被官能化为具有结构I的可聚合有机磷酸酯的微球的水性分散体的方法中，第一微球的水性分散体在聚合条件下和在存在乳化表面活性剂(如磷酸酯或烷基苯磺酸酯或硫酸酯)的情况下与第一级单体接触，以第一级单体的重量计，所述第一级单体包含0.05重量％，优选地0.1重量％并且更优选地0.2重量％到5重量％，优选地到3重量％，更优选到2重量％，并且最优选地到1重量％的结构I的可聚合有机磷酸酯或其盐；和70重量％，更优选地80重量％，并且最优选地90重量％到99.95重量％，优选地99.8重量％的第二单烯键式不饱和非离子单体。第一微球的体积增加(生长出)以形成有机磷酸酯官能化的第二微球的水性分散体，其粒径在1.1μm，并且优选地2.5μm，优选地3.5μm到20μm，并且优选地到15μm的范围内。
第一级单体优选还包含以第一级单体的重量计，优选地浓度范围为0.1重量％，更优选地1重量％，并且最优选地2重量％到15重量％，更优选地到10重量％，并且最优选地到8重量％的多烯键式不饱和非离子单体。合适的多烯键式不饱和非离子单体的实例包括甲基丙烯酸烯丙酯、丙烯酸烯丙酯、二乙烯基苯、三羟甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、丁二醇(1,3)二甲基丙烯酸酯、丁二醇(1,3)二丙烯酸酯、乙二醇二甲基丙烯酸酯和乙二醇二丙烯酸酯。在期望对官能化第二微球进行进一步分级的情况下，包含这些多烯键式不饱和非离子单体是特别优选的。
第一级单体以及第二微球优选地包含基本上不存在的羧酸单体的结构单元。如本文所用，基本上不存在的羧酸单体的结构单元意指以微球的重量计，小于5重量％、优选地小于3重量％，更优选地小于1重量％，并且最优选地小于0.2重量％羧酸单体(如甲基丙烯酸或丙烯酸)的结构单元。
第二微球优选地包含90重量％到98重量％第二单烯键式不饱和非离子单体的结构单元，所述重量百分比可与第一单烯键式不饱和非离子单体相同或不同。进一步优选地，在第二单烯键式不饱和单体中，以与对于磷酸官能化聚合物颗粒描述相同的浓度范围包括酮官能化单体。应当理解，“单体”是指一种或多种单体。
优选地，第一微球的水性分散体在聚合条件下与过量的可聚合有机磷酸酯(或其盐)接触，使得所得有机磷酸酯官能化第二微球的分散体包含未反应的有机磷酸酯。如果期望对第二微球进行进一步分级，那么存在未反应的(残留的)可聚合有机磷酸酯或其盐是尤其有利的。举例来说，可能期望制备如通过福克斯方程计算的Tg小于25℃的第二微球的分散体，然后用残留有机磷酸酯和额外单烯键式不饱和非离子单体(第二级烯键式不饱和非离子单体)(其可与第一级单烯键式不饱和非离子单体相同或不同)对第二微球进行进一步分级，以产生具有Tg小于25℃的结构域和Tg大于50℃的结构域的有机磷酸酯官能化第三微球的分散体。
在使用引发剂/氧化还原对的情况下，已经发现，如果在pH为比剩余可聚合有机磷酸酯的第一pKa高至少一个pH单位下进行聚合，那么凝胶的进一步形成显著减弱。优选地，用于制备第三微球的水性分散体的聚合步骤在至少3，更优选地至少4，更优选地至少5并且最优选地至少6到优选地12，更优选地到10并且最优选地到8的pH下进行。因此，用于制备第三微球的水性分散体的可聚合有机磷酸酯优选地主要以盐，优选地如锂、钠、钾、三烷基铵或铵盐的形式存在。
可在第二微球的进一步分级中添加额外的可聚合有机磷酸酯，优选地在使用引发剂氧化还原/对的期望pH范围内。尤其优选地使用式II的盐制备微球，其中每个R2为H，并且每个R1为CH3，或每个R2为CH3并且每个R1为H；或式III。
由优选方法A产生的聚合微球的水性分散体包含被官能化为具有以微球的重量计0.05重量％到5重量％的式I的结构单元的交联微球。
在制备聚合多级交联微球的水性分散体的另一种优选方法(优选方法B)中，第一微球的水性分散体(如优选方法A中所描述制备)与包含70重量％到100重量％的第二单烯键式不饱和非离子单体的第一级单体接触，以生长出第一微球，以形成第二微球的水性分散体，如上文所描述，不同之处在于在存在二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐的情况下进行聚合。二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或阴离子聚环氧烷盐由式IV化合物表示：
其中每个R'独立地为C1-C4烷基；R1'为H、CH2CR＝CH2、CH＝CHCH3或1-苯乙基-(R')p；每个R2'独立地为H、烯丙基、甲基、丙烯酸酯、甲基丙烯酸酯、或-CH2CHR3OX；每个R3'独立地为H、甲基或乙基；m为0到5；n为6到40；p为0、1或2；并且O-X为羟基、甲氧基、硫酸酯基或磷酸酯基。优选地，R1'为1-苯乙基-(R')n；R2'优选地为H、CH3或烯丙基；m优选地为0、1或2；n为10到20；p为0；并且O-X是硫酸酯基或磷酸酯基。更优选的三苯乙烯基苯酚的聚环氧乙烷盐由式V化合物表示：
其中X为-SO3H、-SO3Y、-H2PO3、-HPO3Y或-PO3Y2，其中Y为Li+、Na+、K+或NH4 +。可商购的具有式II化合物的实例为聚芳基苯基醚硫酸酯的Solvay Soprophor 4D/384铵盐。
二苯乙烯基苯酚或三苯乙烯基苯酚的另一种优选的环氧乙烷盐由式VI化合物表示，其中m是非零的。
其中n优选地为12到18。式VI化合物的商业实例为E-Sperse RS-1684反应性表面活性剂。二苯乙烯基苯酚的聚环氧乙烷盐的另一个实例由式VII化合物表示：
式IV化合物的商业实例为Hitenol AR-1025反应性表面活性剂。
结构IV(m＝0)的化合物的亚类可通过使二苯乙烯基或三苯乙烯基苯酚与环氧烷(环氧乙烷、1,2-环氧丙烷或1,2-环氧丁烷)在存在如碱金属或碱土金属氢氧化物、碳酸盐或碳酸氢盐，或碱金属氢化物的碱的情况下反应来制备；此中间体然后可中和成相应的二醇，用卤代甲烷甲氧基化，用磺酰氯磺化或用聚磷酸磷酸化。式VI化合物可以相同的方式制备，不同之处在于二苯乙烯基或三苯乙烯基苯酚在存在碱的情况下首先与如表氯醇等表卤代醇反应以形成二苯乙烯基或三苯乙烯基苯酚的相应单缩水甘油醚，然后与烯化氧反应。
优选地，第一微球的水性分散体在聚合条件下与式V化合物的盐或过量的式VI化合物或式VII的盐接触，使得所得第二微球的分散体优选地包含式V化合物的盐或未反应的式VI式VII化合物的盐。如果对第二微球进行进一步分级，那么存在式V、VI或VII化合物的盐尤其有利。举例来说，可能期望制备如通过福克斯方程计算的Tg小于25℃的第二微球的分散体，然后在聚合条件下用式V、VI或VII化合物的盐和额外单烯键式不饱和非离子单体(第二级单烯键式不饱和非离子单体)(其可与第一级单烯键式不饱和非离子单体相同或不同)对第二微球进行进一步分级以产生Tg小于25℃的结构域和Tg大于50℃的结构域的第三微球的分散体。
优选地，用于制备第三微球的水性分散体的聚合步骤在至少3，更优选地至少4，更优选地至少5并且最优选地至少6到优选地12，更优选地到10并且最优选地到8的pH下进行。
额外式IV化合物，特别是式IV化合物的盐，可在第二微球的进一步分级中添加，优选地在使用引发剂/偶合剂的情况下在期望的pH范围内。
通过优选方法B形成的微球的粒径和粒径分布与优选方法A所获得的分布相似。
还可能并且有时优选制备具有不同大小的微球的组合物，每个微球具有低的变异系数；这类配制物可由例如D50粒径为8μm的微球的水性分散体和D50粒径为12μm的微球的水性分散体的共混产生，每种分散体的变异系数<20％，以形成两种模式具有控制的粒径的微球的双峰分散体。
在优选的方面，由优选方法B产生的聚合微球的水性分散体包含被官能化为具有以微球的重量计0.01重量％到5重量％的式VI化合物的结构单元的交联微球；在另一个优选方面，以微球的重量计，组合物还包含0.01重量％，优选地0.05重量％，更优选地0.1重量％，并且最优选地0.2重量％到5重量％，优选地到3重量％，更优选地到2重量％，并且最优选地到1重量％的结构V化合物。
优选地，被官能化为具有式I、式VI或式VII化合物的结构单元的聚合有机微球以及还包含式V化合物的组合物包含基本上不存在的甲基丙烯酸磷酸乙酯(PEM)，即以聚合有机微球的重量计，小于0.09重量％，更优选地小于0.05重量％，更优选地小于0.01重量％，并且最优选地0重量％PEM的结构单元。
聚合物颗粒与交联微球的重量:重量比在1.1:1，优选地1.3:1，并且更优选地1.5:1到20:1，更优选地到10:1，更优选地到5:1，并且最优选地到3:1的范围内。
聚硅氧烷为直链和/或分支链聚合物，其包含Si-O-Si基团和Si-烷基的重复单元；聚硅氧烷任选地包含例如Si-O-烷基、Si-O-芳基、Si-OH、Si-H和/或Si-O-三烷基硅烷基。优选地，聚硅氧烷为由以下结构表示的线性聚合物：
其中每个R4独立地为C1-C30烷基、O-C1-C6烷基或H，其条件是至少一个R4为C1-C30烷基；每个R5独立地为C1-C30烷基、H或Si(R6)3；其中每个R6独立地为C1-C6烷基；并且n为4，优选地10到10,000，优选地到5000。优选地，每个R4独立地为C1-C6烷基，更优选地乙基或甲基，并且最优选地甲基；优选地，每个R5为H；并且优选地R6为甲基。
如通过Malvern粒径分析仪3000粒径分析仪所测量的聚硅氧烷聚合物颗粒的D50平均粒径在1μm，优选地2μm到20μm，更优选地到15μm，并且最优选地到10μm的范围内。
流变改性剂可为能够将配制物的粘度控制到期望水平的任何增稠剂。优选地，以组合物的重量计，流变改性剂的浓度在0.2重量％，更优选地0.5重量％到优选地3，更优选地到2重量％的范围内。合适的流变改性剂的实例包括疏水改性环氧乙烷氨基甲酸酯聚合物(HEUR)、羟基乙基纤维素(HEC)、碱可溶胀的聚合物(ASE)、和疏水改性的碱可溶胀的聚合物(HASE)。
组合物还包含折射率>1.9的不透明颜料，优选地TiO2。对于深色基础漆组合物，TiO2的颜料体积浓度(PVC)在1和10之间；在这类组合物中，以漆组合物的重量计，漆还包含5重量％到20重量％固体的非白色着色剂。着色剂可为有机或无机的；有机着色剂的实例包括酞菁蓝、酞菁绿、单苯胺黄、联苯胺黄、苯并咪唑酮黄、杂环黄、DAN橙、喹吖啶酮品红、喹吖啶酮紫、有机红，包括金属化的偶氮红和非金属化的偶氮红。无机着色剂包括碳黑、灯黑、黑色氧化铁、黄色氧化铁、褐色氧化铁和红色氧化铁。
对于非深色基础漆组合物，优选的TiO2的PVC在12，更优选地15到25，更优选到22的范围内。TiO2 PVC由以下方程定义：
PVC(TiO2)＝(TiO2固体体积/总固体体积)x 100
其中“总固体体积”包括TiO2、增量剂(如果存在)、聚合物颗粒和微球以及构成最终干燥涂层体积的其它固体(例如不透明聚合物)的贡献。
优选地，如使用Brookhaven BI90颗粒分析仪所测量的TiO2颗粒的z均粒径在200nm，更优选地250nm到400nm，更优选地到350nm，并且最优选地到300nm的范围内。
本发明的组合物还包含小于10重量％，更优选地小于5，更优选地小于1重量％，并且最优选地0重量％的聚氨酯，更具体地分散的聚氨酯颗粒。
在另一个方面，本发明的组合物包含浓度在5重量％，优选地10重量％到20重量％固体的范围内的非白色着色剂和基本上不存在的折射率在1.0到1.9的范围内的无机增量剂。如本文所用，“基本上不存在”是指小于15，优选地小于5，更优选地小于1并且最优选地0PVC的任何具有指定范围内的折射率的增量剂。组合物中基本上不存在的增量剂的实例包括二氧化硅、硅酸盐和铝硅酸盐，如滑石、粘土、云母和绢云母；CaCO3；霞石正长岩；长石；硅灰石；高岭石；磷酸二钙；和硅藻土。
本发明的组合物方便地通过将聚合物颗粒的水性分散体(即胶乳)与聚合有机交联微球的水性分散体、聚硅氧烷的水性分散体、不透明白色颜料的浆液或粉末和流变改性剂混合在一起制备。组合物中还可包括其它添加剂，如聚结剂、表面活性剂、分散剂、杀生物剂、其它不透明颜料，如不透明聚合物、着色剂、蜡、消泡剂和中和剂。
本发明的组合物提供制备具有半光漆的耐磨光性的哑光面漆涂层的方式。
实例
丙烯酸低聚物种子的分子量确定
将丙烯酸低聚物种子(0.1g)的分散体溶解在四氢呋喃(THF，8g，HPLC级)中，然后通过0.45μm PTFE过滤器进行过滤。尺寸排阻色谱法(SEC)在配备有安捷伦(Agilent)1100型等度泵、真空脱气器、可变注射尺寸自动取样器和安捷伦1100HPLC G1362A折射率检测器的液相色谱仪上进行。用安捷伦化学工作站B.04.03版和安捷伦GPC-Addon B.01.01版来处理数据。使用由两根PLgel Mixed D柱(300×7.5mm ID，5μm)和保护柱(50×7.5mm ID，5μm)构成的GPC柱组以1mL/分钟的流速使用THF作为洗脱液来进行GPC分离。用1阶拟合校准曲线来拟合十个聚苯乙烯标准物。标准物的重均分子量(Mw)如下：630；1,370；2,930；4,900；10,190；22,210；50,550；111,400；214,700；和363,600。使用折射率(RI)检测器来收集数据。
用于丙烯酸低聚物种子和微球的DCP粒径设定法
使用经由蔗糖梯度通过离心和沉降的分离模式的盘式离心光测沉淀计(DCP，路易斯安那州普雷里维尔)来测量粒径和分布。通过将1到2滴低聚物种子分散体或微球分散体添加到10mL含有0.1％月桂基硫酸钠的去离子(DI)水中，然后将0.1mL样品注射到填充有15g/mL蔗糖梯度的旋转盘中来制备样品。对于低聚物种子，使用以10,000rpm旋转的0-4％蔗糖梯度盘，并且在注射样品之前注射596-nm聚苯乙烯校准标准物。对于微球，使用以3,000rpm旋转的2％-8％蔗糖梯度盘，并且在注射样品之前注射9-μm聚苯乙烯校准标准物。使用仪器的算法来计算中值重均(D50)粒径和变异系数(CV)。
耐磨光性测试方法
使用3密耳Bird施涂器在Leneta黑色乙烯基卡上对每种涂料进行一次刮涂，然后在25℃和50％相对湿度下干燥7天。在干燥期之后，使用BYK微型三角度光泽度仪(Micro-Tri-gloss meter)在膜上三个不同部分处测量初始光泽度值。使用Gardner研磨测试仪进行磨光测试。研磨舟皿用四层新鲜的粗棉布缠绕并且放置在涂层上。用缠绕粗棉布的研磨舟皿将涂层擦洗500个循环。在完成500个循环之后，在相同的三个部分上测量涂层的光泽度值。报告Δ85°光泽度的平均变化。
中间体实例1-制备其中添加磷酸酯的丙烯酸珠粒的水性分散体
基本上如US 8,686,096实例1和5(第19和20栏)中所描述的制备丙烯酸低聚物种子(33％固体，67丙烯酸丁酯/18正十二烷基硫醇/14.8甲基丙烯酸甲酯/0.2甲基丙烯酸)的水性分散体，其中如通过DCP确定的，中值重均粒径(D50)为885nm并且变异系数为5％，并且重均分子量为2532g/mol。此种子用于制备本文所描述的所有实例和比较实例的微球。
通过在单独的小瓶中组合去离子水(4.9g)、Rhodacal DS-4支链烷基苯磺酸盐(DS-4，0.21g，22.5％水溶液)、4-羟基-2,2,6,6-四甲基哌啶(4-羟基TEMPO，0.4g，5％水溶液)、过氧基-2-乙基己酸叔戊酯(TAPEH，5.42g，98％活性)，然后用匀质器以15,000rpm乳化10分钟来制备引发剂乳液。然后将引发剂乳液添加到在另一个小瓶中的丙烯酸低聚物种子(4.2g，32％固体)分散体中，并混合60分钟。通过将去离子水(109.5g)、PPG单甲基丙烯酸酯的Solvay Sipomer PAM-600磷酸酯(PAM-600，2.18g，60％活性)、DS-4(4.13g，22.5％溶液)、4-羟基TEMPO(0.2g，5％水溶液)、丙烯酸正丁酯(BA，234.8g)和甲基丙烯酸烯丙酯(ALMA，15.1g)在单独的烧瓶中组合来制备注料单体乳液(注料ME)。向装有搅拌器、冷凝器和温度探针的5-L圆底烧瓶(反应器)中添加去离子水(1575g)。将反应器加热到70℃，此后将引发剂和低聚物种子混合物添加到反应器中，并在15分钟内将注料ME进料到反应器中。在30分钟的诱导期后，所得放热导致反应器温度上升到80℃。
然后在55分钟内将第一单体乳液(ME1，通过将去离子水(328.5g)、PAM-600(6.5g)、DS-4(12.4g，22.5％溶液)、4-羟基TEMPO(0.6g，5％水溶液)、BA(738.7g)和ALMA(47.2g)组合制备)进料到反应器中。在保持20分钟之后，在3分钟内将NH4OH(0.8g，28％水溶液)进料到反应器中。
将反应器温度冷却到并保持在75℃，此后将FeSO4·7H2O(11g，0.15％水溶液)和EDTA四钠盐(2g，1％水溶液)混合并加入到反应器中。通过将去离子水(90g)、DS-4(3.2g，22.5％溶液)、PAM-600(2.20g)、甲基丙烯酸甲酯(MMA，250.0g)和丙烯酸乙酯(EA，10.5g)在单独的烧瓶中组合制备第二单体乳液(ME2)。在45分钟内将ME2、叔丁基过氧化氢溶液(t-BHP，1.44g(70％水溶液)于100g水中)和异抗坏血酸(IAA，1.05g于100g水中)进料到反应器中。然后通过在20分钟内将t-BHP溶液(2.54g(70％水溶液)于40g水中)和IAA(1.28g于40g水)进料到反应器中冲洗剩余单体。所得分散体通过45-μm筛过滤；收集保留在筛上的凝胶并且干燥(655ppm)。分析滤液固体百分比(32.8％)、变异系数(<20％)，并且粒径(8.7μm，如通过DCP测量)。
中间体实例2-制备硅酮分散体1
将DOWSIL 3-3602PDMS(225.0g，运动粘度＝80,000厘沲(cSt)，在25℃下测量)，支链烷基苯磺酸的Polystep A-16-22钠盐(A-16-22，8.1g，22.0％水溶液)和去离子水(9.6g)添加到塑料杯(1L大小，其设计用于快速混合器DAC 600FVZ)。将塑料杯盖上盖并将其放置在混合器中，并且将杯以2350rpm混合2分钟。将另外的去离子水(57.4g)添加到杯子中，然后将其在混合器中再混合2分钟。分析硅酮分散体1的固体百分比(75.5％)和粒径(4.6μm，如通过Malvern粒径分析仪3000粒径分析仪测量)。
中间体实例3-制备硅酮分散体2
将DOWSIL SFD-12PDMS(225.0g，运动粘度＝4000cSt，在25℃下测量)、A-16-22(8.1g，22.0％水溶液)和去离子水(9.7g)添加到1-L塑料杯(设计用于快速混合器DAC600FVZ混合器)。将塑料杯盖上盖并将其放置在混合器中，并且将杯以2350rpm混合2分钟。将另外的去离子水(54.4g)添加到杯子中，然后将其在混合器中再混合2分钟。分析硅酮分散体2的固体百分比(75.2％)和粒径(3.3μm，如通过Malvern粒径分析仪3000粒径分析仪测量)。
中间体实例4-制备硅酮分散体3
使用快速混合器DAC 150FVZ混合器在3500rpm下混合XIAMETERTMOFX-5563流体(4g)、TERGITOLTM15-S-40表面活性剂(10g)和UCONTM75-H-90000润滑剂(4g)30秒。(XIAMETER、TERGITOL和UCON为陶氏化学公司或其附属公司的商标(The Dow ChemicalCompany or Its Affiliates)。)
将此混合物的一部分(12.6g)与α,ω-羟基封端的聚二甲基硅氧烷(35g，运动粘度＝2千万cSt)和玻璃珠(16g，3mm直径)组合。将内容物在3500rpm下混合2分钟，然后使其冷却到室温；然后重复混合2分钟。然后将水(2.5g)添加到混合物，并且将内容物在3500rpm下混合1分钟。分三份添加额外的水(19.7g)，每次添加随后在3500rpm下混合30秒；所得分散体(68％固体)的体积平均中值直径为3.5μm，如通过Malvern Masterizer 3000颗粒分析仪测量。
比较实例1-制备没有聚有机硅氧烷的漆
将RHOPLEXTMVSR-1049LOE丙烯酸乳液(194.99g)和中间体实例1丙烯酸珠粒(116.99g)在具有顶部搅拌的0.5-L容器中混合在一起2分钟，随后缓慢添加Kronos4311TiO2(131.42g)。继续混合5分钟，之后将Texanol聚结剂(5.19g)和BYK-022消泡剂(0.13g)缓慢加入到混合物。再继续混合2到3分钟，此时搅拌速度升高；然后缓慢添加ACRYSOLTMRM-2020NPR流变改性剂(14.15g)，随后在高速搅拌下添加ACRYSOLTMRM-8W流变改性剂(2.23g)和水(42.50g)；然后添加28％氨水(0.11g)，并且再继续混合5到10分钟。最终混合物为含有被着色微球体的漆。(ACRYSOL和RHOPLEX为陶氏化学公司或其附属公司的商标。)
比较实例2-制备具有水溶性聚有机硅氧烷的漆
将DOWSILTM402LS聚有机硅氧烷(0.20g)在搅拌下后添加到比较实例1配制物的一部分(70.0g)。由于此聚有机硅氧烷为水溶性的，所以未形成离散颗粒的分散体。
比较实例3-制备具有<1-微米大小的聚有机硅氧烷颗粒的漆
将ROSILKTM2000聚有机硅氧烷(0.454g，D50粒径＝0.5μm)在搅拌下后添加到比较实例1配制物的一部分(70.0g)。
实例1-制备具有>1-μm大小聚有机硅氧烷的漆
将硅酮分散体1(0.27g)在搅拌下后添加到比较实例1配制物的一部分(70.0g)。
实例2-制备具有>1-μm大小的聚有机硅氧烷的漆
将硅酮分散体2(0.27g)在搅拌下后添加到比较实例1配制物的一部分(70.0g)。
实例3-制备具有>1-μm大小的聚有机硅氧烷微球的漆
将硅酮分散体3(0.30g，～4μm)在搅拌下后添加到比较实例1配制物的一部分(70.0g)。
表1说明聚有机硅氧烷添加剂对耐磨光性的影响。添加剂是指聚有机硅氧烷添加剂。在其中使用添加剂的所有实例中，以粘结剂固体和丙烯酸珠粒计，添加剂重量百分比为1重量％。
表1-耐磨光性数据
| 漆ID | 添加剂 | Δ85°(平均) | std |
| 比较实例1 | 无 | 10.2 | 0.4 |
| 比较实例2 | DOWSIL<sup>TM</sup>402LS | 3.1 | 0.3 |
| 比较实例3 | ROSILK<sup>TM</sup>2000 | 3.6 | 0.3 |
| 实例1 | 硅酮分散体1 | 1.0 | 0.2 |
| 实例2 | 硅酮分散体2 | 0.5 | 0.0 |
| 实例3 | 硅酮分散体3 | 1.0 | 0.2 |
结果示出，在硅酮粒径>1μm的情况下，在存在硅酮分散体的情况下，耐磨光性显著改善。显著地，硅酮添加剂的分子量对耐磨光性没有任何明显的影响，表明只要粒径>1μm，各种聚硅氧烷均有效。
Claims (10)
1.一种漆组合物，其包含以下的水性分散体：
a）平均粒径在80 nm到500 nm的范围内的聚合物颗粒；
b）平均粒径在1 µm到20 µm的范围内的聚合有机交联微球；
c）平均粒径在1 µm到30 µm的范围内的聚硅氧烷颗粒；
d）流变改性剂；
e）颜料体积浓度在1到30的范围内的折射率> 1.9的不透明白色颜料，其条件是当所述不透明白色颜料的所述颜料体积浓度小于10时，以所述漆组合物的重量计，所述漆组合物包含在5重量%到20重量%固体的范围内的非白色着色剂；和
f）以所述聚合物颗粒的重量计，小于10重量%的Tg < 0℃的聚氨酯；
其中以所述漆组合物的重量计，所述聚合物颗粒和所述交联微球的浓度在10重量%到65重量%的范围内；
其中聚合物颗粒与交联微球的重量:重量比在1.1:1到20:1的范围内；以所述漆组合物的重量计，聚硅氧烷颗粒的浓度在0.05重量%到5重量%的范围内；并且以所述漆组合物的重量计，所述流变改性剂的浓度在0.1重量%到5重量%的范围内。
2.根据权利要求1所述的漆组合物，其中所述聚硅氧烷为由以下结构表示的线性聚合物：
其中每个R4独立地为C1-C30烷基、O-C1-C6烷基或H，其条件是至少一个R4为C1-C30烷基；每个R5独立地为C1-C30烷基、H或Si(R6)3；其中每个R6独立地为C1-C6烷基；并且n为4到10,000。
3.根据权利要求1所述的漆组合物，其中a）所述聚合物颗粒为Tg < 20℃的丙烯酸类聚合物颗粒；并且b）所述聚合有机交联微球包含Tg ≤ 20℃的第一级交联聚合物；和Tg > 30℃的第二级；其中所述聚合有机交联微球的中值重均粒径在2 µm到15 µm的范围内。
4.根据权利要求2所述的漆组合物，其中聚合物颗粒与交联微球的重量:重量比在1.3:1到10:1的范围内；以所述聚合物颗粒的重量计，所述聚合物颗粒包含至少30重量%的一种或多种甲基丙烯酸酯和/或丙烯酸酯单体的结构单元；其中每个R4独立地为甲基或乙基。
5.根据权利要求4所述的漆组合物，其中以所述聚合物颗粒和所述聚合有机交联微球的重量计，所述聚合物颗粒还包含0.05重量%到12重量%具有酮官能团的单体的结构单元，并且以所述聚合物颗粒和所述聚合有机交联微球的重量计，所述组合物还包含0.1重量%到小于10重量%的聚胺交联剂的二酰肼。
6.根据权利要求4所述的漆组合物，其中所述折射率> 1.9的不透明白色颜料为颜料体积浓度在12到22的范围内的TiO2；其中每个R4独立地为甲基。
7.根据权利要求3所述的漆组合物，其中至少50重量的所述交联微球的所述第一级包含丙烯酸丁酯和多烯键式不饱和非离子单体的结构单元，其中丙烯酸丁酯与所述多烯键式不饱和非离子单体的重量:重量比在99.5:0.5到90:10的范围内；其中所述第二级包含甲基丙烯酸甲酯均聚物。
8.根据权利要求2所述的漆组合物，其中所述聚合有机交联微球的平均粒径在2 µm到15 µm的范围内，其中所述聚合有机交联微球被官能化为具有以所述微球的重量计0.05重量%到5重量%的式I化合物的结构单元：
或其盐；其中R为H或CH3，其中R1和R2各自独立地为H或CH3，其条件是没有两个相邻的CR2CR1基团各自被甲基取代；每个R3独立地为直链或支链C2-C6亚烷基；m为1到10并且n为0到5，其条件是当m为1时，n为1到5；x为1或2；并且y为1或2；并且x + y = 3。
9.根据权利要求1所述的漆组合物，其中所述折射率> 1.9的不透明白色颜料为颜料体积浓度在1到10的范围内的TiO2；其中以所述漆组合物的重量计，所述漆组合物还包含在5重量%到20重量%固体的范围内的非白色着色剂以及小于15 颜料体积浓度的折射率在1.0到1.9的范围内的无机增量剂。
10.根据权利要求2所述的漆组合物，其还包括选自由以下组成的组的一种或多种添加剂：聚结剂、表面活性剂、分散剂、杀生物剂、不透明聚合物、着色剂、蜡、消泡剂和中和剂。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1944342A1 (en) * | 2006-03-15 | 2008-07-16 | Rohm and Haas Company | Aqueous compositions comprising polymeric duller particles |
| CN102108232A (zh) * | 2009-12-25 | 2011-06-29 | 罗门哈斯公司 | 不含二氧化钛的多层涂料体系 |
| CN104781352A (zh) * | 2012-09-18 | 2015-07-15 | 罗门哈斯公司 | 水性涂料组合物和由其形成的防眩光涂层 |
| CN106029716A (zh) * | 2014-02-28 | 2016-10-12 | 罗门哈斯公司 | 用于弹性体墙面和屋顶涂料的梯度聚合物组合物 |
| CN106479298A (zh) * | 2015-08-31 | 2017-03-08 | 罗门哈斯公司 | 用于皮革上衣的水性多段共聚物组合物 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2073609B (en) | 1980-04-14 | 1984-05-02 | Ici Ltd | Coating process |
| DE69120125T2 (de) * | 1990-03-28 | 1996-12-12 | Japan Synthetic Rubber Co Ltd | Polysiloxancompositpolymerpartikel |
| EP2295473B1 (en) | 2005-09-16 | 2016-12-28 | Rohm and Haas Company | Swellable particles |
| US7829626B2 (en) | 2006-03-15 | 2010-11-09 | Rohm And Haas Company | Aqueous compositions comprising polymeric duller particle |
| US7768602B2 (en) | 2007-10-16 | 2010-08-03 | Rohm And Haas Company | Light diffusing article with GRIN lenses |
| CN102952462B (zh) | 2011-08-25 | 2016-06-29 | 罗门哈斯公司 | 底涂层/透明涂层涂料 |
| CN110023426B (zh) | 2016-10-14 | 2022-09-23 | 陶氏环球技术有限责任公司 | 水性无光泽涂料组成物 |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1944342A1 (en) * | 2006-03-15 | 2008-07-16 | Rohm and Haas Company | Aqueous compositions comprising polymeric duller particles |
| CN102108232A (zh) * | 2009-12-25 | 2011-06-29 | 罗门哈斯公司 | 不含二氧化钛的多层涂料体系 |
| CN104781352A (zh) * | 2012-09-18 | 2015-07-15 | 罗门哈斯公司 | 水性涂料组合物和由其形成的防眩光涂层 |
| CN106029716A (zh) * | 2014-02-28 | 2016-10-12 | 罗门哈斯公司 | 用于弹性体墙面和屋顶涂料的梯度聚合物组合物 |
| CN106479298A (zh) * | 2015-08-31 | 2017-03-08 | 罗门哈斯公司 | 用于皮革上衣的水性多段共聚物组合物 |
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| CN112739734A (zh) | 2021-04-30 |
| EP3870617A1 (en) | 2021-09-01 |
| AU2019364355A1 (en) | 2021-05-27 |
| BR112021005400A2 (pt) | 2021-06-22 |
| KR20210087039A (ko) | 2021-07-09 |
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