CN103748181A - 作为水性分散性涂料的除气的润湿剂和分散剂的支化聚亚烷基二醇醚 - Google Patents
作为水性分散性涂料的除气的润湿剂和分散剂的支化聚亚烷基二醇醚 Download PDFInfo
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- CN103748181A CN103748181A CN201280004209.4A CN201280004209A CN103748181A CN 103748181 A CN103748181 A CN 103748181A CN 201280004209 A CN201280004209 A CN 201280004209A CN 103748181 A CN103748181 A CN 103748181A
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- paint
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Abstract
本发明的主题是分散性涂料,其包含水和(A)至少一种聚合物分散体,所述聚合物分散体包含烯属不饱和烯烃单体的均聚物或共聚物,(B)至少一种无机白色颜料或无机填料,(C)至少一种有机彩色颜料或炭黑颜料,(D)至少一种式(I)化合物,其中,A为由具有至少3个活性氢原子的多元的醇或烷醇胺所衍生的基团,R为甲基或乙基,R’为氢原子或甲基、乙基、丙基或丁基,n为1至250的整数,m为1至500的整数,x为小于或等于衍生成A的多元的醇或烷醇胺中的活性氢原子的数目,并且其中聚氧亚乙基和聚氧亚烷基以相应于式(I)中所示的顺序呈嵌段地排列。
Description
本发明的主题是水性分散性涂料,所述涂料包含作为除气的润湿剂和分散剂的支化聚亚烷基二醇醚,以及支化聚亚烷基二醇醚作为水性分散性涂料的除气的润湿剂和分散剂的用途。
水性分散性涂料包含聚合物分散体(也被称为胶结材、胶乳或聚合物乳液);无机白色颜料和填料、以及助剂如润湿剂和分散剂;流变添加剂;消泡剂;防腐剂;杀真菌剂;杀藻剂;成膜助剂;溶剂和缓冲物质。在水性分散性涂料的调色时,将颜料制剂以体积或重量的方式来计量并且均匀地分散到分散性涂料中。所述分散可以用手搅拌来进行或者借助电子搅拌器进行或者在涂料混合装置例如振动机中进行或者在振动台(也被称为墨水振动器或涂料振动器)上进行。
在用包含有机颜料或炭黑颜料的颜料制剂调色时,经常出现条纹和由于色调差异不一致的颜色构成。有机颜料在涂料中且在干燥过程中絮凝,使得色强度降低。在刷涂或辊涂时,再次发生颜料聚集,但是是不同程度的,使得发生观察到的色调差异。在实验室,于擦去(Rubout)测试中模拟该现象。所述擦去测试描述于文献US-3840383中。
为了避免色调差异和擦去,向分散性涂料中添加合适的润湿剂。
US-2006/207476描述了胶乳相容的表面活性剂,所述表面活性剂选自壬基酚醚磷酸酯、壬基酚乙氧基化物、烷基聚乙二醇醚、二壬基磺基琥珀酸酯、二官能化的氧化丙烯/氧化乙烯嵌段聚合物(具有仲OH-基团)、仲醇乙氧基化物等,具有40摩尔的氧化乙烯的氢化蓖麻油乙氧基化物、和用于通用色浆的分散剂,所述色浆作为调色浆不仅可以用于水性分散性涂料而且还可以用于含溶剂的醇酸漆。
US-2008/110368描述了由颜料粉末和非离子表面活性剂构成的涂料制剂,所述表面活性剂选自乙炔表面活性剂、烷基酚乙氧基化物、氧化乙烯/氧化丙烯嵌段共聚物、醇乙氧基化物和它们的混合物。
尽管根据现有技术建议了许多化合物作为合适的润湿剂和分散剂,但是在具有有机颜料制剂的分散性涂料调色之后,在实践中总是遇到擦去的问题。
在文献中已经对于许多应用和以不同的化学组成描述了烷氧基化物。所述的烷氧基化物的主体为直链的醇烷氧基化物或线性氧化乙烯/氧化丙烯-嵌段共聚物。
DE-A-10332527描述了聚环氧化物用于避免用保护胶体稳定的水性聚合物分散体变稠的用途。
EP-A-0115926描述了水溶性聚氧丙烯/聚氧乙烯/聚氧丙烯嵌段共聚物在水性金属加工冷却润滑剂中的用途。
EP-A-1167452描述了嵌段共聚物型磷酸酯和其盐作为颜料润湿剂用于颜料糊剂,水性的含溶剂、贫溶剂和不含溶剂的漆和印刷油墨的用途。所述嵌段共聚物型磷酸酯通过烷基醇与氧化苯乙烯、氧化乙烯和任选地与另外的氧化烯烃的嵌段反应制备并随后反应成磷酸酯。
EP-A-1771520描述了醇烷氧基化物作为发泡润湿剂用于由胶结材、颜料、填料、添加剂和溶剂构成的涂料。
US-3945964描述了醇烷氧基化物作为分散剂用于水性环氧树脂分散体。
US-4091164描述了氧化乙烯/氧化丙烯-嵌段共聚物作为分散剂用于热塑性塑料中的填料和无机颜料。
US-5114607描述了氧化乙烯/氧化丙烯-嵌段共聚物作为液态金属清洁剂中的低发泡表面活性剂。
US-5500219描述了氧化乙烯/氧化丙烯-嵌段共聚物作为分散剂用于水可分散的农药颗粒。
US-6083998描述了氧化乙烯/氧化丙烯-嵌段共聚物作为消泡剂组分用于发酵工艺。
US-A-2003/144397描述了醇烷氧基化物作为乳化剂用于水性醇酸树脂涂料。
US-A-2004/254295描述了醇烷氧基化物作为乳化剂用于乳液聚合物。
US-A-2005/288389描述了氧化乙烯/氧化丙烯-嵌段共聚物作为润湿剂疏水性污渍。
WO-02/16471描述了醇烷氧基化物作为分散剂用于含溶剂的漆中的有机颜料。
具有氧化乙烯/氧化丙烯侧链的接枝聚合物和支化的烷氧基化物也在文献中描述为润湿剂和分散剂。
EP-A-1643833描述了作为渗透促进剂的烷醇烷氧基化物以及乙二胺烷氧基化物衍生物在植物保护制剂中作为结晶抑制剂或者作为乳液稳定剂。
EP-A-1650246描述了具有大于500g/mol的数均分子量的烷氧基化的环氧化物-胺加合物,其可通过单环氧化物和聚环氧化物、伯胺或仲胺和烷醇胺和氧化烯烃的反应来制备,所述加合物作为润湿剂和分散剂用于颜料制剂中的有机和无机颜料和填料。在同一篇文献中,还描述了基于烷氧基化的乙二胺的碱性聚氧化烯烃作为如现有技术的润湿剂和分散剂。
US-4540442描述了乙二胺-氧化乙烯/氧化丙烯-嵌段共聚物作为清洁组分用于水性漆去除浸蚀剂。
US-5629260描述了支化的氧化乙烯/氧化丙烯-嵌段共聚物作为润湿剂用于除草剂水溶液。
US-6028046描述了烷氧基化的聚亚胺作为抗再沉积剂用于织物洗涤剂。
US-6300304描述了烷氧基化的聚亚胺作为洗涤剂的“易去污”聚合物的。
US-A-2007/299228描述了支化的氧化乙烯/氧化丙烯-嵌段共聚物作为乳化剂用于水性醇酸分散体和水性醇酸涂料。
WO-2009/130282描述了醇烷氧基化物和支化的氧化乙烯/氧化丙烯-嵌段共聚物作为分散剂水性农药悬浮液的用途。
根据现有技术,特别推荐乙二胺-氧化乙烯/氧化丙烯-嵌段共聚物作为润湿剂用于分散性涂料。推荐具有27-30℃的浊点的乙二胺-氧化乙烯/氧化丙烯-嵌段共聚物(所述浊点以5g,在25cm325%的二乙二醇丁醚水溶液中测量)作为润湿剂和颜色增强改进剂用于水性涂料的有机颜料和炭黑。乙二胺-氧化乙烯/氧化丙烯-嵌段共聚物的不利之处在于深的颜色和氨味。
现在发现,式(I)化合物增强了用有机彩色颜料和炭黑颜料调色的分散性涂料的色强度并防止擦去。式(I)化合物在不影响分散性涂料的流变性质的情况下改进了分散性涂料的润湿能力,并且它们在制备涂料时起消泡和除气的作用。
因此本发明的目的在于找到适合的化合物,将所述化合物添加到分散性涂料中,以避免所述的擦去问题并且不显示负面的副作用。
令人惊讶地发现,式(I)的支化的烷氧基化物实现了该目的。
因此,本发明的主题是分散性涂料,其包含水和
(A)至少一种聚合物分散体,所述聚合物分散体包含烯属不饱和单体的均聚物或共聚物,
(B)至少一种无机白色颜料或无机填料,
(C)至少一种有机彩色颜料或炭黑颜料,
(D)至少一种式(I)化合物
其中,
A为由具有至少3个活性氢原子的多元的醇或烷醇胺所衍生的基团,
R为甲基或乙基,
R’为氢原子或甲基、乙基、丙基或丁基,
n为1至250,优选5至100,且特别优选10至50的整数,
m为1至500,优选10至200,且特别优选20至100的整数,
x为小于或等于衍生成A的多元的醇或烷醇胺中的活性氢原子的数目,
并且其中聚氧亚乙基和聚氧亚烷基以相应于式I所示的顺序呈嵌段地排列。
本发明的另一个主题是式(I)化合物作为上述分散性涂料中的除气的润湿剂和分散剂的用途。
本发明的又一个主题是通过向分散性涂料中添加至少一种式(I)化合物来对上述分散性涂料除气的方法。
为了本发明的目的,根据US-3840383所述的测试来测定擦去。
在一个优选的实施方案中,根据本发明的分散性涂料还包含
(E)常规的对于分散性涂料所使用的助剂,所述助剂选自润湿剂;分散剂;消泡剂;流变添加剂;杀生物剂;杀真菌剂;杀藻剂;成膜助剂;缓冲物质,如氢氧化钠溶液;氨溶液;胺,如2-氨基-2-甲基-1-丙醇;酸,如硫酸、盐酸和乙酸。
在另一个优选的实施方案中,根据本发明的分散性涂料还包含
(F)另外的添加剂,所述添加剂选自无机彩色颜料、硅树脂、钾水玻璃或醇酸树脂分散体。
基于不饱和单体的聚合物分散体适合作为组分(A)。优选的烯属不饱和单体例如是
-乙烯基单体,如乙烯醇的羧酸酯,例如乙酸乙烯酯、丙酸乙烯酯、异壬酸的乙烯醚或异癸酸的乙烯醚,
-芳基取代的烯烃,如苯乙烯和茋,
-烯属不饱和羧酸酯,如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸2-乙基己酯、丙烯酸羟乙酯以及相应的甲基丙烯酸酯,
-烯属不饱和二羧酸酯,如马来酸二甲酯、马来酸二乙酯、马来酸二丙酯、马来酸二丁酯、马来酸二戊酯、马来酸二己酯和马来酸二(2-乙基己基)酯,
-烯属不饱和羧酸和二羧酸,如丙烯酸、甲基丙烯酸、衣康酸、马来酸和富马酸以及它们的钠盐、钾盐和铵盐,
-烯属不饱和磺酸和膦酸以及它们的碱金属盐和铵盐,如丙烯酰氨基甲基丙磺酸及其碱金属盐和铵盐、烷基铵盐和羟烷基铵盐、烯丙磺酸及其碱金属盐和铵盐,丙烯酰氧乙基膦酸及其铵盐和碱金属盐以及相应的甲基丙烯酸衍生物,
-烯属不饱和胺、铵盐、腈和酰胺,如二甲基氨基乙基丙烯酸酯、丙烯酰氧乙基三甲基卤化铵、丙烯腈、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-丙基丙烯酰胺、N-羟甲基丙烯酰胺以及相应的甲基丙烯酸衍生物和乙烯基甲基乙酰胺。
在一个优选的实施方案中,将用于制备聚合物分散体的上述单体与其它共聚单体聚合聚合,所述共聚单体优选为具有2至8个碳原子的卤代烯烃或烯烃,如乙烯、丙烯、丁烯、戊烯、1,3-丁二烯、氯丁二烯、氯乙烯、偏二氯乙烯、偏二氟乙烯和四氟乙烯。
适合作为组分(B)的是无机白色颜料和填料,例如二氧化钛、碳酸钙、滑石、高岭土、硫酸钡、硫化锌、氧化锌。优选地,还使用所述无机白色颜料的混合物。一种特别优选的无机白色颜料混合物包含二氧化钛、碳酸钙、滑石和高岭土。
作为组分(C),考虑单偶氮颜料、双偶氮颜料、色淀偶氮颜料、β-萘酚和萘酚AS颜料、苯并咪唑啉酮颜料、双偶氮缩合物颜料、偶氮金属络合物颜料和多环的颜料,如酞菁颜料、喹吖啶酮颜料、芘颜料、芘酮(Perinon)颜料、硫靛颜料、蒽嵌蒽二酮颜料、蒽醌颜料、黄烷士酮颜料、阴丹酮颜料、异紫蒽酮颜料、皮蒽酮颜料、二噁嗪颜料、喹酞酮(Chinophthalon)酮颜料、异吲哚酮颜料、异二氢吲哚颜料和二酮吡咯并吡咯颜料或炭黑。
在此,作为示例性选择的特别优选的有机彩色颜料为炭黑颜料,如气黑或炉黑;单偶氮颜料和双偶氮颜料,尤其是染料索引颜料:颜料黄1、颜料黄3、颜料黄12、颜料黄13、颜料黄14、颜料黄16、颜料黄17、颜料黄73、颜料黄74、颜料黄81、颜料黄83、颜料黄87、颜料黄97、颜料黄111、颜料黄126、颜料黄127、颜料黄128、颜料黄155、颜料黄174、颜料黄176、颜料黄191、颜料黄213、颜料黄214、颜料黄219、颜料红38、颜料红144、颜料红214、颜料红242、颜料红262、颜料红266、颜料红269、颜料红274、颜料橙13、颜料橙34或颜料棕41;β-萘酚和萘酚AS颜料,尤其是染料索引的颜料:颜料红2、颜料红3、颜料红4、颜料红5、颜料红9、颜料红12、颜料红14、颜料红53:1、颜料红112、颜料红146、颜料红147、颜料红170、颜料红184、颜料红187、颜料红188、颜料红210、颜料红247、颜料红253、颜料红256、颜料橙5、颜料橙38或颜料棕1;色淀偶氮颜料和金属络合物颜料,尤其是染料索引颜料:颜料红48:2、颜料红48:3、颜料红48:4、颜料红57:1、颜料红257、颜料橙68或颜料橙70;苯并咪唑啉酮颜料,尤其是染料索引颜料:颜料黄120、颜料黄151、颜料黄154、颜料黄175、颜料黄180、颜料黄181、颜料黄194、颜料红175、颜料红176、颜料红185、颜料红208、颜料紫32、颜料橙36、颜料橙62、颜料橙72或颜料棕25;异吲哚酮颜料和异二氢吲哚颜料,尤其是染料索引颜料:颜料黄139或颜料黄173;酞菁颜料,尤其是染料索引颜料:颜料蓝15、颜料蓝15:1、颜料蓝15:2、颜料蓝15:3、颜料蓝15:4、颜料蓝15:6、颜料蓝16、颜料绿7或颜料绿36;蒽嵌蒽二酮颜料、蒽醌颜料、喹吖啶酮颜料、二噁嗪颜料、阴丹酮颜料、芘颜料、芘酮(Perinon)颜料、硫靛颜料,尤其是染料索引颜料:颜料黄196、颜料红122、颜料红149、颜料红168、颜料红177、颜料红179、颜料红181、颜料红207、颜料红209、颜料红263、颜料蓝60、颜料紫19、颜料紫23或颜料橙43;三芳基碳鎓颜料,尤其是染料索引颜料:颜料红169、颜料蓝56或颜料蓝61;二酮吡咯并吡咯颜料,尤其是染料索引颜料:颜料红254、颜料红255、颜料红264、颜料红270、颜料红272、颜料橙71、颜料橙73、颜料橙81。
组分(D)是多元的醇或烷醇胺的支化烷氧基化产物。在式(I)中,A表示由多元的醇或醇胺衍生的基团。术语“衍生”理解为形式上夺取能够烷氧基化的氢原子。优选的衍生成A的多元醇为甘油、丁三醇、己三醇、三羟甲基丙烷、季戊四醇、木糖醇、糖醇(Alditole)如甘露醇、异麦芽糖醇、乳糖醇、山梨糖醇、木糖醇、苏糖醇和赤藓糖醇。通常,多元醇具有如它所包含的OH-基团那么多的能够烷氧基化的氢原子。
在本发明的又一个优选的实施方案中,A由烷醇胺如乙醇胺、二乙醇胺和三乙醇胺衍生。通常,烷醇胺具有如它所包含的OH-基团和NH-基团那么多的能够烷氧基化的氢原子,以及如它所包含的OH-基团和NH2-基团两倍那么多的能够烷氧基化的氢原子。能够用于烷氧基化的氢原子在此也称为活性氢原子。
A优选地包含最多至8个活性氢原子,尤其是4至6个活性氢原子。x优选地等于A中的活性氢原子数。在另一个优选的实施方案中,x等于3、4、5或6。
组分(E)为常规的对于分散性涂料所使用的助剂,如润湿剂;分散剂;消泡剂;流变添加剂;杀生物剂;杀真菌剂;杀藻剂;缓冲物质,如氢氧化钠溶液;氨溶液;胺,如2-氨基-2-甲基-1-丙醇;酸,如硫酸、盐酸和乙酸。
作为润湿剂和分散剂,合适的是非离子型表面活性剂,所述非离子表面活性剂选自以下类别:烷基聚乙二醇醚;脂肪酸乙氧基化物;烷基聚糖苷;脱水山梨醇酯乙氧基化物;炔基二醇乙氧基化物;氧化乙烯和氧化丙烯-嵌段共聚物以及氧化乙烯和氧化丙烯加成到醇上的加成产物;甲基端基封闭的、丁基端基封闭的和苄基端基封闭的醇乙氧基化物和烷基酚乙氧基化物。此外,例如使用阴离子型表面活性剂类别的润湿剂和分散剂,所述阴离子型表面活性剂选自脂肪酸的钠盐、钾盐和铵盐;烷基苯磺酸钠、烷基磺酸钠、烯烃磺酸钠、聚萘磺酸钠、二烷基二苯基醚二磺酸钠;烷基硫酸钠、烷基硫酸钾和烷基硫酸铵;烷基聚乙二醇醚硫酸钠、烷基聚乙二醇醚硫酸钾和烷基聚乙二醇醚硫酸铵;烷基酚聚乙二醇醚硫酸钠、烷基酚聚乙二醇醚硫酸钾和烷基酚聚乙二醇醚硫酸铵;单烷基磺基琥珀酸钠、单烷基磺基琥珀酸钾和单烷基磺基琥珀酸铵,二烷基磺基琥珀酸钠、二烷基磺基琥珀酸钾和二烷基磺基琥珀酸铵,和单烷基聚氧乙基磺基琥珀酸钠、单烷基聚氧乙基磺基琥珀酸钾和单烷基聚氧乙基磺基琥珀酸铵;以及烷基聚乙二醇醚磷酸单酯、烷基聚乙二醇醚磷酸二酯和烷基聚乙二醇醚磷酸三酯和它们的混合物,以及其钠盐、钾盐和铵盐。
作为用于无机颜料和填料的分散剂,使用丙烯酸、甲基丙烯酸、马来酸、富马酸和丙烯酸酯和甲基丙烯酸酯及其钠盐、钾盐和铵盐。
适合作为消泡剂的是矿物油消泡剂、有机硅消泡剂或基于聚亚烷基二醇醚的消泡剂。所述的消泡剂类别的消泡组分是疏水性的固体颗粒,如疏水改性的二氧化硅;二价和三价阳离子的脂肪酸盐,如硬脂酸铝和硬脂酸钙;酰胺蜡,如亚乙基双硬脂基酰胺和硅树脂。
常规的流变添加剂为膨润土、二氧化硅、纤维素醚、疏水性改性的聚氨酯和碱溶性丙烯酸酯增稠剂。
根据本发明的分散性涂料通常包含防腐剂,用以防止微生物的侵害。常规的防腐剂为甲醛和释放甲醛的化合物,如二羟基-2,5-二噁烷、氯甲基异噻唑啉酮、苄基异噻唑啉酮、苯并咪唑啉酮和溴硝丙二醇。为了防止真菌和藻类的侵害,尤其是在将分散性涂料涂覆到外壁、房屋立面、屋顶板和金属部件和塑料部件,如外部区域的雨水槽之后,可以向分散性涂料中添加膜防腐剂。作为膜防腐剂,合适的是例如敌草隆、多菌灵、辛基异噻唑啉酮、二氯辛基异噻唑啉酮、吡啶硫酮锌、特丁净和Irgarol。
作为成膜助剂,使用将最低成膜温度降低至5℃以下的物质,例如涂料溶剂油、甲基丙二醇、甲基二丙二醇、甲基三丙二醇、乙二醇丁醚、二乙二醇丁醚、二丙二醇丁醚和三丙二醇丁醚、二乙二醇苯甲酸酯、三甲基戊烷-1,3-二醇单异丁酸酯、苯甲酸异癸酯、苯甲酸异壬酯、单乙二醇和单丙二醇单油酸酯和具有6至30个碳原子的醇的乳酸酯。
对于根据本发明的分散性涂料而言,作为缓冲物质,使用酸和碱,如氢氧化钠溶液;氨溶液;胺,如2-氨基-2-甲基-1-丙醇、三乙醇胺、二甲基氨基乙醇,以及酸,如硫酸、盐酸、乙酸和甲酸。
根据本发明的分散性涂料可以任选地添加另外的组分(F)。分散性涂料还可以任选地添加无机彩色颜料,以用由有机和无机颜料构成的混合物来提供期望的色调。
合适的无机彩色颜料为氧化铁、磁铁矿、氧化铁锰、氧化铬、群青、镍或铬锑钛氧化物、锰钛金红石、氧化钴、钴和铝的混合氧化物、金红石混合相的颜料、稀土硫化物、钴与镍和锌的尖晶石、基于铁和铬与铜的尖晶石、锌和锰、钒酸铋以及惰性颜料。尤其使用染料索引的颜料:颜料黄184、颜料黄53、颜料黄42、颜料棕24、颜料红101、颜料蓝28、颜料蓝36、颜料绿50、颜料绿17、颜料黑11和颜料黑33。
此外,根据本发明的分散性涂料可以包含其它成膜组分,如硅树脂、钾水玻璃或醇酸树脂分散体。
根据本发明的分散性涂料包含
优选为1至75重量%的(A),尤其是5至50重量%的(A),
优选为1至70重量%的(B),尤其是2至50重量%的(B),
优选为0.1至10重量%的(C),尤其是0.2至5重量%的(C),
优选为0.05至2重量%的(D),尤其是0.1至0.5重量%的(D),
优选为0.01至10重量%的(E),尤其是0.1至2重量%的(E)和
优选为1至70重量%的(F),尤其是2至50重量%的(F)。
优选地,根据本发明的分散性涂料含有至少20重量%,尤其是20至80重量%,特别是添加至100重量%的量的水。
实施例
根据本发明的分散性涂料以常规的方式制备,通过首先将白色颜料与填料分散,并且随后计量添加聚合物分散体。然后将制备的白色分散性涂料与一种或多种颜料制剂调色成希望的色调。
白色分散性涂料的制备
表1:白色分散性涂料的配制
首先预置组分1-5,且随后用溶解皿与组分6和7在高搅拌速率下分散成颜料分散体(实验室溶解器,3000转/分钟)。随后在缓慢搅拌下添加组分8-11,因为所使用的胶结材可能易受剪切的影响(实验室溶解器,500转/分钟)。
使用以下物质作为润湿剂。
表2:根据本发明分散性涂料的润湿剂和对比实施例
根据实施例8、9和10的润湿剂为嵌段烷氧基化物。
白色分散性涂料的空气含量
白色分散性涂料的表面活性物质如润湿剂和分散剂以及所使用的胶结材的乳化剂可能倾向于起泡,这可能妨碍和延长制备过程。由于白色分散性涂料的相对高的粘度,因此气泡包含在分散性涂料中,使其不能再逸出。为了避免气泡形成而使用消泡剂,所述消泡剂的浓度与表面活性化合物的起泡倾向有关。因此有利的是,所使用的润湿剂和分散剂是低起泡的物质或者甚至起到消泡的作用。因此,所制备的分散性涂料的密度采用Elcometer Ltd.Manchester公司的Pyknometer来测定。分散性涂料的密度越高,空气包裹物就越少。
白色分散性涂料的粘度
为了调节流变性质,向根据本发明的分散性涂料中添加流变添加剂,例如纤维素醚、聚氨酯增稠剂和丙烯酸酯增稠剂。在流变添加剂与润湿剂之间,特别是与聚氨酯增稠剂可以出现相互作用,使得粘度在添加润湿剂时可以降低。因此有利的是,所使用的润湿剂不降低分散性涂料的粘度。白色分散性涂料的粘度在1天后采用Brookfield粘度计,4号转子在100转/分钟下测定。白色分散性涂料应当在添加润湿剂之后没有明显改变。
白色分散性涂料的表面张力
如测量白色分散性涂料的润湿作用那样来测量表面张力。为此,将白色分散性涂料用水以重量比1:1来稀释,并且用Lauda张力计来测定表面张力,依据ASTM D971根据铂环法来进行。所使用的润湿剂的作用显示出表面张力的降低。经稀释的白色分散性涂料的表面张力越低,所使用的产品的润湿作用越有效。
分散性涂料的调色
为了调整确定的色调,向白色分散性涂料添加调色浆。为了测试调色浆的色强度和相容性,将200g由98重量%白色分散性涂料与2重量%的蓝色颜料糊剂组成的经调色的分散性涂料装入金属罐中,并在Olbrich Know How,Hemer公司的Inkshaker500中均质化60秒。所使用的蓝色颜料糊剂具有以下组成。
表3:用于分散性涂料调色的蓝色颜料糊剂的组成
为了测定色浆在白色分散性涂料中的色强度和相容性,将经调色的分散性涂料在1天后在测试卡上用120μm刮刀在膜牵拉装置Erichsen GmbH,Hemer公司的509MC型上刮涂。在7分钟后,以在文献US-3840383中所述的方式在干燥的色膜上进行擦去测试。在24小时后,采用Konica-Minolta光谱仪CM3600型测定完全干燥的膜的比色分析值。
表4:分散性涂料的性质
实施例8至10的根据本发明的分散性涂料与实施例5(对比)一起相对于现有技术显示出最好的结果:来自实施例1(对比)的润湿剂明显倾向于起泡,这导致了大约1.33g/ml的降低的密度以及比实施例8至10的润湿剂更高的空气包裹物。实施例2(对比)和6(对比)的润湿剂相对于实施例8至10中的润湿剂显示出更低的润湿作用以及大约36mN/m的更高的表面张力。使用实施例3(对比)和4(对比)的润湿剂导致了比使用实施例8至10的润湿剂时更低的分散性涂料粘度。实施例5(对比)的润湿剂显示出与实施例8至10的润湿剂相当的结果,但与后者相反,其具有氨味和深的颜色,而实施例8至10的润湿剂没有氨味并显示出明亮至清澈的颜色。实施例5(对比)中的润湿剂的深色是由于使用乙二胺作为烷氧基化的起始分子而造成的。相反,实施例8至10的润湿剂是无色至黄色的且没有氨味。实施例7(对比)中的润湿剂是完全不适合的,因为色强度与实施例1(对比)相似,远不如实施例8至10的色强度。
Claims (14)
1.分散性涂料,其包含水和
(A)至少一种聚合物分散体,所述聚合物分散体包含烯属不饱和烯烃单体的均聚物或共聚物,
(B)至少一种无机白色颜料或无机填料,
(C)至少一种有机彩色颜料或炭黑颜料,
(D)至少一种式(I)化合物
其中
A为由具有至少3个活性氢原子的多元的醇或烷醇胺所衍生的基团,
R为甲基或乙基,
R’为氢原子或甲基、乙基、丙基或丁基,
n为1至250的整数,
m为1至500的整数,
x为小于或等于衍生成A的多元的醇或烷醇胺中的活性氢原子的数目,
并且其中聚氧亚乙基和聚氧亚烷基以相应于式(I)中所示的顺序呈嵌段地排列。
2.根据权利要求1的分散性涂料,其还包含0.01至10重量%的(E)常规的对于分散性涂料所使用的助剂,所述助剂选自润湿剂;分散剂;消泡剂;流变添加剂;杀生物剂;杀真菌剂;杀藻剂;成膜助剂;缓冲物质,如氢氧化钠溶液;氨溶液;胺,如2-氨基-2-甲基-1-丙醇;酸,如硫酸、盐酸和乙酸。
3.根据权利要求1和/或2的分散性涂料,其还包含1至70重量%(F)另外的添加剂,所述添加剂选自无机彩色颜料、硅树脂、钾水玻璃或醇酸树脂分散体。
4.根据权利要求1至3中一项或多项的分散性涂料,其中所述烯属不饱和单体选自乙烯基单体、芳基取代的烯烃、烯属不饱和羧酸酯、烯属不饱和二羧酸酯、烯属不饱和羧酸和二羧酸、烯属不饱和磺酸和磷酸以及碱金属盐和铵盐、烯属不饱和胺、铵盐、腈和酰胺、具有2至8个碳原子的卤代烯烃或烯烃。
5.根据权利要求1至4中一项或多项的分散性涂料,其中A包含最多至8个的活性氢原子。
6.根据权利要求1至5中一项或多项的分散性涂料,其中x等于3、4、5或6。
7.根据权利要求1至6中一项或多项的分散性涂料,其中n为5至100的整数。
8.根据权利要求1至7中一项或多项的分散性涂料,其中m为10至200的整数。
9.根据权利要求1至8中一项或多项的分散性涂料,其包含1至75重量%的(A)。
10.根据权利要求1至9中一项或多项的分散性涂料,其包含1至70重量%的(B)。
11.根据权利要求1至10中一项或多项的分散性涂料,其包含0.1至10重量%的(C)。
12.根据权利要求1至11中一项或多项的分散性涂料,其包含0.05至2重量%的(D)。
13.根据权利要求1至12中一项或多项的分散性涂料,其包含20至80重量%的水。
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ES2538097T3 (es) | 2015-06-17 |
PT2686390E (pt) | 2015-08-28 |
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