CN102341163B - 分散剂组合物 - Google Patents
分散剂组合物 Download PDFInfo
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- CN102341163B CN102341163B CN201080010121.4A CN201080010121A CN102341163B CN 102341163 B CN102341163 B CN 102341163B CN 201080010121 A CN201080010121 A CN 201080010121A CN 102341163 B CN102341163 B CN 102341163B
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Abstract
本发明涉及包含粒状固体、有机或含水介质、和具有衍生自磷酸的头基的化合物的组合物。本发明进一步涉及新的化合物,和所述化合物作为分散剂的应用。
Description
发明领域
本发明涉及包含粒状固体、有机或含水介质,和具有衍生自磷酸的头基的化合物的组合物。本发明进一步涉及新的化合物,和所述化合物作为分散剂的应用。
发明背景
在片材模塑复合物(SMC)应用中,制备分散体或糊剂,其中将填料,通常是碳酸钙或三水合氧化铝(ATH)混合到聚酯树脂中。将该糊剂倒在、铺在或喷在传送带上的载膜上,在上面加入短切的玻璃纤维。这些纤维将提供最终复合物的增强。将氧化镁粉末或糊剂连同过氧化物和其他添加剂一起加入混合物,随后加入第二载膜并且使所得混合物通过辊子以引入加入的组分。氧化镁的作用是在复合物内构建网络,由此显著并且迅速地使粘度增加至整个混合物为半固体的点。由此形成的片材复合物然后可以卷成辊(比如卷起的垫子或地毯),并且在冷冻条件下储存和运输。由此形成的SMC的最终使用者可以从辊上切下片段至所需的尺寸,将片放入一对模具中并且通过加热和由模具赋予的压力,使片材压成匹配模具对的形状并且使复合物交联形成硬的熔融部件或制品。
当加入氧化镁时,迅速发生增稠机理并且至高的程度(比如在几天内从8000毫泊到500,000毫泊),使得SMC形成与片材的成辊和储存之间的时间间隔最小化。尽管当形成原始填充的糊剂时提供良好的粘度降低和良好的润湿能力,但酸性分散剂可能对随后MgO引发的增稠或熟化阶段有不利影响,如果它们过于强酸性的话。据信高度酸性的分散剂固定在氧化镁颗粒表面,由此防止颗粒与不饱和聚酯中较少酸性的基团成键。因此可以看出具有最优化酸性水平的分散剂将表现出优于更强酸性的分散剂的显著优点。
在预制整体模塑复合物(BMC)中可以观察到这种最优化酸性的分散剂的类似加工和优点,在该复合物中冷冻和储存的材料为整体材料例如球或膏团块的形式,而不是片材或辊。
在专利文献中有许多公开了衍生自聚(C2-4-亚烷基亚胺)例如连接聚酯链的聚乙烯亚胺的聚酯胺分散剂的公开物。如US4,224,212中公开的,聚酯链可以衍生自12-羟基硬脂酸,或者如US5,700,395和US6,197,877中公开的,其可以衍生自两种或多种不同的羟基羧酸或其的内酯。这些分散剂对于常用的工业涂料,尤其是线圈涂料油漆配方中的无机颜料和填料有效。然而,它们容易使最终油漆涂料泛黄并且使最终涂料的光泽/雾度值降低。如US5,300,255中公开的包含连接磷酸酯基团的类似聚酯链的聚酯磷酸酯分散剂不容易使最终油漆涂料泛黄,但由于聚酯链与油漆配方的不相容性,因此漆膜的光泽和雾度值可能下降。聚酯胺和聚酯磷酸酯分散剂的其他缺点是它们在室温下可能在各种极性溶剂中遭受接种或结晶。因此,寻求可以使无机颜料或填料分散在有机介质例如极性有机液体中并且不会遭受上述缺点的酸性分散剂。
包含末端酸性基团的分散剂例如磷酸酯是已知的并且通常通过羟基末端的聚合物链与五氧化磷、氧氯化磷、三氯化磷和五氯化磷或聚磷酸反应制备。聚合物链通常是包含端羟基的聚酯或聚烷氧基化物链。
US专利5,151,218和5,130,463公开了一种磷酸酯及其盐分散剂,其中酯基是没有Zerewitinoff氢、包含至少一个醚氧原子(-O-)和至少一个羧酸酯基团(-COO-)和/或氨基甲酸酯基团(-NCOO-)的脂族、环脂族和/或芳族部分。所述分散剂可以用于许多涂料或热固性复合物应用。US专利5,130,463还公开了包含衍生自与聚磷酸反应的ε-己内酯的聚醚/聚酯的分散剂。所述分散剂可在极性介质例如酮和酯中使用。US专利6,562,897公开了包含衍生自与聚磷酸反应的ε-己内酯和δ-戊内酯的聚醚/聚酯的分散剂。所有三篇专利的分散剂可在极性介质例如酮和酯中使用。
US专利5,464,895和5,412,139均公开了适用于热固性组合物的聚芳基有机磷酸酯分散剂。
US专利6,051,627公开了包括衍生自与聚磷酸反应的环氧乙烷和环氧丙烷的聚醚的分散剂。所述分散剂可在极性介质例如酮、酯和水中使用。
US专利2,213,477;2,454,542;3,004,056;3,004,057;3,010,903;3,033,889;3,099,676;3,235,627;4,456,485;4,720,514;4,872,916;和5,914,072全部公开了包含与各种磷酸化试剂反应的端羟基的聚烷氧基化物。
US专利3,462,520公开了线型C8-20链聚烷氧基化物的磷酸酯的制备。其中的参考物公开了烷基化酚的乙氧基化物、支链脂族醇的乙氧基化物和C10-15原子的线型伯醇的乙氧基化物的磷酸酯的制备。所有这些组合物在含水应用中用作乳化剂、润湿剂、分散剂、清净剂等。
US5,160,725公开了甲氧基聚乙二醇磷酸酯的制备和它们作为水溶液中磁性颗粒例如氧化铁的分散剂的应用。
US6,500,917公开了由相应的二芳基或二芳烷基磷酸酯制备甲氧基聚乙二醇磷酸酯。
发明内容
本发明的发明人发现拥有可用于包含有机介质的组合物中的分散剂将是有利的。有机介质可以包括油漆和塑料(例如热固性材料)。
本发明的发明人发现拥有包含能够提供以下的至少一种的化合物的热固性(包括(i)热固性树脂,或(ii)交联或熔融的热固性塑料)组合物将是有利的:(i)利用包含末端酸性基团的化合物的分散剂性能,(ii)提供可接受的分散性,(iii)提供可接受的剪切稳定性,(iv)提供可接受的储存稳定性,和(v)提供可接受的粘度控制(增稠性能)。
在一个实施方案中,本发明提供式(1)的化合物(通常是单酯)及其盐:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R可以是C1-6(或C1-4)烃基或酰基(hydrocarbonyl,通常R可以是甲基或乙基);
m可以为4-40,或4-30;和
n可以为1或2(通常n可以为1)。
在一个实施方案中,本发明提供一种包含粒状固体、有机或含水介质,和具有衍生自式(1)的化合物及其盐的头基的化合物的组合物。所述组合物可以是分散体。该分散体可以特别适用于涂料例如油漆,和塑料。塑料可以是热固性树脂或者交联或熔融的热固性塑料。
在一个实施方案中,本发明提供一种包含粒状固体、(i)热固性树脂或(ii)交联或熔融的热固性塑料;和式(1)的化合物(通常是单酯)及其盐的组合物:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R可以是C1-6(或C1-4)烃基或酰基(通常R可以是甲基或乙基);
m可以为4-40,或4-30;和
n可以为1或2(通常n可以为1)。
[]n内的基团“RO-(CH2CH2O)m”可以具有350-1700,或350-1350,或者350-1100的数均分子量。
在一个实施方案中,本发明提供本文公开的化合物提供给热固性树脂剪切稳定性或储存稳定性的一种或两种的应用。
在一个实施方案中,本发明提供一种化合物作为热固性组合物中的分散剂的应用,其中所述化合物由式(1)及其盐表示:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R是C1-6烃基或酰基;
m为4-40;和
n为1或2。
在一个实施方案中,本发明提供一种化合物作为油漆中的分散剂的应用,其中所述化合物由式(1)及其盐表示:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R是C1-6烃基或酰基;
m为4-40;和
n为1或2。
在一个实施方案中,本发明提供一种包含粒状固体(通常是颜料或填料)、有机液体、具有衍生自式(1)化合物的头基的化合物的组合物。当本发明的组合物是油漆时,本领域技术人员将从普通公知常识知道油漆组合物还包含成膜树脂或树脂粘合剂。这类树脂的例子包括聚酰胺,例如VersamidTM和WolfamidTM,和纤维素醚例如乙基纤维素和乙基羟乙基纤维素,硝基纤维素和纤维素乙酸酯丁酸酯树脂,包括其的混合物。油漆树脂的例子包括短油醇酸/蜜胺-甲醛、聚酯/蜜胺-甲醛、热固性丙烯酸/蜜胺-甲醛、长油醇酸、聚醚多醇和多介质树脂例如丙烯酸和脲/醛。这将包括在环境温度下在所谓的2包体系中与反应性硬化剂交联的树脂,例子是羟基丙烯酸类、多醇、氨基甲酸酯和环氧化物。
发明详述
在一个实施方案中,本发明提供式(1)的化合物作为本文公开的组合物中的分散剂的应用。
本发明提供如上文公开的组合物。
R可以是甲基、乙基、丙基、丁基、戊基、己基、乙酰基、丙酰基、异丙基、异丁基,或其的混合物。
式(1)的化合物可以通过包括任选地在惰性溶剂和/或惰性气氛存在下使磷化试剂和聚亚烷基二醇单烷基醚反应的方法制备。
磷化试剂与聚亚烷基二醇单烷基醚的摩尔比可以为3∶1-1∶3,或1∶1。
反应可以在40℃-150℃,或60℃-130℃的温度下进行。为了使式(1)化合物的脱色最小化,温度可以小于125℃。
磷化试剂可以包括POCl3、P2O5、P4O10、聚磷酸,或其的混合物。
聚亚烷基二醇单烷基醚可以包括聚乙二醇单甲醚、聚乙二醇单乙醚、聚乙二醇单丙醚,或其的混合物。
合适的惰性溶剂的例子包括脂族烃例如辛烷、石油醚、轻石油、矿物精和煤油;芳烃例如苯、甲苯和二甲苯;卤代脂族烃例如三氯乙烷、四氯乙烷和芳族氯代烃例如二和三氯苯。在一个实施方案中,式(1)的化合物可以在没有惰性溶剂存在下制备。
一般而言,反应可以在惰性气氛中进行。惰性气氛可以通过周期表的任一种惰性气体提供。在一个实施方案中,惰性气体可以是氮气。
工业应用
在一个实施方案中,式(1)的化合物可以是分散剂。
在不同实施方案中,式(1)的化合物可以选自0.1-50wt%,或0.25-35wt%和0.5-30wt%的范围存在于本发明的组合物中。
存在于组合物中的粒状固体可以是在涉及的温度下基本不溶于有机介质并且被希望以细碎形式稳定在其中的任何无机固体材料。粒状固体可以为粒状材料、纤维、小板的形式或者粉末的形式,通常是吹制的粉末。在一个实施方案中,粒状固体可以是颜料。
合适的固体的例子包括用于油漆和塑料材料的颜料、增量剂、填料、发泡剂和阻燃剂;用于油基和反向乳液钻探泥浆的固体;干洗流体中的污垢和固体颗粒;金属;用于陶瓷、压电陶瓷印刷、研磨剂、电容器、燃料电池、铁磁流体、导电油墨、磁性记录介质、水处理和烃土壤修复的粒状陶瓷材料和磁性材料;无机纳米分散固体;用于复合材料的纤维例如木材、纸、玻璃、钢、碳和硼;和作为有机介质中的分散体使用的杀生物剂、农业化肥和药物。在一个实施方案中,粒状固体可以是颜料或填料。
在一个实施方案中,固体可以是有机颜料。有机颜料的例子包括偶氮色淀、金属复合颜料以及酸、碱和媒染料的色淀,和炭黑,炭黑尽管严格地无机,但其的分散性能行为更像有机颜料。
无机颜料的例子包括金属氧化物例如二氧化钛、金红石二氧化钛和表面涂覆的二氧化钛,不同颜色例如黄色和黑色的氧化钛,不同颜色例如黄色、红色、褐色和黑色的氧化铁,氧化锌,氧化锆,氧化铝,氧金属化合物例如钒酸铋、铝酸钴、锡酸钴、锌酸钴、铬酸锌,和锰、镍、钛、铬、锑、镁、钴、铁或铝的两种或多种的混合金属氧化物,普鲁士蓝,朱砂,群青,磷酸锌,硫化锌,钙和锌的钼酸盐和铬酸盐,金属效果颜料例如铝薄片、铜和铜/锌合金,珠光薄片例如碳酸铅和氧氯化铋。
无机固体包括增量剂和填料,例如研磨和沉淀碳酸钙、硫酸钙、氧化钙、草酸钙、磷酸钙、膦酸钙、硫酸钡、碳酸钡、氧化镁、氢氧化镁、天然氢氧化镁或水镁石、沉淀氢氧化镁、碳酸镁、白云石、三氢氧化铝、氢过氧化铝或勃姆石、钙和镁硅酸盐,铝硅酸盐,包括纳米粘土、高岭土,蒙脱土,包括膨润土、锂蒙脱石和皂石,云母,滑石,包括白云母、金云母、锂云母和绿泥石,白垩,合成和沉淀二氧化硅,煅制二氧化硅,金属纤维和粉末,锌,铝,玻璃纤维,难熔纤维,炭黑,包括单和多壁碳纳米管,增强和非增强炭黑,石墨,Buckminsterfullerene,金刚石,氧化铝,石英,硅胶,木粉,粉末状纸/纤维,纤维素纤维例如大麻、剑麻、亚麻、棉、黄麻、米糠、椰子纤维、香蕉叶、灰叶剑麻叶、马尼拉麻、稻草等,蛭石,沸石,水滑石,来自发电站的飞灰,灰化的污水污泥灰,火山灰,爆炸炉渣,石棉,温石棉,直闪石、青石棉,硅灰石,凹凸棒石等,粒状陶瓷材料例如氧化铝、氧化锆、氧化钛、氮化硅、氮化铝、氮化硼、碳化硅、碳化硼、混合的硅-铝氮化物和金属钛酸盐;粒状磁性材料例如过渡金属,通常是铁和铬的磁性氧化物,例如γ-Fe2O3、Fe3O4和钴掺杂的氧化铁,铁氧体例如钡铁氧体;和金属颗粒,例如金属铝、铁、镍、钴、铜、银、金、钯和铂,及其的合金。
在一个实施方案中,存在于本发明组合物中的有机介质可以是塑性材料并且在另一个实施方案中是有机液体。有机液体可以是非极性或极性有机液体。与有机液体相关的术语“极性”是指如在Crowley等在Journal of Paint Technology,Vol.38,1966,269页上的题为“A ThreeDimensional Approach to Solubility”的论文中所述,有机液体能够形成中等到强的键。如上述论文中定义,这类有机液体通常具有5或更多的氢键数。
合适的极性有机液体的例子包括胺,醚,尤其是低级烷基醚,有机酸,酯,酮,二醇,二醇醚,二醇酯,醇和酰胺。这些适度强的氢键液体的许多具体例子在Ibert Mellan的题为“Compatibility andSolubility”的书籍(于1968年由Noyes Development Corporation出版),39-40页表2.14中给出,并且这些液体全部落入本文使用的术语极性有机液体的范围。
在一个实施方案中,极性有机液体包括二烷基酮、烷烃羧酸和链烷醇的烷基酯,尤其是包含至多并且包括总计6个碳原子的这类液体。作为极性有机液体的例子,包括二烷基和环烷基酮,例如丙酮、甲乙酮、二乙基酮、二异丙基酮、甲基异丁酮、二异丁酮、甲基异戊酮、甲基正戊酮和环己酮;烷基酯例如乙酸甲酯、乙酸乙酯、乙酸异丙酯、乙酸丁酯、甲酸乙酯、丙酸甲酯、甲氧基乙酸丙酯和丁酸乙酯;二醇以及二醇酯和醚,例如乙二醇、2-乙氧基乙醇、3-甲氧基丙基丙醇、3-乙氧基丙基丙醇、2-丁氧基乙酸乙酯、3-甲氧基乙酸丙酯、3-乙氧基乙酸丙酯和2-乙氧基乙酸乙酯;链烷醇例如甲醇、乙醇、正丙醇、异丙醇、正丁醇和异丁醇(也已知为2-甲基丙-1-醇)、萜品醇以及二烷基醚和环醚例如二乙醚和四氢呋喃。在一个实施方案中,溶剂包括链烷醇、烷烃羧酸和烷烃羧酸的酯。在一个实施方案中,本发明可以适合于可以基本不溶于含水介质的有机液体。另外,本领域技术人员将知道少量极性介质(例如二醇、二醇醚、二醇酯和醇)可以存在于有机液体中,只要整个有机液体基本不溶于含水介质中。
有机液体可以是多醇,即具有两个或多个羟基的有机液体。在一个实施方案中,多醇包括α-ω二醇或α-ω二醇乙氧基化物。
在一个实施方案中,非极性有机液体包括含脂族基团、芳族基团或其的混合物的化合物。非极性有机液体包括非卤代芳烃(例如甲苯和二甲苯)、卤代芳烃(例如氯苯、二氯苯、氯甲苯)、非卤代脂族烃(例如包含6个或更多的全部和部分饱和的碳原子的线型和支化的脂族烃)、卤代脂族烃(例如二氯甲烷、四氯化碳、氯仿、三氯乙烷)和天然非极性有机物(例如植物油、葵花油、菜籽油、亚麻子油、萜烯和甘油酯)。
在一个实施方案中,基于总的有机液体,有机液体包含至少0.1重量%或1重量%或更多的极性有机液体。有机液体任选地进一步包含水。在一个实施方案中,有机液体可以不含水。
热固性树脂可以包括当加热、催化或经受紫外、激光、红外、阳离子、电子束或微波辐射时经历化学反应并且变得相对不熔的树脂。热固性树脂中的典型反应包括不饱和双键氧化,涉及环氧/胺、环氧/羰基、环氧/羟基的反应,环氧与路易斯酸或路易斯碱、多异氰酸酯/羟基、氨基树脂/羟基部分的反应,聚丙烯酸酯的自由基反应,环氧树脂和乙烯基醚的阳离子聚合,以及硅醇缩合。不饱和树脂的例子包括通过一种或多种二酸或酐与一种或多种二醇反应制备的聚酯树脂。这些树脂普遍作为与反应性单体例如苯乙烯或乙烯基甲苯的混合物提供,并且通常被称为邻苯二甲酸树脂和间苯二甲酸树脂。另一些例子包括在聚酯链中使用二环戊二烯(DCPD)作为共反应物的树脂。另一些例子还包括双酚A二缩水甘油醚与不饱和羧酸例如甲基丙烯酸的反应产物,其随后作为苯乙烯中的溶液提供,普遍称为乙烯酯树脂。
具有羟基官能度的聚合物(通常是多醇)广泛用于热固性体系中以与氨基树脂或多异氰酸酯交联。多醇包括丙烯酸多醇、醇酸多醇、聚酯多醇、聚醚多醇和聚氨酯多醇。典型的氨基树脂包括蜜胺甲醛树脂、胍胺甲醛树脂、脲醛树脂和甘脲甲醛树脂。多异氰酸酯是具有两个或多个异氰酸酯基团的树脂,包括单体脂族二异氰酸酯、单体芳族二异氰酸酯和它们的聚合物。典型的脂族二异氰酸酯包括六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和氢化二苯基甲烷二异氰酸酯。典型的芳族异氰酸酯包括甲苯二异氰酸酯和二苯基甲烷二异氰酸酯。
在一个实施方案中,热固性复合物或者交联或熔融的热固性塑料可以是聚酯树脂、于苯乙烯中的聚酯树脂、聚酯树脂与聚乙酸乙烯酯的混合物,或者聚酯树脂与聚苯乙烯聚合物的混合物。
如果希望,本发明的组合物可以包含其他组分,例如不同于本发明的化合物的分散剂、防雾剂、成核剂、发泡剂、阻燃剂、加工助剂、表面活性剂、增塑剂、热稳定剂、相容剂、UV吸收剂、抗氧剂、香料、脱模助剂、抗静电剂、抗菌剂、杀生物剂、偶联剂、润滑剂(外和内)、冲击改性剂、滑爽剂、空气释放剂和粘度抑制剂。
本组合物通常含有1-95重量%粒状固体,确切量取决于固体的性质,并且数量取决于固体的性质以及固体和极性有机液体的相对密度。例如,在一个实施方案中,其中固体可以是有机材料例如有机颜料的组合物包含15-60重量%的固体,而在一个实施方案中,其中固体可以是无机材料例如无机颜料、填料或增量剂的组合物包含40-90重量%的固体,基于组合物的总重量。
本发明的组合物可以通过已知用于制备分散体的任一种常规方法制备。因此,可以将粒状固体、热固性复合物或者交联或熔融的热固性塑料和式(1)的化合物以任何顺序混合,然后例如通过高速混合、球磨、筐研磨、珠粒研磨、砂砾研磨、砂磨、磨碎机研磨、双辊或三辊研磨、塑性研磨使混合物进行机械处理以使固体颗粒减小至合适的尺寸直到形成分散体。作为选择,可以独立地或者以与(i)热固性复合物或者交联或熔融的热固性塑料或(ii)式(1)的化合物的混合物处理粒状固体以减小其的粒径,然后加入其他组分并且搅拌混合物以提供组合物。也可以通过将干燥粒状固体与式(1)的化合物研磨并且然后加入液体介质而制备组合物。作为选择,可以通过在颜料冲洗工艺中使固体与式(1)的化合物在液体介质中混合制备组合物。
在一个实施方案中,本发明的组合物可适用于液体分散体。在一个实施方案中,该分散体组合物包含:(a)0.5-40份粒状固体,(b)0.5-30份式(1)的化合物,和(c)30-99份有机或含水介质;其中所有相对份数以重量计并且数量(a)+(b)+(c)=100。
如果需要包括干燥形式的粒状固体和式(1)化合物的组合物,则通常使有机液体挥发使得可以通过简单的分离方式例如蒸发使其从粒状固体中容易地除去。在一个实施方案中,组合物包括有机液体。
如果干燥组合物基本由式(1)的化合物和粒状固体组成,则其通常包含至少0.2%,至少0.5%或至少1.0%的式(1)的化合物,基于粒状固体的重量。在一个实施方案中,干燥组合物包含不大于100重量%,不大于50重量%,不大于20重量%或不大于10重量%的式(1)的化合物,基于粒状固体的重量。
如上所述,本发明的组合物可以适用于制备分散体,其中可以在式(1)的化合物及其盐的存在下在有机液体中研磨粒状固体。
在一个实施方案中,本发明提供一种包含粒状固体、热固性复合物或者交联或熔融的热固性塑料,和式(1)的化合物及其盐的分散体。
一般而言,基于分散体的总重量,分散体包含20-90重量%的粒状固体。在一个实施方案中,粒状固体可以不少于分散体的10重量%或不少于20重量%。
分散体中式(1)的化合物的量可以取决于粒状固体的量,但通常为分散体的0.5-5重量%。
由本发明的组合物制备的分散体可以适用于其中能量固化体系(紫外、激光、红外、阳离子、电子束、微波)用于配方中存在的单体、低聚物等或组合的含水、非含水和无溶剂配方。它们特别适用于涂料例如漆,和塑料。合适的例子包括它们在以下中的应用:低、中等和高固体漆,通常是工业漆,包括烘焙的2组分和金属涂料漆(例如线圈和罐涂料),粉末涂料,UV可固化涂料,木漆;多醇和塑料溶胶分散体;陶瓷工艺,尤其是带浇铸、凝胶浇铸、刮刀、挤出和注塑型工艺,另外的例子将是用于等静压制的干燥陶瓷粉末的制备;复合物例如片材模塑和预制整体模塑复合物,树脂传递模塑、拉挤成型、人工铺层和喷射铺层工艺、合模模塑;建筑材料比如压延树脂,个人护理比如指甲涂料,遮光剂,粘合剂,塑料和电子材料例如用于显示器,包括OLED器件、液晶显示器和电泳显示器中的色滤系统的涂料配方,玻璃涂料,包括光学纤维涂料、反射涂料或抗反射涂料,导电和磁性涂料。它们可用于颜料和填料的表面改性以改进用于上述应用的干燥粉末的分散性。涂料的另一些例子在Bodo Muller,Uirich Poth,Lackformulierung und Lackrezeptur,Lehrbuch fr Ausbildung und Praxis,Vincentz Verlag,Hanover(2003)和P.G.Garrat,Strahlenhartung,Vincentz Verlag,Hanover(1996)中给出。
在一个实施方案中,本发明的组合物进一步包括一种或多种另外已知的分散剂。
以下实施例提供本发明的解释。这些实施例不是穷举并且不意在限制本发明的范围。
实施例
比较例A(COMPA):类似于US专利6,562,897中公开的磷酸盐化分散剂的分散剂,其中聚醚-聚酯链由分子量350的甲氧基聚乙二醇与己内酯和戊内酯制备。
比较例B(COMPB):类似于US 6,051,627,其中的实施例19中公开的磷酸盐化分散剂的分散剂,除了由分子量550的甲氧基聚乙二醇和具有175数均分子量的聚丙二醇制备。
比较分散剂C(COMPC)是EP 164817的实施例4。
比较分散剂D(COMPD)是US 5,700,395的实施例12。
实施例1(EX1):将聚乙二醇单甲醚(Mn 350,得自Fluka,100份)和聚磷酸(得自Fluka,22.7份)在炉中在70℃下加热直到可倒出,然后装入150ml烧瓶。将混合物设置为在氮气氛下剧烈搅拌,然后将浸入油浴中的烧瓶加热至120℃。在该温度下继续搅拌6小时,得到黄色粘稠液体。
实施例2(EX2):将聚乙二醇单甲醚(Mn 550,得自Fluka,100份)和聚磷酸(得自Fluka,14.5份)在炉中在70℃下加热直到可倒出,然后装入150ml烧瓶。将混合物设置为在氮气氛下剧烈搅拌,然后将浸入油浴中的烧瓶加热至120℃。在该温度下继续搅拌6小时,得到黄色粘稠液体。
实施例3(EX3):将聚乙二醇单甲醚(Mn 750,得自Fluka,100份)和聚磷酸(得自Fluka,10.6份)在炉中在70℃下加热直到可倒出,然后装入150ml烧瓶。将混合物设置为在氮气氛下剧烈搅拌,然后将浸入油浴中的烧瓶加热至120℃。在该温度下继续搅拌6小时,得到黄色粘稠液体。
实施例4(EX4):将聚乙二醇单甲醚(Mn 1100,得自Fluka,100份)和聚磷酸(得自Fluka,7.23份)在炉中在70℃下加热直到可倒出,然后装入150ml烧瓶。将混合物设置为在氮气氛下剧烈搅拌,然后将浸入油浴中的烧瓶加热至120℃。在该温度下继续搅拌6小时,得到白色蜡状固体。
分散体制备(DEX1-DEX4和DCOMPA-DCOMPB):通过制备基于下表中所示的组成(提供的量以份计)的热固性复合物而制备一系列分散体。分散体DEX1-DEX4分别包含EX1-EX4的产物。同样,DCOMPA-DCOMPB分别包含COMPA和COMPB的产物。制备的分散体为:
分散体组成 | DCOMPA | DCOMPB | DEX1 | DEX2 | DEX3 | DEX4 |
PalapregTM H | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
PalapregTM P | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
MillicarbTM OG | 105.0 | 105.0 | 105.0 | 105.0 | 105.0 | 105.0 |
LuvatolTM MK25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
分散剂 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
脚注:
A-PalapregTM H是PalapregTM H880-01,其是由DSM Resins提供的改性聚乙酸乙烯酯低形态添加剂。
B-PalapregTM P是PalapregTM P18-03,其是由DSM resins提供的于苯乙烯中的不饱和聚酯树脂。
C-MillicarbTM OG是由Omya提供的具有2.7微米中值粒径的石灰石衍生的碳酸钙填料
D-LuvatolTM MK 25是由Lehmann and Voss提供的氧化镁增稠剂。
分散体制备:上述分散体通过以下步骤制备。将两种PalapregTM树脂称量到不锈钢夹套式研磨容器中。将每一试验样品加入树脂混合物并且将三种组分在DispermatTM F1高剪切混合机上在1500rpm下混合30秒。将混合速度增至3000rpm并且在1分钟内加入MillicarbTM OG。在3000rpm下再继续混合15分钟,然后停止混合机。取出小的所得分散体样品用于初始粘度测量。将LuvatolTM MK 25加入研磨容器并且在2000rpm下重新启动混合2分钟。停止混合机并且将分散体转移到储存容器中。在15分钟、1小时、1天、2天和5天后测量储存的分散体的粘度。
在TA InstrumentsTM AR500控制应力流变仪上以流动测量模式,使用40mm交叉影线不锈钢板测量每一糊剂样品。测量在25℃下进行。将样品在0.1s-1-126.5s-1的速率下剪切。得到的粘度数据(Pa s)如下:
本发明的样品通常具有比DCOMPA和DECOMPB低的粘度。这表示加工更容易,或者允许更高的填料装载量。
在加入氧化镁增稠剂后在Brookfield RV粘度计上使用No.7锭子和5rpm的速度测量储存粘度。一般而言,没有达到500,000毫泊粘度的样品试验失败。得到的粘度数据(mP)如下:
从试验获得的数据表明,本发明的组合物具有比公开的类似分散剂低的剪切,同时具有足够的增稠。
将上面制备的分散剂配制到聚酯线圈涂漆体系中。使用下面列出的配方和组分制备以下白色最终漆。
白色漆制备
将分散剂配制到聚酯线圈涂漆体系中。使用下面列出的配方和组分制备以下白色最终漆。
研磨基质组合物
涂料排出组分
总称 | 功能 | 来源 | 份 |
研磨基质 | 着色剂 | 7.14 | |
Uralac SN833 S2-55 | 聚酯树脂 | DSM | 6.60 |
Resimene 747 | MF交联剂树脂 | Cytec | 1.07 |
二元酯(DBE) | 溶剂 | Aldrich | 1.32 |
Dowanol PMA | 溶剂 | Dow | 1.72 |
总的漆重量 | 17.85 | ||
最终颜料% | 30 |
将Solvesso 100和DBE加入125g玻璃罐。然后将分散剂连同Uralac聚酯树脂和Modaflow III一起加入。然后加入120g 3mm玻璃珠,随后是Tipure R960颜料。将罐密封并且在Skandex 1au上研磨混合物90分钟。将白色漆通过400微米筛网筛分以除去玻璃珠,并且使其冷却至室温。在Bohlin V88粘度计上在20℃测量研磨基质粘度(单位Pa s)。将额外量的Solvesso 100(5份)加入研磨基质。然后,通过彻底混合在上表的排出部分公开的材料制备最终漆。使用自动K-涂覆机(Sheen)和No.6K-棒(Sheen)将最终漆涂覆在Leneta黑白拉伸金属板上,得到60μ的膜厚。使涂料图案在230℃固化45秒并且然后使其冷却。
拉伸测试
在固化阶段后使用Byk-Gardner光泽和雾度计测量光泽和雾度测量值。在Macbeth Colour Eye上测量色值和Berger白度。得到的结果是:
表:各个剪切速率下研磨基质的粘度
表:涂料性能
分散剂 | 60′光泽 | 20′光泽 | 雾度 | Berger白度 |
COMBP | 89.7 | 56.3 | 193 | 91.73 |
COMPC | 67.8 | 29.6 | 413 | 88.59 |
COMPD | 85.6 | 59.5 | 240 | 75.72 |
EX1 | 93.6 | 68.0 | 181 | 90.24 |
EX2 | 101.0 | 87.3 | 94.2 | 92.74 |
希望拥有低粘度研磨基质以制备具有高白度值和不透明度的高光泽、低雾度漆。这表明优良的分散和与有机介质好的相容性。显然,与非本发明的现有技术的类似分散剂例子B相比,根据本发明使用的分散剂表现出较高的光泽、较低的雾度和相当的白度值和粘度。当与非本发明的现有技术的类似分散剂C相比时,本发明的分散剂表现出较低的粘度、较高的光泽、较低的雾度和较高的白度和不透明度结果。当与非本发明的现有技术的类似分散剂例子D相比时,本发明的分散剂表现出较高的光泽、较低的雾度、高得多的白度值和较高的不透明度。
上面提及的每篇文献在此引入作为参考。除了在实施例中或者另外明确说明,本说明书中指定材料的量、反应条件、分子量、碳原子数等的所有数值量将被理解为由词语“约”修饰。除非另外说明,本文提及的每一化学物质或组合物应该被解释为可以包含异构体、副产物、衍生物和通常被理解为以商业等级存在的其他这类材料的商业等级材料。然而,每一化学组分的量表示为不包括可能常规地存在于商业材料中的任何溶剂或稀释剂油,除非另外说明。将理解本文所述的上限和下限量、范围和比例范围可以独立地合并。类似地,用于本发明的每一要素的范围和量可与用于任何其他要素的范围或量一起使用。
尽管已经相对于其的优选实施方案解释了本发明,但将理解的是当阅读说明书时,其的各个改进将变得对于本领域那些技术人员而言显而易见。因此,将理解本文公开的发明意在覆盖落入附属的权利要求范围内的这些改进。
Claims (12)
1.组合物,包含:粒状固体、有机或含水介质、和具有衍生自式(1)的化合物及其盐的头基的化合物:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R是C1-6烃基或酰基;
m为4-40;和
n为1或2,
其中粒状固体是颜料或填料。
2.权利要求1的组合物,其中[]n内的基团RO-(CH2CH2O)m具有350-1700,或350-1350,或者350-1100的数均分子量。
3.权利要求1的组合物,其中所述化合物以选自组合物的0.25-35wt%和0.5-30wt%的范围存在。
4.权利要求1的组合物,其中式(1)的化合物是单酯。
5.权利要求1的组合物,其中R是甲基或乙基。
6.任一项前述权利要求1-5的组合物,其中所述组合物是分散体。
7.权利要求6的组合物,其中分散体用于涂料和塑料。
8.权利要求7的组合物,其中涂料包括漆。
9.权利要求7的组合物,其中塑料是热固性树脂或者交联或熔融的热固性塑料。
10.权利要求9的组合物,其中所述组合物包含粒状固体、(i)热固性树脂或(ii)交联或熔融的热固性塑料;和式(1)的化合物及其盐:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R是C1-6烃基或酰基;
m为4-40;和
n为1或2。
11.化合物作为热固性组合物中的分散剂的应用,其中所述化合物由式(1)及其盐表示:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R是C1-6烃基或酰基;
m为4-40;和
n为1或2。
12.化合物作为漆中的分散剂的应用,其中所述化合物由式(1)及其盐表示:
[RO-(CH2CH2O)m]n-P(=O)(OH)3-n
式(1)
其中
R是C1-6烃基或酰基;
m为4-40;和
n为1或2。
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JP6277719B2 (ja) * | 2013-01-09 | 2018-02-14 | 日油株式会社 | 非水系分散剤、および非水系分散体組成物 |
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- 2010-02-23 WO PCT/US2010/025042 patent/WO2010101737A1/en active Application Filing
- 2010-02-23 JP JP2011552976A patent/JP5964051B2/ja active Active
- 2010-02-23 US US13/254,037 patent/US8703850B2/en active Active
- 2010-02-23 ES ES10705522.0T patent/ES2528729T3/es active Active
- 2010-03-02 TW TW099105897A patent/TWI526451B/zh active
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US6500917B1 (en) * | 1997-07-25 | 2002-12-31 | Amersham Health As | Process for the preparation of polyether phosphates |
US7208554B2 (en) * | 2004-04-07 | 2007-04-24 | Rhodia Inc. | Polyoxyalkylene phosphonates and improved process for their synthesis |
CN101213620A (zh) * | 2005-06-30 | 2008-07-02 | 巴斯福股份公司 | 磁流变液 |
CN101100507A (zh) * | 2006-07-07 | 2008-01-09 | 戈尔德施米特股份公司 | 用作乳化剂及分散剂的磷酸酯 |
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BRPI1009763A2 (pt) | 2016-03-15 |
EP2403634B1 (en) | 2015-01-14 |
TWI526451B (zh) | 2016-03-21 |
US20110319538A1 (en) | 2011-12-29 |
TW201036987A (en) | 2010-10-16 |
EP2403634A1 (en) | 2012-01-11 |
KR20110124353A (ko) | 2011-11-16 |
US8703850B2 (en) | 2014-04-22 |
WO2010101737A1 (en) | 2010-09-10 |
ES2528729T3 (es) | 2015-02-12 |
JP2012519583A (ja) | 2012-08-30 |
CN102341163A (zh) | 2012-02-01 |
JP2014132093A (ja) | 2014-07-17 |
JP2015221912A (ja) | 2015-12-10 |
JP5964051B2 (ja) | 2016-08-03 |
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