CN100471918C - 氨基酸衍生物及其作为流挂控制剂的用途 - Google Patents
氨基酸衍生物及其作为流挂控制剂的用途 Download PDFInfo
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- CN100471918C CN100471918C CNB2004800192311A CN200480019231A CN100471918C CN 100471918 C CN100471918 C CN 100471918C CN B2004800192311 A CNB2004800192311 A CN B2004800192311A CN 200480019231 A CN200480019231 A CN 200480019231A CN 100471918 C CN100471918 C CN 100471918C
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- alkyl
- rheology modifiers
- polyisocyanates
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Abstract
本发明涉及流变改进剂在涂料组合物中作为流挂控制剂(SCA)的用途,所述流变改进剂通过使一种或多种多异氰酸酯与一种或多种旋光氨基酸衍生物反应得到。
Description
本发明涉及通过使一种或多种多异氰酸酯与一种或多种旋光氨基酸衍生物反应得到的流变改进剂在涂料组合物中作为流挂控制剂(SCA)的用途。
基于二异氰酸酯和氨基酸的双脲型凝胶剂在文献中已有提及。例如,L.A.Estroff和A.D.Hamilton在Angew.Chem.Int.Ed.,2000,第39卷,No.19,第3447-3450页中公开了基于直链烷基二异氰酸酯和L-谷氨酸单酯的双脲型水凝胶剂。类似地,A.J.Carr,R.Melendez,S.J.Geib和A.D.Hamilton在Tetrahedron Letters,1998,第39卷,第7447-7450页中公开了基于苯二亚甲基-1,4-二异氰酸酯和L-丙氨酸、L-苯丙氨酸和L-缬氨酸的叔丁基酯的双脲型凝胶剂。这些双脲化合物在各种有机溶剂中形成凝胶。流挂控制剂在涂料组合物中的应用也是众所周知的。例如,US 4,311,622中公开了由基料和流挂控制剂制备得到的触变涂料组合物,该流挂控制剂是二异氰酸酯和单胺或羟基单胺的反应产物。类似地,EP-A-0 261 863公开了用于油漆的流动控制剂,当用于油漆时,其为涂膜提供触变性能,并且在厚的涂层形成中,几乎不产生流挂。
JP 2003/183583公开了用于由聚酰胺、聚酯或聚氨酯组成的非水涂料的防流挂试剂,其可以通过使二聚的脂肪酸与二甲基或二乙基氨基反应获得。
US2002/082324公开了触变氨基甲醛树脂,其可通过在氨基甲醛树脂存在下,使多异氰酸酯官能化合物与单胺官能化合物反应,或相反地使单异氰酸酯官能化合物与多胺官能化合物反应,形成缠结于树脂的脲官能化合物而得到。
流变改进剂在涂料组合物中作为流挂控制剂的成功应用的需求是广泛的。优选地,流挂控制剂能够兼具在高和中等剪切应力(>5Pa)下的低粘度和在相当于非水平基材上湿涂层中由重力产生的力的剪切应力(<1Pa)下的高粘度,为了获得有效的防流挂行为和良好的水平性能,触变性质需要在在特定窗口喷涂后显示依赖于时间的粘度恢复,该性质随着溶剂水平、层厚度或基材与垂直面的角度的变化需要有利于使流挂-流平平衡稳固。当流变结构在涂料配制剂中固化时,它的稳定性必须在固化周期中保持,以便在允许最好的整体流平时保持良好的流挂控制。溶剂的量要能够允许例如通过喷涂的实施,不能在流挂控制剂存在下过分增加。此外,使用的任何流变控制剂必须具有允许长时间储存而不会发生不可逆变化的流挂性能。
除了流变性能外,光学性能(除了流挂或流平之外对涂层外观的影响)也是最重要的。这意味着当施用于薄膜时,任何流挂控制添加剂必须足够精细以至不会产生任何可见的干扰(如从薄膜中突出)。尤其对透明涂料施用而言,它还意味着在固化周期完成之后,不应存在可检测的薄雾或混浊,并且其存在不应引起色彩的形成。此外,这些性质还不应当随着储存时间发生不可逆变化。当然,为了控制成本和不干扰其他涂料性能,优选在低浓度下可发挥作用的高效流挂控制剂。
尽管已知许多流变控制剂,极少能够满足上面列出的全部需要。尤其是对应用于其中使用较低的固化温度(例如低于100℃)的涂料组合物和不包含甲醛衍生的固化剂或添加剂(例如,广泛使用的异氰酸酯-多元醇固化体系或基于丙烯酰官能树脂(通过自由基化学固化)的体系的配制剂而言,需要兼具高效的防流挂性能和优异的光学性能的良好流挂控制剂。
令人惊奇地,我们发现一类特定的脲化合物能够在宽的温度范围内传递流变性能和光学性能,这是在涂料组合物用作流挂控制剂所需要的。
因此,本发明涉及提供使一种或多种多异氰酸酯与一种或多种式(I)的旋光氨基酸、其酯和/或其盐(不是外消旋混合物)反应得到的流变改进剂在涂料组合物中作为流挂控制剂的用途,其中R1、R2和R3各自独立地选自氢和直链、环状或支化、取代或未取代、饱和或不饱和的烃基,或含杂原子基团,其中R1和R2各自不同以使碳原子C*为手性中心。以下,“氨基酸、其酯和/或其盐”也称为“氨基酸衍生物”。
特征“在涂料组合物中作为流挂控制剂的用途”是指一种制备具有理想的流挂控制性能的涂料组合物的方法,其包括掺入本发明的流变改进剂的步骤。优选地,在所述步骤中使用的流挂控制剂可通过使常规的多异氰酸酯与式(I)的旋光氨基酸酯反应得到,其中R1、R2和R3如上定义。
根据本发明的第一实施方案特别优选的SCA可通过使一种或多种旋光氨基酸衍生物与一种或多种多异氰酸酯反应而得到,所述多异氰酸酯选自在两个异氰酸酯基团之间的链中具有偶数个碳原子的取代或未取代的直链脂族多异氰酸酯(以及它们的二聚衍生物如缩脲二酮(uretdione)和相应的三聚异氰脲酸酯或缩二脲)、取代或未取代芳基、芳烷基和亚环己基多异氰酸酯。
任选地,可以在制备用作流挂控制剂的流变改进剂的反应中可存在可能影响最终产物的结晶性能的少量的一种或多种额外化合物,例如不同于流挂控制剂中主要化合物的反应性氨基酸衍生物和/或其他胺(包括多官能胺)或非常规的异氰酸酯反应物。对上述目的而言,特别优选的氨基酸衍生物是甘氨酸(Gly)、脯氨酸(Pro)和它们的酯。
多异氰酸酯的前缀“多”的使用表示在各自“多”化合物中存在至少两个提及的官能度。应当注意的是当制备多脲产物,即氨基酸酯与多异氰酸酯的反应产物时,优选制备二脲或三脲产物。
在制备多脲产物的本发明优选实施方案中,可以制备具有通式X-[脲-手性中心]n的多脲产物,X是分子的连接基团且n是[脲-手性中心]部分的数目(n是2或更大),优选其中n是2-5,更优选其中n是2或3,最优选其中n是2。
应注意在本说明书中通用术语“流变改进剂”用于表示在涂料组合物中用作流挂控制剂的合适流变改进剂。
还应注意的是,尽管使用了至少一个旋光氨基酸衍生物,所获得的最终反应产物并不必须是旋光的。最终产物可以是d-、l-和/或内消旋型。
如果式(I)的R1和/或R2是烃基,烃基优选各自独立地选自满足上述条件的直链、环状或支化,取代或未取代,饱和或不饱和,任选含杂原子的C1-C24烷基、芳基、芳烷基和链烯基,更优选选自直链或支化C1-C24烷基,甚至更优选选自直链或支化C1-C4烷基,最优选烃基是甲基或乙基。
在优选的实施方案中,R1和R2之一是氢,另一个是选自上面提及的C1-C25基团之一的烃基。如果R1和/或R2是含杂原子的C1-C25基团,其优选为醚单元的形式。任选地,R1和R2可以与它们连接的手性碳原子C*一起形成取代或未取代的含有4-8个碳原子的环,条件是所述环保持碳原子C*处的手性。
如果存在的话,R1和/或R2和上述环上的取代基优选选自烷基、芳基、烷氧基、羟基、(优选非伯)胺、羧酸、酯、膦酸、膦酸酯、酮、酮亚胺、脲烷、脲基甲酸酯、酰胺、硫醇、咪唑、吲哚、胍、烷基硫化物和脲基团,最优选选自烷基或烷氧基。
如果R3是如上定义的烃基,其优选选自直链、环状或支化,取代或未取代,饱和或不饱和,任选含杂原子的C1-C25烷基、芳基、芳烷基和链烯基;更优选地,R3选自直链或支化、取代或未取代,任选含杂原子的C1-C25烷基,甚至更优选选自直链或支化、取代或未取代的C1-C8烷基、醚和/或任选被酯化的C1-C8(聚)烷氧基,最优选选自直链C1-C4烷基,和任选烷氧基化的直链C1-C4烷氧基。如果被烷氧基化的话,优选使用乙氧基化的、丙氧基化的和/或丁氧基化的化合物。
如果存在的话,R3上的取代基优选选自单醚醇和烷氧基化化合物。在优选的实施方案中,根据本发明的流变改进剂通过使一种或多种多异氰酸酯与一种或多种式(I)的旋光氨基酸衍生物反应得到,其中氨基酸衍生物优选为自然形成的构型,选自如下化合物:
精氨酸(Arg),
天冬氨酸(Asp),
组氨酸(His),
鸟氨酸(Orn),
丝氨酸(Ser),
苏氨酸(Thr),
它们的酯衍生物和盐。
多异氰酸酯优选选自脂族、环脂族、芳亚烷基和亚芳基多异氰酸酯,更优选选自在两个异氰酸酯基团之间的链中具有偶数个碳原子的取代或未取代的直链脂族多异氰酸酯(以及它们的异氰脲酸酯、缩二脲、缩脲二酮)和取代或未取代的亚芳基、芳亚烷基和亚环己基多异氰酸酯。多异氰酸酯通常包含2-40个,优选4-8个碳原子。多异氰酸酯优选包含至多4个异氰酸酯基团,更优选至多3个异氰酸酯基团,最优选两个异氰酸酯基团。甚至更优选使用对称的脂族或亚环己基二异氰酸酯。合适的二异氰酸酯的实例优选选自四亚甲基-1,4-二异氰酸酯、六亚甲基-1,6-二异氰酸酯(HMDI)、ω,ω’-二丙醚二异氰酸酯、硫代二丙基二异氰酸酯、反式环己基-1,4-二异氰酸酯、二环己基甲烷-4,4’-二异氰酸酯、1,5-二甲基-(2,4-ω-二异氰酸酯基甲基)苯、1,5-二甲基(2,4-ω-二异氰酸酯基乙基)苯、1,3,5-三甲基(2,4-ω-二异氰酸酯基甲基)苯、1,3,5-三乙基(2,4-ω-二异氰酸酯基甲基)苯、间苯二亚甲基二异氰酸酯、对苯二亚甲基二异氰酸酯、二环己基二甲基甲烷-4,4’-二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯和二苯甲烷-4,4′-二异氰酸酯(MDI)。其他适合的多异氰酸酯优选选自基于HMDI的多异氰酸酯以及已知为“聚合MDI”的多异氰酸酯,所述基于HMDI的多异氰酸酯包括HMDI的缩合衍生物,例如缩脲二酮、缩二脲、异氰脲酸酯(三聚体)和不对称三聚体,其中许多以 N和 HDB和HDT市售。聚合MDI通常是纯的MDI和MDI的低聚物的混合物。特别优选的多异氰酸酯选自HMDI、它的异氰脲酸酯三聚体、它的缩二脲、反式环己基-1,4-二异氰酸酯、间苯二亚甲基二异氰酸酯和甲苯二异氰酸酯。最优选HMDI。
取代的多异氰酸酯通常通过直链多异氰酸酯的形成二聚体和/或三聚体的反应而形成。
本领域熟练技术人员应理解的是,还可以使用就地产生两种或更多种异氰酸酯的常规封端多异氰酸酯,只要在裂解后该封端剂不阻碍本发明的流变改进剂的形成。在本文件中,术语“多异氰酸酯”用于命名所有多异氰酸酯和产生多异氰酸酯的化合物。
应注意的是,还可以使一种或多种旋光氨基酸衍生物和一种或多种旋光(多)异氰酸酯反应。然而出于经济原因,不太优选该方法及其生产的流变改进剂。
在用于制备流变改进剂的一种或多种异氰酸酯与一种或多种氨基酸衍生物之间的反应中,优选过量使用异氰酸酯或氨基酸衍生物,而不以化学计量使用。例如,氨基酸衍生物的氨基数目与(产生的)异氰酸酯基团数目之比可以在0.7-1.5范围内。优选该比例为约0.9至1.1。
应理解的是,任何手性氨基酸衍生物的非外消旋对映体混合物可用来制备本发明的流变改进剂,条件是该混合物包含本发明的旋光氨基酸衍生物。在本说明书中,术语“对映体过量”,在下文中也称作“ee”,表示包含手性化合物的两种对映体的样品中一种对映体超出外消旋材料的量。对映体过量用百分数表示:外消旋样品,即两种对映体50:50的混合物,具有0%的ee;对映体纯的样品具有100%的ee。应注意尽管不应当使用50:50比例的两种对映体,当两种对映体的比例不是100:0时可以很好地获得理想的结果。换言之,对映体混合物的ee不应当是0%。ee优选是至少10%(也就是比例55:45),更优选至少20%(也就是比例60:40),甚至更优选至少40%(也就是比例70:30),最优选至少50%(也就是比例75:25)。
在本发明的一个实施方案中,优选使用ee为至少55%,最优选至少75%的对映体混合物,由于在此实施方案中使用仅一种对映体的显著对映体过量,即ee为至少55%,得到具有改进的流变控制性能的流变改进剂。
正如本领域熟练技术人员清楚的那样,异氰酸酯和氨基酸衍生物之间的反应可以以任何随意选择的方式通过混合反应组分进行,任选在高温下进行。优选地,反应在0-150℃,特别是20-80℃下进行。尽管通常反应组分可以任何随意选择的方式混合,但是优选将异氰酸酯加入到氨基酸衍生物中,如果需要的话,可以几步进行。任选地,反应可以在惰性溶剂存在下进行,例如丙酮、甲基异丁基酮、N-甲基吡咯烷酮、苯、甲苯、二甲苯或脂族烃如石油醚、醇和水或它们的混合物。这里,术语“惰性”表示溶剂在多脲形成过程中不产生干涉,这意味着当溶剂存在时形成的多脲的量是不存在溶剂时生成的量的至少80%。
流变改进剂的制备还可以任选在基料存在下进行。这可以通过将基料和异氰酸酯的混合物与氨基酸衍生物混合或者将异氰酸酯与基料和氨基酸衍生物的混合物混合,或者通过将基料与氨基酸衍生物的混合物和基料与NCO的混合物混合。显而易见的是,如果基料对氨基酸衍生物或者异氰酸酯呈高反应性,则不能将基料与特别敏感的那种化合物预混。术语“高反应性”是指在氨基酸衍生物和异氰酸酯混合以制备流变改进剂之前,超过30%的敏感的氨基酸衍生物或异氰酸酯与基料发生反应。混合操作可按任何方便的方式进行,其中反应物被剧烈搅拌。可以将氨基酸衍生物加入异氰酸酯中或者可以将异氰酸酯加入氨基酸衍生物中,采用其中最方便的方式。如果使用了基料且氨基酸衍生物或异氰酸酯对基料呈高反应性,优选将对基料呈较高反应性的化合物加入到基料和对基料呈较小反应性的化合物的混合物中。
在本发明的一个实施方案中,流变改进剂在最终涂料组合物的基料或固化组分中以低浓度,优选0.1-8%制备,以便于基料分散体仍可作为流体处理且可随后用于涂料组合物中,任选使用其他基料、固化组分和/或其他(常规)添加剂。当流变改进剂在基料中制备时,优选在20-80℃的温度范围内,在充分搅拌下制备。
在制备流变改进剂的另一个实施方案中,基料和其量如下所述的异氰酸酯和氨基酸衍生物混合,所述量应使在反应结束时,混合物以固体状材料获得,其可用作流变改进剂的母料,所述混合物由5-99,优选6-50,更优选7-25重量份的流变改进剂与95-1,优选94-50,更优选93-75重量份的基料所组成。任选地,可以存在其他稀释剂或助剂。最终涂料组合物中和流变改进剂母料中的基料可具有相同或不同的组成。优选的浓缩物在惰性气体气氛下、在20-80℃的温度下合适地制备,其中首先将氨基酸衍生物加入到基料材料中,在混合物被匀化后,在搅拌下将异氰酸酯缓慢加入到混合物中。
尽管不太理想,包含流变改进剂的基料组合物或固化组合物还可以在所述流变改进剂的存在下制备或者通过同时制备基料或固化化合物与流变改进剂而制备。本领域熟练技术人员将毫无问题地将流变改进剂或用于流变改进剂的原料与用于基料或固化化合物的原料混合,随后反应,形成包含流变改进剂的基料组合物或固化组合物。
如果流变改进剂不在基料或固化化合物中制备,它可以优选作为浓缩溶液与涂料组合物的一种或多种组分,优选与基料或任何其他液体组分混合,结果获得精细分散体。优选实施方案的混合物优选形成流变改进剂在液体组分如基料中的分散体,所述液体组分可以是无溶剂的、基于溶剂的或基于水的。
本发明进一步涉及包含基料和本发明的流变改进剂的涂料组合物。当流变改进剂用于配制涂料组合物时,得到的涂料组合物显示出触变性,并且可以具有不透明的、乳色的,或甚至是透明的外观,这取决于流变改进剂的分散颗粒的大小和折射率。
任选地,在本发明的任何涂料组合物中可以存在常规添加剂,例如溶剂和/或分散添加剂、颜料分散剂、染料、颜料、紫外固化添加剂、流动添加剂、其他流变控制添加剂、溶剂和固化反应加速剂,例如酸性化合物如对甲苯磺酸或其封端产物。涂料组合物可包含其他可以是基于溶剂的或者无溶剂的常规流变改进剂。在另一实施方案中,液态的其他常规流变改进剂是基于水的。
触变涂料组合物可以以任何需要的方式施用于基材上,例如通过辊涂、气动或静电喷涂、刷涂、喷洒、浇铸和浸涂。
存在流变改进剂的组合物的流变性变化的程度尤其取决于流变改进剂的比例和流变改进剂的性质和组合物的组分。通常,触变性的理想程度可以通过以基于组合物的总重量优选至少0.01%,更优选至少0.05%,甚至更优选至少0.10%,最优选至少0.15%,并且优选至多30%,更优选至多10%,甚至更优选至多3%,最优选至多1.5%的量使用流变改进剂来获得。
本发明的触变组合物可以包含极性和/或非极性溶剂。优选地,触变性不仅在室温下,而且在高温下均存在,因此本发明的流变改进剂适合在室温下和烘漆(固化)中,在2-120分钟时间内使用,例如在50-250℃,优选低于125℃,更优选低于100℃下使用。
本发明的用作流挂控制剂的流变改进剂还具有相当大的优点,它从不或者很少降低组合物,尤其是透明涂料的光泽和亮度。
流变改进剂优选用于基于异氰酸酯的涂料组合物、基于多元醇的涂料组合物、基于丙烯酰的涂料组合物、可环氧固化涂料组合物和可双重固化涂料组合物,后者还称为可混合固化涂料组合物。可双重固化涂料组合物例如是基于丙烯酰的可紫外固化体系和基于异氰酸酯的可化学固化体系的组合,其中两种可固化体系可以任意顺序固化,并且异氰酸酯可以在室温至最高140℃的温度下固化。
通过下面实施例说明本发明。
实施例1-3和对比例A
1767 VV-65 购自Akzo Nobel的丙烯酸多元醇
丙氨酸丁基酯/HDI 丙氨酸丁基酯/六亚甲基二异氰酸酯
166 SS-80 购自Akzo Nobel的聚酯多元醇
制备了四种油漆配制剂(对比配制剂A和根据本发明的配制剂1-3)(见表1)。将油漆喷涂到具有13个直径为1cm的孔的立式镀锡板上,并且按照指定的程序立式烘烤。流挂极限以发生流挂的孔和其之前的孔之间的层厚度测定。另一测定流挂的方法是测量流挂长度为1cm处的层厚度。
这些实施例表明本发明的流变改进剂作为流挂控制剂具有良好的作用,并且在透明涂料中具有优异的透明度。此外,在140℃下24分钟,在60℃下60分钟,并在室温下干燥七天后,施用于玻璃上的透明涂层完全透明。使用Hunterlab的ColorQuest分光光度计测定玻璃上的膜厚度为40微米的透明涂层的透过率(以%表示)。如果透过率值相互比较,较低透过率值意味着较多薄雾和较小的透明度。
表I
实施例4-18和对比例B-D
166 SS-80 购自Akzo Nobel的聚酯多元醇
1767 购自Akzo Nobel的丙烯酸多元醇
树脂 X 如WO02/098942的实施例3所述得到的树脂
HDT-LV 购自Rhodia的脂族多异氰酸酯
HDI-BA 六亚甲基二异氰酸酯-苄基胺
氨基酸 购自Aldrich
所有流挂控制剂在提及的主体树脂(见表II)上以基于固体相当于3.7重量%的浓度就地制备。配制涂料组合物以获得基于总的固体浓度为1.0-1.2重量%的流挂控制剂。对于所有NCO-多元醇固化配制剂而言,以1:1OH-NCO摩尔化学计量使用 HDT-LV( HDT)作为交联剂。用乙酸丁酯稀释配制剂以允许在约0.8Pas的高剪切粘度下测量它们的流变性能。所有NCO配制剂在60℃下固化30分钟; 890在室温下使用紫外光固化。
使用锥板式流变性测定仪,在受控剪切应力模式下,起始于高(1,000Pa)剪切应力来测定粘度。在膜的高的剪切应力干扰后,施用0.5Pa的剪切应力并监控其随时间变化的累积运动来测定可挠性。第一次测量得到显示平衡流变性结构的数值,第二次测量明确考虑了结构恢复的速率:低的值表示低的累积流动。
Claims (19)
2.根据权利要求1的用途,其中所述一种或多种多异氰酸酯选自在两个异氰酸酯基团之间的链中具有偶数个碳原子的取代或未取代的直链脂族多异氰酸酯,缩合的二聚体和三聚体衍生物,以及取代或未取代的亚芳基、芳亚烷基和亚环己基多异氰酸酯。
3.根据权利要求2的用途,其中所述缩合的二聚体为缩脲二酮,三聚体衍生物为异氰脲酸酯或缩二脲三聚体。
5.根据权利要求1的用途,其中若R1和/或R2是烃基,则烃基独立地选自直链、环状或支化,取代或未取代,饱和或不饱和C1-C24烷基、芳基、芳烷基和链烯基。
6.根据权利要求5的用途,其中R1和/或R2含有杂原子。
7.根据权利要求5或6的用途,其中R1和/或R2包括C1-C4烷基。
8.根据权利要求1的用途,其中若R3是烃基,则烃基选自直链、环状或支化,取代或未取代,饱和或不饱和C1-C25烷基、芳基、芳烷基和链烯基。
9.根据权利要求8的用途,其中R3含有杂原子。
10.根据权利要求8或9的用途,其中R3包括C1-C8烷基、醚和/或任选被酯化的C1-C8烷氧基或C1-C8聚烷氧基。
11.根据权利要求10的用途,其中R3包括直链C1-C4烷基和任选烷氧基化的直链C1-C4烷氧基。
12.根据权利要求1的用途,其中涂料组合物是基于异氰酸酯的涂料组合物。
13.根据权利要求1的用途,其中涂料组合物是基于丙烯酰的涂料组合物。
14.根据权利要求1的用途,其中涂料组合物是可环氧固化的涂料组合物。
15.根据权利要求1的用途,其中涂料组合物是可双固化的涂料组合物。
16.根据权利要求1的用途,其中涂料组合物是异氰酸酯反应性的二组分涂料体系,其在至少25℃且低于150℃的温度下用一种或多种多元醇化合物、硫醇化合物和/或胺官能化合物固化。
17.根据权利要求1的用途,还包括在涂料组合物的涂膜固化前将所述涂膜施用于基材上的步骤。
18.包含基料和如权利要求1-17中任一项所定义的流变改进剂的涂料组合物。
19.通过使用如权利要求1-17中任一项所定义的流变改进剂得到的涂料组合物。
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- 2004-07-08 EP EP04740876A patent/EP1641887B1/en not_active Expired - Lifetime
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- 2004-07-08 DE DE602004029466T patent/DE602004029466D1/de not_active Expired - Lifetime
- 2004-07-08 ES ES04740876T patent/ES2358404T3/es not_active Expired - Lifetime
- 2004-07-08 US US10/564,046 patent/US7851530B2/en active Active
- 2004-07-08 CN CNB2004800192311A patent/CN100471918C/zh not_active Expired - Lifetime
- 2004-07-08 JP JP2006518166A patent/JP5336043B2/ja not_active Expired - Lifetime
- 2004-07-08 PL PL04740876T patent/PL1641887T3/pl unknown
- 2004-07-08 KR KR1020067000442A patent/KR101103105B1/ko active IP Right Grant
- 2004-07-08 WO PCT/EP2004/007597 patent/WO2005005557A1/en active Application Filing
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101864055A (zh) * | 2010-06-13 | 2010-10-20 | 东南大学 | 一种旋光螺旋聚氨酯材料及其制备方法 |
CN101864055B (zh) * | 2010-06-13 | 2012-06-13 | 东南大学 | 一种旋光螺旋聚氨酯材料及其制备方法 |
CN103403052A (zh) * | 2011-02-22 | 2013-11-20 | 巴斯夫欧洲公司 | 用于可辐射固化的涂料材料的流变剂 |
CN103403052B (zh) * | 2011-02-22 | 2015-06-17 | 巴斯夫欧洲公司 | 用于可辐射固化的涂料材料的流变剂 |
Also Published As
Publication number | Publication date |
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DE602004029466D1 (de) | 2010-11-18 |
PL1641887T3 (pl) | 2011-04-29 |
US20060289828A1 (en) | 2006-12-28 |
ES2358404T3 (es) | 2011-05-10 |
JP5336043B2 (ja) | 2013-11-06 |
EP1641887A1 (en) | 2006-04-05 |
CN1816598A (zh) | 2006-08-09 |
ATE483769T1 (de) | 2010-10-15 |
BRPI0412310B1 (pt) | 2015-08-18 |
KR20060086931A (ko) | 2006-08-01 |
KR101103105B1 (ko) | 2012-01-04 |
CN1816597A (zh) | 2006-08-09 |
BRPI0412310A (pt) | 2006-08-22 |
JP2009513739A (ja) | 2009-04-02 |
WO2005005557A1 (en) | 2005-01-20 |
CN100457837C (zh) | 2009-02-04 |
EP1641887B1 (en) | 2010-10-06 |
US7851530B2 (en) | 2010-12-14 |
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