CN101675132B - 基于氨基甲酸酯的水基双层涂料体系,其用途和用其涂覆的基材 - Google Patents
基于氨基甲酸酯的水基双层涂料体系,其用途和用其涂覆的基材 Download PDFInfo
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- CN101675132B CN101675132B CN2008800147920A CN200880014792A CN101675132B CN 101675132 B CN101675132 B CN 101675132B CN 2008800147920 A CN2008800147920 A CN 2008800147920A CN 200880014792 A CN200880014792 A CN 200880014792A CN 101675132 B CN101675132 B CN 101675132B
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- urethane
- polyacrylic ester
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
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Abstract
本发明涉及用于制备基于氨基甲酸酯的水基双层涂料体系的水性清漆,其包含至少一种聚丙烯酸酯二次分散体,所述二次分散体具有聚丙烯酸酯的玻璃化转变温度Tg≥20℃,和至少一种聚丙烯酸酯-聚氨酯-复合分散体,所述二次分散体的聚丙烯酸酯部分与所述复合分散体的聚丙烯酸酯-聚氨酯部分的重量比为1∶1至4∶1,优选2∶1至3∶1,特别优选2.2 5∶1至2.75∶1,和作为固化剂的至少一种低粘度的氨基磺酸多异氰酸酯,且涉及一种用于制备水基双层涂料体系的水性底漆,其包含至少一种聚氨酯分散体、至少一种聚丙烯酸酯-聚氨酯-复合分散体和至少一种蜜胺树脂。本发明还涉及包含所述水性清漆和所述水性底漆的水基双层涂料体系,其制备方法,其用于涂覆基材的用途,以及用其涂覆的基材。
Description
本发明涉及基于氨基甲酸酯的水基双层涂料体系,用于制备这些双层涂料体系的水性底漆和水性清漆,它们的用途,以及用它们涂覆的基材。
在汽车OEM涂漆领域中,由底漆和清漆组成的双层涂料体系属于现有技术,它们一起也被称作面漆。这些涂料体系的作用是保护位于它们之下的层,并且赋予整个涂层构造以所期望的光学性能和需要的耐候性。底漆含有赋予颜色和/或赋予效果的颜料。清漆保护底漆并强化其光学效果。面漆可为含溶剂的或水性的。
基于聚氨酯的水基双涂料体系在现有技术中是已知的(BASFHandbuch Lackiertechnik,Vincentz Verlag,2002,第98~99页)。它们可以基于水性聚氨酯分散体并基于聚丙烯酸酯-聚氨酯复合树脂(Winnacker,K üchler,Chemische Technik-Prozesse und Produkte,第7卷-Industrieprodukte,Wiley VCH,2004,第662-669页)。
在此,水性聚氨酯分散体可通过将疏水聚氨酯借助外部乳化剂在水中乳化而制备。但是,还可以通过引入亲水基团,实现聚氨酯的可自分散性。在此,水分散性可例如通过羧酸酯基获得,该羧酸酯基可被胺转化为阴离子基团(阴离子聚氨酯分散体)。还可以通过使叔氨基醇与还含有自由的异氰酸酯官能团的预聚物反应,并随后用酸中和而获得水分散性(阳离子聚氨酯)。另一个可选择的方案是用水溶性长链聚醚使具有自由的异氰酸酯官能团的预聚物改性(非离子聚氨酯)。聚氨酯的水性分散体可通过各种方法制备,所述方法描述在Winnacker,Küchler,Chemische Technik-Prozesse und Produkte,第7卷-Industrieprodukte,Wiley VCH,2004。这些方法为丙酮法、预聚物 混合法和熔体分散法。
使用聚丙烯酸酯-聚氨酯复合树脂的目的在于,将所使用的这两种聚合物的有利性能组合,并且使不利的性质最小化。它们根据种类区分为单纯由不同分散体混合而产生的复合体系(共混物);其中在不同的聚合物之间至少以一定比例存在化学键的那些;和其中不同种类的聚合物形成互穿网络(IPN)的复合分散体的那些。
基于所述的聚氨酯-聚丙烯酸酯分散体的水性涂料体系是已知的,并且在漆料工业中是普遍使用的。通常聚氨酯-聚丙烯酸酯复合分散体是通过乙烯基聚合物(“聚丙烯酸酯”)在水性聚氨酯分散体中的乳液聚合而制得的。但是,也可以制备聚氨酯-聚丙烯酸酯复合分散体作为二次分散体。
术语“二次分散体”是指那些水性分散体,它们首先在均质有机介质中进行聚合,并随后在中和条件下一般在不添加外部乳化剂的情况下在水性介质中重新分散。
例如,WO-A 95/16004描述了基于低聚氨基甲酸酯-丙烯酸酯共聚物的可水稀释的漆料粘结剂。在那种情况下,使由烯属不饱和单体组成的单体混合物,在用水稀释的有机溶剂中并在分子量为750至1000的水溶性低聚氨基甲酸酯的存在下进行自由基聚合。然后,将这种二次分散体用于配制烤漆。
在DE-A 4010176中公开了氧化性干燥漆料,其中使用聚合物作为粘合剂,该粘结剂可由此获得:在有机溶剂中将烯属不饱和单体在含有可聚合的双键的聚氨酯树脂的存在下进行聚合。
在EP-A 657483中描述了水性双组分涂层材料,其由多异氰酸酯组分和作为多元醇组分的水性聚氨酯分散体组成。在此,所述多元醇组分通过将用酸基亲水化的、并且具有侧乙烯基和/或端乙烯基的不饱和聚氨酯大分子单体进行中和并分散而制得。随后,任选地在添加其他乙烯基单体之后,使这些PUR大分子单体在水相中进行自由基聚合。
最后,EP-A 742239公开了基于多异氰酸酯交联剂和水性的、羟基封端的聚氨酯预聚物/丙烯酸复合体的双组分涂料体系。这些复合聚 合物是通过如下方法获得的:使可水分散的NCO官能的氨基甲酸酯预聚物与至少一种羟基官能的丙烯酸酯单体和链烷醇胺反应生成羟基官能的氨基甲酸酯预聚物/单体混合物,并在水中分散。然后,向该分散体中添加自由基引发剂和含羟基的扩链剂,并随后通过加热该水性反应混合物,不仅进行并完成了丙烯酸酯单体的自由基聚合,而且进行并完成了聚氨酯的扩链步骤。然后,通过在搅拌下加入亲水化的多异氰酸酯,可将如此获得的羟基官能的聚氨酯预聚物/丙烯酸复合分散体配制成随时可用的双组分涂布剂。在此,不利的是使用最高至6%的分子量调节剂(例如硫醇),基于丙烯酸酯单体计,这可能对重要的涂料性能如耐久性和薄膜硬度产生不利的影响。
适用于制备双组分(2K)涂布剂的聚氨酯-聚丙烯酸酯复合二次分散体,公开于DE-A 10308103中。在该文献中所描述的聚氨酯-聚丙烯酸酯复合分散体是由分子量Mn为1100至10000的聚氨酯和一种或多种烯属不饱和单体制备的,使它们在均质的非水相中自由基聚合,至少部分地中和,并在水相中分散。它们适于各种应用领域。
但是,特别地,作为塑料基材上的双层涂料体系,这些双组分涂布剂显示不足的粘附性:在不用粘附促进剂直接用水性底漆形式的涂料体系涂覆的塑料基材上,显得直接粘附性不足。水性底漆形式的涂料体系在涂覆有粘附促进剂的塑料基材上的粘附性也无法满足要求。而且,在构造了(Aufbau)水基清漆之后,基于该体系的水性底漆会溶胀,如尤其是在40℃下进行100小时的浸泡试验之后所示的那样。另外,它们或它们的水性清漆没有表现出在塑料基材上所期望的在良好的耐洗刷性和良好的耐化学性的同时具有高柔性的组合的性能特征。
因此,本发明的一个目的在于,提供一种用于制备基于氨基甲酸酯的水基聚双层涂料体系的水性清漆,其满足通常对涂料体系所提出的要求,尤其是对光泽度(通过大于85的光泽度值)和与对雾度形成所提出的要求。此外,应提供一种用于制备基于氨基甲酸酯的水基双层涂料体系的水性清漆,其在塑料上具有在良好的耐洗刷性和良好的耐化学性的同时具有高柔性的组合的性能特征。
本发明的另一个目的是提供一种用于制备基于氨基甲酸酯的水基聚氨酯双层涂料体系的水性底漆,其在所有的基材,尤其是塑料基材上,在加入或不加入粘附促进剂时,都表现出良好的粘附性。此外,本发明的一个优选的目的是提供一种相应的水性底漆,其在构造了水性清漆之后,仅仅表现出微小的溶胀。
本发明提供了一种用于制备基于氨基甲酸酯的水基双层涂料体系的水性清漆,其包括至少一种聚丙烯酸酯二次分散体,所述二次分散体具有由差示扫描量热仪(DSC)测得的聚丙烯酸酯的玻璃化转变温度Tg≥20℃,和至少一种聚丙烯酸酯-聚氨酯-复合分散体,所述二次分散体的聚丙烯酸酯部分与所述复合分散体的聚丙烯酸酯-聚氨酯部分的重量比为1∶1至4∶1,优选2∶1至3∶1,特别优选2.25∶1至2.75∶1,以及作为固化剂的至少一种低粘度的氨基磺酸多异氰酸酯。
本发明的水性清漆在具有良好的耐洗刷性和良好的耐化学性的同时表现出高柔性。此外,本发明的用于制备水基双层涂料体系的水性清漆满足对光泽度和低雾度形成的要求。
所述聚丙烯酸酯二次分散体优选地具有2.5至4.5重量%的OH部分,基于固体份计。进一步优选地,其具有由DSC测得的玻璃化转变温度为20至70℃的聚丙烯酸酯。进一步优选地,所述聚丙烯酸酯二次分散体在23℃下具有约200至约2500mPa·s的粘度,按照DIN ENISO 3219/A.3测定。优选的商业产品为由Bayer Material Science的Bayhydrol XP 2469、Bayhydrol A 145和Bayhydrol XP 2470。特别优选的是Bayhydrol XP 2470,其OH部分为3.9重量%、23℃下的粘度为约2000mPa·s,按照DIN EN ISO 3219/A.3测定,且玻璃化转变温度Tg为50℃(通过DSC测定)。
所述聚丙烯酸酯-聚氨酯-复合分散体可通过聚氨酯前体制备,所述聚氨酯前体可通过至少一种二异氰酸酯与至少一种线性聚酯反应,并随后用二乙醇胺封闭预聚物而制得。优选使用二异氰酸酯TMXDI。所述线性聚酯优选基于作为酸组分的二聚脂肪酸和/或间苯二甲酸,并基于作为醇组分的新戊二醇和/或己二醇。然后为了制备所述复合分散体,将这种前体在有机相中预置。然后,在这种聚氨酯前体的存在下,在一个阶段或在多个连续阶段中,使(甲基)丙烯酸和/或(甲基)丙烯酸酯与烯属不饱和化合物聚合。在此,在多阶段聚合的情况下,反应进程可通过分阶段加入各个化合物或者各类化合物和/或分阶段加入至少两类化合物的混合物而进行。在优选的多阶段反应进程中,将苯乙烯、丙烯酸丁酯、丙烯酸羟乙酯和甲基丙烯酸环己酯聚合,并且在此在至少一个阶段中与丙烯酸进行反应。在进行聚合之后,将产物中和,并除去加工溶剂。固含量为35重量%。
所述低粘度的氨基磺酸多异氰酸酯可为基于HMDI或基于IPDI的多异氰酸酯。所述氨基磺酸多异氰酸酯优选为基于HMDI多异氰酸酯。所述低粘度的氨基磺酸多异氰酸酯优选具有23℃下为2000至8000mPas的粘度,按照DIN EN ISO 3219/A.3测定。进一步优选地,其具有17.0-25.0重量%的NCO含量。甚至更优选地,其NCO官能度F为2.5至3.8。相应的商业产品为,例如,Bayer Material Science的Bayhydur XP 2487/1和Bayhydur XP 2570。特别优选使用可以以Bayhydur XP 2570的形式商业获得的氨基磺酰基HMDI三聚体,其具有在23℃下为3500mPa·s的粘度,按照DIN EN ISO 3219/A.3测定,20.5重量%的NCO含量,NCO官能度F=3.0。
双层涂料体系的清漆可进一步包括作为固化剂的具有低粘度的疏水多异氰酸酯,其能导致更快速的固化和固化剂粘度的降低。此外,降低了固化的涂层对水的敏感性。这种低粘度的多异氰酸酯优选具有小于1500mPa·s的粘度,在23℃下按照DIN EN ISO 3219/A.3测定。为此目的,优选使用HDI三聚体。这类疏水多异氰酸酯的例子为Bayer Material Science的Desmodur N 3600和Desmodur XP 2410,其具 有23.0或者24.0重量%的NCO含量,在23℃下1200或者700mPa·s的粘度(按照DIN EN ISO 3219/A.3测定),3.2或者3.1的NCO官能度F,和180或者175的当量。作为疏水低粘度多异氰酸酯,特别优选使用Desmodur XP 2410。
除了所述的成分,本发明的双层涂料体系的清漆还可进一步含有至少一种添加剂,例如,润湿剂和分散剂、粘附促进剂、腐蚀抑制剂、流动调节剂、消泡剂、杀生物剂、光稳定剂、蜡、粒度小于25nm的硫酸钡、消光剂和/或增稠剂。
用于制备上述种类的水基双层涂料体系的水性底漆表现出清漆与水性底漆之间的良好粘附性,以及对基底(直接对塑料基材或者与用阴极沉积涂漆所涂覆的基材)的良好粘附性,所述体系包含至少一种聚氨酯分散体、至少一种所述种类的聚丙烯酸酯-聚氨酯-复合分散体、和至少一种蜜胺树脂。即使是在按照本发明所使用的清漆的情况下,这些水性底漆也仅仅很轻微地溶胀或者不溶胀,并且可良好地加工。特别是它们具有所期望的环管稳定性。
所述水性底漆的至少一种聚氨酯分散体的聚氨酯粘结剂部分与所述至少一种聚丙烯酸酯-聚氨酯-复合分散体的聚丙烯酸酯-聚氨酯复合粘结剂部分的重量比为3∶1至5.5∶1,优选4∶1至4.5∶1。
用于所述水性底漆的聚氨酯分散体可由UV稳定的二或多异氰酸酯、摩尔质量Mn为600-2000的聚醚和/或聚酯、和低分子量的二醇和/或乙醇胺制备。在该上下文中的低分子量的二醇和/或乙醇胺是指摩尔质量范围为62至600的化合物。作为二异氰酸酯,优选使用六亚甲基二异氰酸酯、四亚甲基二甲苯二异氰酸酯、1,3-异氰酸根合甲基环己烷、异佛尔酮二异氰酸酯和双(对异氰酸根合环己基)甲烷。还可以使用所述化合物的混合物或相应的低聚物,例如异氰脲酸酯、脲基甲酸酯和脲二酮。特别优选的是可作为商业产品Desmodur W获得的单体的双(对异氰酸根合环己基)甲烷,其具有在25℃下按照DIN EN ISO3219/A.3的约30mPa·s的粘度,和31.8重量%的NCO含量,以及异佛尔酮二异氰酸酯。作为聚酯,优选使用基于作为酸组分的二聚脂肪酸和/或间苯二甲酸和基于作为羟基官能组分的己二醇、新戊二醇和/或二羟甲基丙酸的化合物。随后,优选用三羟甲基丙烷,进行预聚物的扩链反应。在中和、分散、除去加工溶剂之后,获得所述聚氨酯分散体。作为聚醚,优选使用分子量约200至1000的低分子量聚乙二醇或聚丁二醇。
用于所述水性底漆的、已描述的种类的至少一种聚丙烯酸酯-聚氨酯-复合分散体,优选与所述水性清漆中所用的那种相同。
用于所述水性底漆中的至少一种蜜胺树脂的粘结剂部分,与所述至少一种聚氨酯分散体和所述至少一种聚丙烯酸酯-聚氨酯-复合分散体的重量份的总和的重量比,优选为1∶2至1∶8,特别优选为1∶3至1∶4。
作为蜜胺树脂,优选使用烷氧基烷基化的蜜胺树脂,例如甲氧基甲基化的和丁氧基甲基化的商业上可获得的Cymel 1133,以获得良好的耐水性、柔性和储存稳定性。
可通过将上述水性清漆与上述种类的水性底漆组合而获得的双层涂料体系,能够满足对水性清漆和水性底漆的要求,并且具有良好的加工性能。特别地,它们以良好的环管稳定性为特征。
本发明的另一构成是将本发明的双层涂料体系应用于涂覆基材,以及这些涂覆的基材自身。对于涂覆,用所述水性底漆,在预处理的或未预处理的基材的至少一面上,进行涂覆并干燥,然后用所述水性清漆进行涂覆,并且再次干燥。第一涂层施加之后的干燥,优选是在40至100℃下干燥3至15分钟之后的数分钟之后进行。所述水性清漆施加之后的第二干燥步骤,优选是在低于120℃的温度下的30分钟至1小时的闪蒸(优选为60至100℃下,10至30分钟)之后进行。干燥的双层涂料的各涂层的优选的膜厚为:水性底漆薄膜为10至25μm;水性清漆薄膜为30至60μm。
涂覆的基材可包括SMC、PA/PPO、PU/RIM、PC-PBT、GFK、PPO、PP/EPDM。优选地,用本发明的双层涂料体系涂覆通常用于汽车和多用途运载车部件的基材。特别优选地,所要求保护的涂覆的基材是来自 于汽车和多用途运载车的部件的塑料基材。
实施例
用于水性底漆的本发明的聚氨酯分散体1
用于本发明的聚氨酯分散体1的聚酯多元醇A的制备
在适于缩聚反应的钢反应釜中,称量加入4634g Pripol 1012(由Unichema获得的二聚脂肪酸)、2577g 1,6-己二醇、1372g间苯二甲酸和作为夹带剂的110g二甲苯,将该初始装料加热到150℃。如此升高混合物的温度(不超过220℃),使得塔顶温度不超过125℃。从酸值为5起,进行蒸馏并且持续到酸值为3.5。
随后,将聚酯在甲乙酮中稀释至FK为73%。
本发明的聚氨酯分散体1的制备
将1434g聚酯树脂溶液A和384g甲乙酮、85g二羟甲基丙酸、14g新戊二醇、392g异佛尔酮二异氰酸酯一起加热至恒定的异氰酸酯含量。随后,基于NCO含量为1.1%计,加入38g三羟甲基丙烷。在10至14dPas的粘度范围内(在1∶1的N-甲基吡咯烷酮中测得),通过加入40g正丁醇以阻止进一步的反应。在搅拌60分钟之后在82℃下加入43g二甲基乙醇胺。在搅拌30分钟之后在82℃下加入170g丁基乙二醇,并随后在82℃下进一步搅拌30分钟。之后,在搅拌下加入3550g水。通过在约70℃下进行减压蒸馏,除去甲乙酮,直至剩余含量小于0.5%。最后,用去离子水将固含量(1h,130℃)调节为27%。pH值为7.7。该材料是均质的,并且不含斑点和细丝。
用于清漆和水性底漆的本发明的聚丙烯酸酯-聚氨酯复合聚合物1
用于制备聚氨酯树脂溶液的聚酯多元醇的制备
在适于缩聚反应的钢反应釜中,称量加入728.3g Pripol1012(Unichema公司的二聚脂肪酸)、239.2g 1,6-己二醇、294.4g间 苯二甲酸和204.8g新戊二醇,以及作为夹带剂的180g二甲苯,并加热到150℃。如此升高混合物的温度(最高为220℃),使得塔顶温度不超过125℃。从酸值为5起,进行蒸馏并且持续到酸值为3.5。随后,将聚酯在甲乙酮中稀释至FK为73%。
用于制备聚丙烯酸酯-聚氨酯复合聚合物的聚氨酯树脂溶液的制备
在适于制备聚氨酯树脂的、具有回流冷凝器的钢反应釜中,预置2351.2g上文所述的聚酯树脂溶液,107.3g新戊二醇,692.5g TMXDI,和01.75g二月桂酸二丁基锡,并加热到80至90℃。当达到恒定的NCO含量时,加入47.7g N,N-二乙醇胺。在反应结束之后,用丁基乙二醇稀释至固含量为60%。
聚丙烯酸酯-聚氨酯复合聚合物1的制备
在适于聚合的、具有回流冷凝器的反应釜中,预置1355.6g上文所述的有机聚氨酯树脂溶液和759.8g丁基乙二醇并加热至约110℃。在保持温度的情况下,在5h内,均匀地向该初始装料中计量加入679.2g苯乙烯、1824.8g丙烯酸丁酯、775g丙烯酸环己酯和1225.4g丙烯酸羟乙酯的混合物,并且在5.5h内,均匀地计量加入580g丁基乙二醇和495.4g叔丁基过氧化-2-乙基己酸酯的混合物。再过一个小时之后,同时开始,在1h内,均匀地计量加入363.6g丙烯酸丁酯、135.6g苯乙烯、154.4g丙烯酸环己酯、245.0g丙烯酸羟乙酯和299.8g丙烯酸的混合物,并且在1.5h内,均匀地计量加入552g丁基乙二醇和107.8g叔丁基过氧化-2-乙基己酸酯的混合物。在固含量不再有显著提高之后,加热至120℃并在减压下汽提如此长时间,直至残留单体含量小于0.3%,并且粘度(10∶6在丁基乙二醇中)达到约5至5.8dPas。在冷却至约90℃之后,加入224.8g N,N-二乙基乙醇胺,用去离子水将产物稀释并调节至固含量为35%。分散体的pH值为7.4。
实施例:
组成:
2K水性清漆
第一组分:聚丙烯酸酯二次 Bayhydrol XP 52.80重量份
分散体 2470
45重量%的聚丙 26.80重量份
烯酸酯-聚氨酯复
合聚合物1
35重量%的水 10.00重量份
丁基乙二醇 1.66重量份
聚酯K-Flex188 5.70重量份
各种添加剂 5.24重量份
102.20重量份
第二组分:亲水化的HDI多Bayhydur XP 2570 38.00重量份
异氰酸酯
脂肪族HDI多异Desmodur XP 241033.00重量份
氰酸酯
丁基乙二醇乙酸 29.00重量份
酯
100.00重量份
初始组分的混合比例:在所用的漆料中的固化剂:100∶43(重量)
水性底漆:
水 38.59重量%
聚氨酯分散体1.27重量 30.30重量%
%
聚丙烯酸酯-聚氨酯复 5.50重量%
合聚合物1.35重量%
Cymel 1133蜜胺树脂 2.80重量%
颜料膏部分 8.80重量%
其他成分 14.01重重%
100.00重量%
经涂覆的基材的制备:
用所述水性底漆,对用阴极电泳涂漆(Cathoguard 500,BASFCoatings AG)和二道底漆(2840-20,Glasurit GmbH)预处理的金属基材,进行气动涂覆。在闪蒸5分钟后,在80℃下干燥10分钟。这样得到的膜厚为12至20μm。
随后,气动施加所述水性清漆。在闪蒸40分钟后,在80℃下干燥20分钟。得到的膜厚为40至50μm。
以这种方式获得的涂层具有如下特有的性能:
视觉印象:
无气泡,20°光泽 92E
lw 1.9
sw 16
图像清晰度 82
耐化学性:
机械性能值:
粘附性测试
体系 | BL | KI | |||
5 | LY 4506-99-E | LY 4669-23-A | |||
划格 | 抗石击 | 冲击 | 光泽 | 溶胀 | |
ISO 2409 | STD 234 (Scania公司) | ISO 6272-1 | ISO 2813 | ||
未暴露(50 °,过夜老 化) | 0 | 1.5 | i.O. | 90 | |
96h水储存 +1h室温(ISO 2812-2,40 ℃下96h) | 0 | 1.5 | 2 | ||
4h-25℃储存 | 0 | 1.5 | i.O. |
AMTEC(DIN 55668,10个循环)
初始光泽20° | 92 |
光泽20°,没有清洁 | 33 |
光泽20°,清洁 | 68 |
回流时间[min] | 120 |
回流温度[℃] | 80 |
光泽20°,回流,未清洁的一侧 | 39 |
光泽20°,回流,清洁的一侧 | 80 |
Claims (14)
1.用于制备基于氨基甲酸酯的水基双层涂料体系的水性清漆,
其特征在于:
该水性清漆含有
-至少一种聚丙烯酸酯二次分散体,所述二次分散体具有聚丙烯酸酯的玻璃化转变温度Tg≥20℃;和
-至少一种聚丙烯酸酯-聚氨酯-复合分散体,
-所述二次分散体的聚丙烯酸酯部分与所述复合分散体的聚丙烯酸酯-聚氨酯部分的重量比为1∶1至4∶1;以及
-作为固化剂的至少一种低粘度的氨基磺酸多异氰酸酯。
2.如权利要求1所述的水性清漆,其特征在于,所述二次分散体的聚丙烯酸酯部分与所述复合分散体的聚丙烯酸酯-聚氨酯部分的重量比为2∶1至3∶1。
3.如权利要求1或2所述的水性清漆,其特征在于,所述二次分散体的聚丙烯酸酯部分与所述复合分散体的聚丙烯酸酯-聚氨酯部分的重量比为2.25∶1至2.75∶1。
4.如权利要求1或2所述的水性清漆,其特征在于,所述聚丙烯酸酯二次分散体具有2.5至4.5重量%的OH部分,基于固体部分计。
5.如权利要求1或2所述的水性清漆,其特征在于,所述聚丙烯酸酯二次分散体具有20至70℃的聚丙烯酸酯的玻璃化转变温度Tg。
6.如权利要求1或2所述的水性清漆,其特征在于,所述聚丙烯酸酯二次分散体具有23℃下为200至2500mPa·S的粘度。
7.如权利要求1或2所述的水性清漆,其特征在于,所述聚丙烯酸酯-聚氨酯-复合分散体可通过如下过程制备:
-在有机相中,预置聚氨酯前体,所述聚氨酯前体可通过使至少一种二异氰酸酯与至少一种线性聚酯反应,并随后用二乙醇胺将该预聚物封闭而制得,
-在所述聚氨酯前体存在下使(甲基)丙烯酸和/或(甲基)丙烯酸酯与烯属不饱和化合物进行一阶段或多阶段聚合,以及
-中和并去除加工溶剂。
8.如权利要求1或2所述的水性清漆,其特征在于,该水性清漆进一步包含疏水的低粘度多异氰酸酯作为固化剂。
9.用于制备水基双层涂料体系的水性底漆,其特征在于,该水性底漆包含至少一种聚氨酯分散体、至少一种聚丙烯酸酯-聚氨酯-复合分散体和至少一种蜜胺树脂,基于至少一种聚氨酯分散体的粘结剂与至少一种聚丙烯酸酯-聚氨酯-复合分散体的重量份的总和计,至少一种蜜胺树脂的粘结剂的重量比例为1∶3-1∶8,该水性底漆的至少一种聚氨酯分散体的聚氨酯粘结剂部分与至少一种聚丙烯酸酯-聚氨酯-复合分散体的聚丙烯酸酯-聚氨酯复合粘结剂部分的重量比为3∶1至5.5∶1。
10.如权利要求9所述的水性底漆,其特征在于,该水性底漆的至少一种聚氨酯分散体的聚氨酯粘结剂部分与至少一种聚丙烯酸酯-聚氨酯-复合分散体的聚丙烯酸酯-聚氨酯复合粘结剂部分的重量比为3∶1至4.5∶1。
11.基于氨基甲酸酯的水基双层涂料体系,其包括如权利要求1-8任一项所述的水性清漆和水性底漆,该水性底漆包含至少一种聚氨酯分散体、至少一种聚丙烯酸酯-聚氨酯-复合分散体和至少一种蜜胺树脂,基于至少一种聚氨酯分散体的粘结剂与至少一种聚丙烯酸酯-聚氨酯-复合分散体的重量份的总和计,至少一种蜜胺树脂的粘结剂的重量比例为1∶3-1∶8,该水性底漆的至少一种聚氨酯分散体的聚氨酯粘结剂部分与至少一种聚丙烯酸酯-聚氨酯-复合分散体的聚丙烯酸酯-聚氨酯复合粘结剂部分的重量比为3∶1至5.5∶1。
12.如权利要求11所述的水基双层涂料体系,其特征在于,所述水性底漆的至少一种聚丙烯酸酯-聚氨酯-复合分散体,与所述水性清漆的聚丙烯酸酯-聚氨酯-复合分散体相同。
13.制备权利要求11或12任一项所述的水基双层涂料体系的方法,其特征在于,将权利要求1-8任一项所述的水性清漆与水性底漆组合,该水性底漆包含至少一种聚氨酯分散体、至少一种聚丙烯酸酯-聚氨酯-复合分散体和至少一种蜜胺树脂,基于至少一种聚氨酯分散体的粘结剂与至少一种聚丙烯酸酯-聚氨酯-复合分散体的重量份的总和计,至少一种蜜胺树脂的粘结剂的重量比例为1∶3-1∶8,该水性底漆的至少一种聚氨酯分散体的聚氨酯粘结剂部分与至少一种聚丙烯酸酯-聚氨酯-复合分散体的聚丙烯酸酯-聚氨酯复合粘结剂部分的重量比为3∶1至5.5∶1。
14.用如权利要求11或12任一项所述的水基双层涂料体系涂覆的基材。
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CN1753919A (zh) * | 2003-02-26 | 2006-03-29 | 拜尔材料科学股份公司 | 基于聚氨酯-聚丙烯酸酯混合分散体的水性涂料介质 |
CN1837251A (zh) * | 2005-03-09 | 2006-09-27 | 拜尔材料科学股份公司 | 具有活性稀释剂的共聚物水分散体 |
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DE4010176A1 (de) | 1990-03-30 | 1991-10-02 | Basf Lacke & Farben | Verfahren zur herstellung einer mehrschichtigen lackierung und waessriger lack |
AT400440B (de) | 1993-12-06 | 1995-12-27 | Vianova Kunstharz Ag | Verfahren zur herstellung von wasserverdünnbaren lackbindemitteln und deren verwendung |
DE4342384A1 (de) | 1993-12-11 | 1995-06-14 | Hoechst Ag | Wasserverdünnbare Zweikomponenten-Überzugsmasse |
DE4415292A1 (de) * | 1994-04-30 | 1995-11-02 | Herberts Gmbh | Modulsystem und Verfahren zur Herstellung wäßriger Überzugsmittel |
DE4437535A1 (de) * | 1994-10-20 | 1996-04-25 | Basf Lacke & Farben | Polyurethanmodifziertes Polyacrylat |
US5594065A (en) | 1995-05-09 | 1997-01-14 | Air Products And Chemicals, Inc. | Two component waterborne crosslinkable polyurethane/acrylate-hybrid systems |
DE19736535C1 (de) * | 1997-08-22 | 1999-01-28 | Basf Coatings Ag | Basislackzusammensetzung sowie Verfahren zur Herstellung von mehrschichtigen Überzügen |
DE10024624A1 (de) | 2000-05-18 | 2001-11-22 | Bayer Ag | Modifizierte Polyisocyanate |
DE10237193A1 (de) * | 2002-08-14 | 2004-02-26 | Bayer Ag | Polyurethan-Polyacrylathybride als Beschichtungsmittel |
DE102004045533A1 (de) * | 2004-09-20 | 2006-03-23 | Bayer Materialscience Ag | Hydrolysestabile Beschichtungsmittelzusammensetzung |
JP2006257141A (ja) * | 2005-03-15 | 2006-09-28 | Nippon Paint Co Ltd | 二液硬化型水性被覆組成物及び塗膜形成方法 |
JP2009503122A (ja) * | 2005-07-29 | 2009-01-29 | 関西ペイント株式会社 | 水性クリヤ塗料組成物及び上塗り複層塗膜形成方法 |
JP2007283271A (ja) * | 2006-04-20 | 2007-11-01 | Kansai Paint Co Ltd | 複層塗膜形成方法 |
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- 2008-04-30 CN CN2008800147920A patent/CN101675132B/zh active Active
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CN1753919A (zh) * | 2003-02-26 | 2006-03-29 | 拜尔材料科学股份公司 | 基于聚氨酯-聚丙烯酸酯混合分散体的水性涂料介质 |
CN1837251A (zh) * | 2005-03-09 | 2006-09-27 | 拜尔材料科学股份公司 | 具有活性稀释剂的共聚物水分散体 |
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ZA200907410B (en) | 2010-07-28 |
WO2008135210A1 (de) | 2008-11-13 |
ES2601578T3 (es) | 2017-02-15 |
EP2152824A1 (de) | 2010-02-17 |
US8299164B2 (en) | 2012-10-30 |
CN101675132A (zh) | 2010-03-17 |
BRPI0811081A2 (pt) | 2014-12-09 |
AU2008248976B2 (en) | 2013-10-03 |
DE102007021013A1 (de) | 2008-11-06 |
AU2008248976A2 (en) | 2009-11-26 |
EP2152824B1 (de) | 2016-08-03 |
JP2010526194A (ja) | 2010-07-29 |
JP5611034B2 (ja) | 2014-10-22 |
US20100324199A1 (en) | 2010-12-23 |
MX2009011140A (es) | 2009-11-02 |
AU2008248976A1 (en) | 2008-11-13 |
KR20100017655A (ko) | 2010-02-16 |
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