CN104520344A - 包括锌(ii)脒配合物的水性树脂分散体及其制造方法 - Google Patents

包括锌(ii)脒配合物的水性树脂分散体及其制造方法 Download PDF

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CN104520344A
CN104520344A CN201380040904.0A CN201380040904A CN104520344A CN 104520344 A CN104520344 A CN 104520344A CN 201380040904 A CN201380040904 A CN 201380040904A CN 104520344 A CN104520344 A CN 104520344A
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aqueous resin
dispersion
resin dispersion
polyisocyanates
polymkeric substance
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CN104520344B (zh
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V·艾斯瓦拉克里施南
A·格雷
J·A·拉夫
K·摩尔
M·桑德拉
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PPG Industries Ohio Inc
PPG Industries Inc
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PPG Industries Inc
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Abstract

本文中公开的是稳定的水性树脂分散体和制造该水性分散体用的方法,其包括锌(II)脒配合物。

Description

包括锌(II)脒配合物的水性树脂分散体及其制造方法
技术领域
本发明涉及水性树脂分散体、制造该分散体的方法、相关的涂料组合物和涂覆的基材。
背景技术
作为涂层施加方法的电沉积包括:在施加的电势影响下,将成膜组合物沉积在导电的基材上。电沉积已经在涂料产业中得到普及,因为与非电泳涂覆的方法相比,它提供了更高的油漆利用率、突出的耐腐蚀性和低的环境污染。在商业上使用了阳离子和阴离子沉积两者,在需要高防腐水平的应用中,阳离子更流行。
阳离子可电沉积的组合物通常包含水性树脂分散体,其包括(i)含有活性氢、阳离子盐基的成膜性树脂;和(ii)至少部分封端的异氰酸酯交联剂。这种组合物还经常包括树脂和交联剂之间反应用的催化剂,例如尤其是有机锡化合物。近年来,已经采用了替换的催化剂,例如锌(II)脒配合物。这种催化剂被认为在相对低的温度下提供了更好的固化速率(低温固化例如对于减少能量消耗可能是理想的),并且例如与有机锡化合物相比,可能是更少毒性和环境上更合要求的。
然而,使用锌(II)脒配合物作为低温固化组合物中催化剂的一个缺点是不能获得稳定的水分散体,该分散体包含与含活性氢、阳离子盐基的成膜性树脂和至少部分封端的异氰酸酯(其在低温下结封端(deblocks))结合的该种催化剂。结果是,在"低温固化应用"中使用该种催化剂是困难的。然而,本发明提供在该应用中使用这种催化剂的方法。
发明内容
在某些方面,本发明涉及制造水性树脂分散体用的方法。这些方法包括将第一水性树脂分散体与第二水性树脂分散体结合。第一水性树脂分散体包含(i)含有活性氢、含有阳离子盐基的聚合物;和(ii)锌(II)脒配合物。第二水性树脂分散体包含:(i)含有活性氢、含有阳离子盐基的聚合物;和(ii)至少部分封端的多异氰酸酯。
在其它方面,本发明涉及水性树脂分散体,其是稳定的分散体,并且包含:(a)含有活性氢、含有阳离子盐基的聚合物;(b)锌(II)脒配合物;和(c)至少部分封端的多异氰酸酯,选择它以便提供在320°F或以下的温度下固化的水性树脂分散体。
本发明还涉及将水性树脂分散体电泳沉积并固化在基材上的方法,以及由此形成的涂覆基材。
详细说明
为便于下面的详细说明,应理解的是:本发明可假定各种替代变化和步骤顺序,除非明确地有相反指定。此外,除了在任何操作实施例中,或者另外指出的地方,所有的数字表达,例如在说明书和权利要求书中使用的组分的含量,在所有情况下应理解为由术语"约"修饰。因此,除非有相反的指示,在以下说明书和所附权利要求书中提出的数值参数是近似值,其可以根据由本发明将获得的期望性质而改变。至少,但并不是要试图限定相当于权利要求书范围的原理的应用,每个数值参数应至少按照报告的有效数值的数值来解释,并且使用普通的舍入方法。
尽管提出本发明宽范围的数值范围和参数是近似值,在特定实施例中提出的数值被尽可能精确地记录。然而,任何数值固有地含有由在它们各自试验测量中发现的标准偏差必然引起的某些误差。
并且,应该理解的是:本文中列举的任意数值范围意欲包括包含在其中的所有子范围。例如,范围"1至10"意欲包括在列举的最小值1和列举的最大值10之间的(并且包括)所有子范围(也就是说,具有等于或大于1的最小值和等于或小于10的最大值)。
在本申请中,单数的使用包括复数,且复数包绕单数,除非另有具体说明。另外,在本申请中,"或"的使用意指"和/或",除非另外具体说明,虽然在某些情况下可以明确地使用"和/或"。
如指出的,本发明的某些实施方案涉及制造水性树脂分散体的方法。这种方法包含将第一水性树脂分散体与第二水性树脂分散体结合。如本文中使用的,术语"水性树脂分散体"是指两相的透明、半透明或不透明树脂体系,其中聚合物在分散相中,且分散介质(其包括水)在连续相中。在本发明中,这些水性树脂分散体是可电沉积的水性树脂分散体。如在本文中使用的,"可电沉积的水性树脂分散体"是指适合用在可电沉积的涂料组合物中的水性分散体,也就是说,能够在施加的电势影响下沉积在导电基材上的涂料组合物。在某些实施方案中,本文中描述的水性树脂分散体是稳定的分散体。如本文中使用的,术语"稳定的分散体"是指当在25℃温度下维持至少60天时,不凝胶、絮凝或沉淀的分散体,或者如果确实发生了一些沉淀,该沉淀物可以在搅拌下再分散。
如要被理解的,除了水之外,在某些实施方案中,分散介质可以含有一些有机共溶剂。在某些实施方案中,有机共溶剂与水至少部分可溶。这种溶剂的例子包括含氧的有机溶剂,例如乙二醇、二乙二醇、丙二醇和二丙二醇的单烷基醚,其在烷基中含有1至10个碳原子,例如这些二醇的单乙基和单丁基醚。其它至少部分水混溶的溶剂的例子包括醇,例如乙醇、异丙醇、丁醇和二丙酮醇。如果使用的话,在某些实施方案中,有机共溶剂以小于10wt%的量使用,例如小于5wt%,基于分散介质的总重量。
如指出的,在本发明的方法中,第一水性树脂分散体包含(i)含有活性氢、含有阳离子盐基的聚合物;和(ii)锌(II)脒配合物。
如本文中使用的,术语"含有活性氢、含有阳离子盐基的聚合物"是指包括活性氢官能团和至少部分中和的阳离子基团(例如锍基和胺基,其赋予正电荷)的聚合物。如本文中使用的,术语"聚合物"包含但不限于低聚物和均聚物与共聚物两者。如本文中使用的,术语"活性氢官能团"是指那些与异氰酸酯有活性的基团,通过在JOURNAL OF THEAMERICAN CHEMICAL SOCIETY第49卷第3181页(1927)中描述的泽列维季诺夫试验确定的,并且例如包括羟基、伯或仲胺基、和硫醇基。在某些实施方案中,活性氢官能团是羟基、伯胺基和/或仲胺基。
适合在本发明中用作含有活性氢、含有阳离子盐基聚合物的聚合物的例子,尤其包括但不限于:醇酸树脂聚合物、丙烯酸类、聚环氧化物、聚酰胺、聚氨酯、聚脲、聚醚和聚酯。在某些实施方案中,这种聚合物包含胺基和/或羟基。
合适的含活性氢、含阳离子盐基的聚合物的更具体例子包括聚环氧化物-胺加和物,例如多酚(例如双酚A)的聚缩水甘油醚与伯和/或仲胺的加和物,例如在美国专利号4,031,050第3栏第27行至第5栏第50行、美国专利号4,452,963在第5栏第58行至第6栏第66行和美国专利号6,017,432在第2栏第66行至第6栏第26行描述的,通过引用将其这些部分并入至此。在某些实施方案中,与聚环氧化物反应的胺部分是聚胺的酮亚胺,如在美国专利号4,104,147第6栏第23行至第7栏第23行描述的,通过引用将其引用部分并入至此。还适合的是未凝胶的聚环氧化物-聚氧化烯聚胺树脂,例如在美国专利号4,432,850第2栏第60行至第5栏第58行描述的,通过引用将其引用部分并入至此。另外,可以使用阳离子丙烯酸树脂,例如在美国专利号3,455,806第2栏第18行至第3栏61行和3,928,157第2栏29行至第3栏21行描述的那些,通过引用将两者的这些部分并入至此。
除了含胺盐基的树脂,在本发明中还可以使用含季铵盐基的树脂,作为含阳离子盐基的聚合物。这些树脂的例子是由有机聚环氧化物与叔胺酸性盐反应形成的那些。这种树脂描述在美国专利号3,962,165第2栏3行至11栏7行;3,975,346第1栏62行至第17栏25行和4,001,156第1栏37行至16栏7行中,通过引用将其这些部分并入至此。其它合适的阳离子树脂的例子包括含有三元锍盐基的树脂,例如在美国专利号3,793,278第1栏32行至5栏第20行中描述的那些,通过引用将该部分并入至此。并且,还可以使用通过酯交换机理固化的阳离子树脂,例如在欧洲专利申请号12463B1第2页第1行至第6页第25行中描述的,通过引用将其该部分并入至此。
其它合适的含阳离子盐基树脂包括可以形成抗光降解的可电沉积涂料组合物的那些。这种聚合物包括以下的聚合物,其包含衍生自悬垂的和/或末端胺基的阳离子胺盐基团,其公开在美国专利申请公开2003/0054193A1的[0064]至[0088]处,通过引用将其该部分并入至此。还适合的是衍生自多元酚的聚缩水甘油醚的含活性氢、含阳离子盐基的树脂,其本质上不含有向其键合有超过一个芳基的脂族碳原子,其描述在美国专利申请公开US2003/0054193A1第[0096]至[0123]处,通过引用将其该部分并入至此。
在某些实施方案中,含有活性氢、含有阳离子盐基的聚合物在第一水性树脂分散体中以50至99wt%的量存在,例如70至95wt%,基于第一水性树脂分散体的总固体重量。
如之前指出的,第一水性树脂分散体还包含锌(II)脒配合物。在某些实施方案中,锌(II)脒配合物含有脒和羧化物配体。更准确地说,在某些实施方案中,锌(II)脒配合物如描述在美国专利号7,485,729第7栏第43行至第8栏第51行和第10栏第11行至第12栏第61行,通过引用将其该引用部分并入至此。如将要理解的,前述专利描述了具有式Zn(A)2(C)2的化合物,其中A表示脒,且C表示羧化物。更准确地说,A可以由式(1)或(2)表示:
其中,R1-R8例如描述在美国专利号7,485,729第10栏第37行至第11栏第31行;且C是脂族、芳族或聚合物型羧化物,具有45至465的当量重量。
这种锌(II)脒配合物是从Norwalk Connecticut的KingIndustries以产品码可商购获得的。
在某些实施方案中,锌(II)脒配合物在第一水性树脂分散体中以1至40wt%的量存在,例如10至30wt%,基于第一水性树脂分散体的总固体重量。
如将要理解的,第一水性树脂分散体可包括任意的多种任选组分,例如着色剂(例如二氧化钛、炭黑)、抗氧化剂、杀菌剂、消泡剂、表面活性剂、润湿剂、分散助剂、粘土、受阻胺光稳定剂、UV光吸收剂和稳定剂及其组合。
然而,在某些实施方案中,第一水性树脂分散体本质上或有时完全不含有任何交联剂,例如至少部分封端的多异氰酸酯,例如任意下述至少部分封端的多异氰酸酯。如在该段中使用的,当指出水性树脂分散体"本质上不含有"特定物质时,是指相关的物质(例如至少部分封端的多异氰酸酯)在水性树脂分散体中不以足以使水性树脂分散体不稳定的量存在;换句话说,水性树脂分散体仍旧是如之前定义的"稳定分散体"。如在该段中使用的,当指出水性树脂分散体"完全不含有"特定物质时,例如至少部分封端的多异氰酸酯,是指在水性树脂分散体中完全不存在该物质。
此外,在某些实施方案中,第一水性树脂分散体本质上或有时候完全不含有环境不友好的含锡金属催化剂(例如尤其是二月桂酸二丁基锡、二氧化二丁基锡、二新十二酸二丁基锡、二乙酸二丁基锡、二油酸二辛基锡)。如在本段中使用的,当指出水性树脂分散体"本质上不含有"含锡金属催化剂时,是指该材料在水性树脂分散体中以一定量存在,使得当形成涂料组合物时,该材料以小于0.1wt%的量存在,基于涂料组合物中树脂固体的总重量。
本文中的实施例说明了制造第一水性分散体的合适方法。在某些实施方案中,在与锌(II)脒配合物混合之前,形成含有活性氢、含有阳离子盐基的聚合物;而在某些实施方案中,在聚合物材料与阳离子盐基前体反应以形成含阳离子盐基聚合物之前,将含有活性氢的聚合物与锌(II)脒配合物混合。在这些实施方案的任一个中,然后,可以将水加入至混合物。在某些实施方案中,首先将锌(II)脒配合物与水,或者水和酸的混合物混合,在它与聚合物混合之前。用于此目的的示例性酸包括但不限于乳酸、乙酸、甲酸和/或氨基磺酸。
如之前指出的,在本发明的方法中,将第一水性分散体与第二水性分散体结合。此外,在本发明的方法中,第二水性分散体包含(i)含有活性氢、含有阳离子盐基的聚合物;和(ii)至少部分封端的多异氰酸酯。
在第二水性分散体中存在的含有活性氢、含有阳离子盐基的聚合物可以包含上述关于第一水性分散体的任意聚合物。在一些实施方案中,第一水性分散体和第二水性分散体包含相同的含有活性氢、含有阳离子盐基的聚合物。在一些实施方案中,第一水性分散体和第二水性分散体包含彼此不同的含有活性氢、含有阳离子盐基的聚合物。例如,在一些实施方案中,第一水性树脂分散体包含未凝胶的聚环氧化物-聚氧化烯聚胺树脂,如上所述,且第二水性树脂组合物包含聚环氧化物-胺加和物,其中部分与聚环氧化物反应的胺是聚胺的酮亚胺,如上所述。
在某些实施方案中,含有活性氢、含有阳离子盐基的聚合物在第二水性树脂分散体中以50至90wt%的量存在,例如60至80wt%,基于第二水性树脂分散体的总固体重量。
除含有活性氢、含有阳离子盐基聚合物外,第二水性分散体还包含至少部分封端的多异氰酸酯。如本文中使用的,术语"至少部分封端的多异氰酸酯"意指其中至少部分异氰酸酯基已经与化合物反应的多异氰酸酯,使得所得封端的异氰酸酯部分在室温下对羟基或胺基稳定,但在高温下(通常是200°F(93℃)以上)对羟基或胺基有反应性。"部分封端的多异氰酸酯"将含有平均约一个的游离反应性异氰酸酯基,然而,"完全封端的多异氰酸酯"将不含游离反应性异氰酸酯基。
更具体地说,在本发明的某些实施方案中,第二水性分散体包含至少部分封端的多异氰酸酯,选择它以便当与第一水性树脂分散体结合时,提供在320°F(160℃)或以下的温度下,例如250°F(121℃)至320°F(160℃),275°F(135℃)至320°F(160℃),或者有时为275°F(135℃)至300°F(149℃)固化的水性树脂分散体。在一些实施方案中,至少部分封端的多异氰酸酯在温度下去封端,使得可以在275°F(121℃)下获得所得涂料组合物的优异固化。如本文中使用的,术语"固化"是指其中涂料的可交联组分至少部分被交联的工艺。在某些实施方案中,可交联组分的交联密度(即,交联度)从完全交联的5%至100%变化,例如35%至85%,或者有时是50%至85%。本领域技术人员将理解:交联度的存在,即,交联密度,可以通过各种方法来确定,例如在氮气下利用Polymer Laboratories MK HI DMTA分析器实施的动态力学热分析(DMTA)。
可以在制备适合在本发明中使用的至少部分封端多异氰酸酯中使用的多异氰酸酯,包括脂族和芳香族多异氰酸酯。脂族多异氰酸酯的代表性例子是(i)亚烷基异氰酸盐,例如三亚甲基、四亚甲基、五亚甲基、六亚甲基、1,2-亚丙基、1,2-亚丁基、2,3-亚丁基、1,3-亚丁基、亚乙基和亚丁基二异氰酸酯,和(i i)环亚烷基异氰酸酯,例如1,3-环戊烷、1,4-环己烷、1,2-环己烷二异氰酸盐和异氟尔酮二异氰酸酯。合适的芳族多异氰酸酯的代表性例子是(i)亚芳异氰酸酯,如间亚苯基、对亚苯基、4,4′-二苯基、1,5-萘、1,4-萘二异氰酸酯,和(i i)亚烷芳基异氰酸酯,如4,4′-二亚苯基甲烷、2,4-或2,6-苯亚甲基或其混合物、4,4′-甲苯胺和1,4-亚二甲苯基二异氰酸酯。三异氰酸酯,例如三苯基甲烷-4,4′,4″-三异氰酸酯、1,3,5-三异氰酸酯苯和2,4,6-三异氰酸酯甲苯;四异氰酸酯,如4,4′-二苯基二甲基甲烷-2,2′,5,5′-四异氰酸酯;和聚合的异氰酸酯,如甲苯二异氰酸酯二聚体和三聚体等,也可以使用。
在某些实施方案中,在本发明方法的第二水性分散体中存在的至少部分封端的多异氰酸酯包含具有结构(3)部分的含氨基甲酸酯物质:
其中,R是H、烷基、烯基或芳基,且X是氢、烷基、烯基、芳基或-N(R1)(R2),其中R1和R2彼此独立地是H、烷基、烯基或芳基。
这种含氨基甲酸酯的材料和生产它们用的方法描述在美国专利号4,452,963第1栏第47行至第5栏第13行,通过引用将其引用部分并入至此。在某些实施方案中,这种含氨基甲酸酯的材料是通过异氰酸酯与结构(4)的化合物反应制备的:
其中R可以是H或烃基或取代烃基、饱和或不饱和烃基,例如烷基、烯基或芳基,且X可以是H或烃基或取代烃基、饱和或不饱和烃基,例如烷基、烯基或芳基。
其它适合用于本发明中的至少部分封端的多异氰酸酯,包括:(i)那些用具有结构(5)的材料至少部分封端的多异氰酸酯:
其中,n是1至10的数字;m是1至10的数字;且R是H或具有1至30个碳原子的烷基或芳基或取代烷基或芳基,其描述在美国专利号6,017,432第2栏第43-64行和第6栏第33行至第8栏第38行,通过引用将其引用部分并入至此;(i i)酮肟-封端的多异氰酸酯,其描述在美国专利号3,694,389第2栏第24行至第6栏第29行,通过引用将其引用部分并入至此;和(i i i)3,5-二甲基吡唑封端的多异氰酸酯,例如从Baxenden Chemicals,Ltd.,Lancashire,英格兰可商购获得的那些。
在某些实施方案中,至少部分封端的多异氰酸酯在第二水性树脂分散体中以10至50wt%的量存在,例如30至45wt%,基于第二水性树脂分散体的总固体重量。
如将要理解的,第二水性树脂分散体可(如果需要的话)包括任意的多种任选组分,例如着色剂(例如二氧化钛、炭黑)、抗氧化剂、杀菌剂、消泡剂、表面活性剂、润湿剂、分散助剂、粘土、受阻胺光稳定剂、UV光吸收剂和稳定剂及其组合。
本文中的实施例说明了制造第二水性分散体的合适方法。
在本发明的方法中,将第一水性分散体与第二水性分散体结合。这种结合可以发生在任何合适的容器中,包括但不限于合适搅拌下的电沉积浴。此外,如将要理解的,除了第一水性树脂分散体和第二水性树脂分散体外,可以结合其它涂料组合物组分,例如,如包含分散在树脂类材料(通常被认为是颜料研磨载体)中的颜料的颜料分散体。分散体的颜料含量通常标识为颜料-对-树脂重量比。在本发明的实践中当使用颜料时,颜料-对-树脂重量比有时在0.03至0.35的范围内。上述其它添加剂在组合物中通常是0.01至3wt%的量,基于树脂固体的总重量。
按照本发明方法生产的组合物的树脂固体含量取决于其特定的最终用途,并且通常不是关键的。含有至少1wt%树脂固体的组合物是常见的,例如5至40wt%或5至20wt%。树脂固体,是指组合物的不挥发性有机物质含量,即:当加热到110℃15分钟时不挥发的有机物质,并且将排除有机溶剂。
已经惊讶地发现:本发明的方法提供了所得分散体改善的特性。更具体地,惊讶地发现了:将锌(I I)脒配合物直接加入到水性树脂分散体中,该分散体包含含有活性氢、含有阳离子盐基的聚合物和至少部分封端的多异氰酸酯(其在低温下去封端),例如上述的那些,导致形成了分散体,其是不稳定的分散体。另一方面,当按照本文中公开的方法制备涂料组合物时,生产了稳定的水性树脂分散体。
结果,本发明还涉及水性树脂分散体,其是稳定的分散体,并且包含:(a)含有活性氢、含有阳离子盐基的聚合物;(b)锌(I I)脒配合物;和(c)至少部分封端的多异氰酸酯,选择(c)以便提供在320°F(160℃)或以下的温度下固化的水性树脂分散体。
在某些实施方案中,通过将组合物与导电阳极和导电阴极接触,将由本发明方法生产的涂料组合物沉积在导电基材上,表面被涂覆的表面是阴极。在与组合物接触后,将涂料组合物的粘着层沉积在阴极上,并且在两个电极之间施加足够的电压。进行电沉积的条件通常类似于在其它种类涂料电沉积中使用的那些。施加的电压可以改变,并且例如可以是低至一伏特至高达数千伏特,但通常在50至500伏特之间。电流密度通常在0.5安倍至15安倍每平方英尺之间,且在表明绝缘薄膜形成的电沉积期间倾向于降低。
一旦可电沉积的涂料组合物被电沉积在至少部分导电基材上,将涂覆的基材加热到足以将基材上电镀涂层固化的温度保持一定时间。在某些实施方案中,将涂覆的基材加热到250°F至360°F(121.1℃至180℃)的温度,例如250°F至300°F(135℃至149℃)。固化时间可取决于固化温度以及其它变量,例如电沉积涂层的薄膜厚度。对本发明来说,所有必须的是:时间要足以引起基材上涂层的固化。例如,固化时间可以从10分钟至60分钟变化,例如20至40分钟。
在某些实施方案中,将涂覆的基材加热到300°F(149℃)或以下的温度,保持足以引起基材上电沉积涂层固化的时间。所得固化涂层的厚度通常在15至50微米范围内。
通过本发明方法生产的涂料组合物还可以(如果需要的话)通过非电泳涂覆施加技术施加到基材上,例如流动、浸渍、喷雾和辊涂施加。对于电沉积和非电泳涂覆施加,涂料组合物可施加到各种导电基材上,特别是金属,例如钢、铝、铜、镁等,但还包括金属化塑料和导电碳涂覆的材料。对于非电泳涂覆施加,组合物可施加到非金属基材,例如玻璃、木材和塑料。此外,在一些实施方案中,基材可以包含车辆的一部分,例如车身(例如,但不限于,门、车身板、行李箱盖、车顶板、发动机罩、和/或顶板)和/或车辆框架。如本文中使用的,"车辆"或其变形包括但不限于民用、商用和军用陆上车辆,如汽车、摩托车和卡车。还应当理解的是,在一些实施方案中,基材可以用预处理溶液预处理,例如如在美国专利号4,793,867和5,588,989中描述的磷酸锌溶液,或例如在美国专利申请号11/610,073和11/833,525中描述的含锆溶液。
因此,在某些实施方案中,本发明还涉及涂覆导电基材用的方法。在某些实施方案中,该方法包含(a)将本发明的水性树脂分散体电泳沉积在基材上和(b)将涂覆的基材加热到足以将基材上电沉积的涂层固化的温度并持续一定时间。在某些实施方案中,该方法包含(a)将本发明的水性树脂分散体电泳沉积到基材上,以在至少部分基材上形成电沉积涂层;(b)将涂覆的基材加热足以将基材上电沉积涂层固化的温度并保持一定时间;(c)向固化的电沉积涂层施加一种或多种含有颜料的涂料组合物和/或不含一种或多种颜料的涂料组合物,以在至少部分固化的电沉积组成上形成顶涂层;和(d)将步骤(c)的涂覆基材加热到足以将顶涂层固化的温度并保持一定时间。
以下实施例说明了本发明,然而,其不应认为是将本发明限定到它们的细节。除非另有说明,在以下实施例以及遍及本说明书中的所有份数和百分比是重量的。
实施例
实施例1:制备封端的多异氰酸酯
表1
# 材料 份数
1 甲苯二异氰酸酯 7568.8
2 甲基异丁基酮 5300.0
3 三羟基丙烷 1950.0
4 二月桂酸二丁基锡 3.9
5 甲基异丁基酮 25.0
6 二丁二醇酰胺1 8816.0
7 甲基异丁基酮 44.6
8 甲基异丁基酮 880.0
9 双酚A多元醇2 2137.5
10 丙二醇单苯基醚 100.0
11 丙二醇单苯基醚 2400.0
1作为二丁胺和乙醇酸的反应产物形成
2双酚A/6-环氧乙烷加合物
将材料1和2装入反应器,并加热到32℃。然后,将材料3以三部分加入到32℃的反应器。此时,反应放热。将批料在65℃下保持1小时,在该点将批料冷却至60℃,并加入材料4。用材料5冲洗引入到反应器中的线路。之后,将材料6用45分钟加入至反应器,其中反应放热。将发热量保持在低于100℃。之后,用材料7冲洗引入至反应器的线路。然后,将材料8加入反应器,将批料在90℃下保持两小时。然后,将材料9和10装入反应器中,将组合物保持30分钟,在该点处将材料11加入至反应器,并将组合物保持45分钟,在那里形成二丁二醇酰胺交联剂。
实施例2:制备包含含有活性氢、含有阳离子盐基的聚合物和封端异氰酸酯的水性树脂分散体
表2
3可以由Hexion Specialty Chemicals获得的环氧树脂
4作为二亚乙基三胺和甲基异丁基酮的反应产物形成
将材料1、2、3和4装入反应器,并加热到130℃,在该点处反应放热。然后,将反应器内的温度调节至160℃,并将组合物保持1小时。然后,将材料5和6加入到反应器,并将反应器冷却至105℃,在该点处加入材料7和8。然后,将反应器中的温度调节到120℃,并保持两小时。此时,加入材料9和10,并将反应器在95℃下保持20分钟。然后,将反应器内容物倒入另一个包括材料11和12的容器中。将新的容器保持1小时,加入材料13。在真空中从新反应器的内容物除去溶剂,以形成具有36.7%固体的阳离子树脂。所得分散体是单相材料,并表现出随时间无沉降(大于60天)。
实施例3:制备包含含有活性氢、含有阳离子盐基聚合物,封端的多异氰酸酯和锌(II)脒配合物的水性树脂分散体
表3
5从King Industries可商购获得的锌脒催化剂
在这个实施例中,将材料1、2、3和4装入反应器,并加热到130℃,在该点处反应放热。然后,将反应器内的温度调节至160℃,并将组合物保持1小时。然后,将材料5和6加入到反应器,并将反应器冷却至105℃,在该点处加入材料7和8。然后,将反应器中的温度调节到120℃,并保持两小时。此时,加入材料9和10,并将反应器在95℃下保持20分钟。然后,在90℃下将材料11加入到反应器,并允许混合15分钟。然后,将反应器内容物倒入另一个包括材料12和13的容器中。将新的容器保持1小时,加入材料14。在真空中从新反应器的内容物除去溶剂。所得分散体是不稳定的,并且在2天内表现出相分离和沉淀。分散体的不稳定性使得它不适合于引入到阳离子可电沉积涂料组合物中。
实施例4-制备根据本发明方法实施方案的"第一水性分散体"
表4
6可由Huntsman Chemical获得的用伯胺终止的聚环氧丙烷树脂
7可由Rhodia Chemicals获得的表面活性剂
将材料1、2和3顺序地装入反应器中,并加热到125℃。然后,将物品4加入到反应器,并允许发热,调整温度至160℃,并将混合物在160℃下保持1小时,然后,在该点处将材料5加入至反应器。然后,将材料6加入至反应器,同时搅拌10分钟,并允许组合物放热。然后,用材料7冲洗到反应器的线路,在这个点将反应器温度调节到125-130℃,并保持3小时。此时,将材料8和10加入至反应器,并且用材料9冲洗到反应器的线路。将组合物搅拌10分钟。然后,将所得组合物(2380.3份)加入到第二反应器中的材料11和12,并搅拌30分钟。然后,加入材料13。所得树脂组合物具有35.80%的固体含量。所得树脂组合物是单相材料,并且随着时间未表现出沉降(大于60天)。
实施例5-制备根据本发明方法的实施方案的"第一水性分散体"
表5
将材料1、2和3顺序地装入反应器中,并加热到125℃。然后,将物品4加入到反应器,并允许发热,调整温度至160℃,并将混合物在160℃下保持1小时,然后,在该点处将材料5加入至反应器。然后,将材料6加入至反应器,同时搅拌10分钟,并允许组合物放热。然后,用材料7冲洗到反应器的线路,在这个点将反应器温度调节到125-130℃,并保持3小时。此时,将材料8和10加入至反应器,并且用材料9冲洗到反应器的线路。将组合物搅拌10分钟。然后,将所得组合物(973.8份)加入到分离的反应器中的材料10、11和12,并搅拌30分钟。然后,将材料13加入到反应器,以得到具有32.4%固体含量的溶液。所得分散体是单相材料,并且随着时间未表现出沉降(大于60天)。
实施例6:水性树脂分散体的结合
表6
材料 份数
实施例4 125.2
实施例2 1840.4
去离子水 34.3
Kathon LX8 0.1
8可由ROHM and HAAS Company获得的杀菌剂
将材料混合,以得到36%的实施例6最终固体含量。树脂混合物是单相材料,并表现出随时间无沉降(大于60天)。
实施例7:水性树脂分散体的结合
表7
材料 份数
实施例5 137.6
实施例2 1840.4
去离子水 21.9
Kathon LX8 0.1
将材料混合,以得到36%的实施例7最终固体含量。树脂混合物是单相材料,并表现出随时间无沉降(大于60天)。
实施例8:来自实施例6的可电沉积涂料组合物
这个实施例描述使用实施例6的产物和不含锡的颜料浆料以0.1的颜料/粘合剂比例制备的15%固体的电涂覆浴组合物。
表8
材料 份数
实施例6 721.0
颜料浆料9 89.4
去离子水 1189.6
9由PPG Industries,Inc可商购获得的黑色浆料
实施例9:来自实施例7的可电沉积涂料组合物
这个实施例描述使用实施例7的产物和不含锡的浆料CP549以0.1的颜料/粘合剂比例制备的15%固体的电涂覆浴组合物。
材料 份数
实施例7 721.0
CP 5499 89.4
去离子水 1189.6
实施例10:制备对比树脂混合物
这个实施例描述了制备36%固体的对比树脂混合物。该树脂混合物是单相材料,并表现出随时间无沉降(大于60天)。
表10
材料 份数
实施例2 79764.0
聚氧化烯多胺-聚环氧加成物10 5230.0
去离子水 1691.0
卡松 3.9
10如在专利US 4432850A中描述的
实施例11:制备对比的可电沉积涂料组合物
这个实施例描述了以0.1p/b使用实施例10的产物和含有DBTO的浆料CP 524(可从PPG工业获得)制造的15%固体的对比电涂覆浴组合物。
表11
材料 份数
CR 65911 840.2
CP 52412 124.0
去离子水 1435.8
11由PPG Industries,Inc可商购获得的POWERCRON阳离子树脂
12由PPG Industries,Inc可商购获得的含阳离子树脂的颜料浆料
实施例12:可电沉积的涂料组合物的比较
分别在涂层外部条件(90°F/120″/225V)和(90°F/120″/250V)下以0.8密尔所需薄膜构造下,将实施例8、9和11的组合物涂覆,并在温度范围内检查固化(在煤气炉中峰值金属温度下20分钟)。结果示于下表12中。
表12
尽管在上文中为了说明的目的已经描述了本发明的特定实施例,对本领域技术人员将是显而易见的是:在不偏离如在所附权利要求书中限定的本发明下,可以作出本发明细节的许多改变。

Claims (19)

1.一种水性树脂分散体,包括:
(a)含有活性氢、含有阳离子盐基的聚合物;
(b)锌(II)脒配合物;和
(c)至少部分封端的多异氰酸酯,选择该多异氰酸酯以提供在320°F或以下的温度下固化的水性树脂分散体,
其中所述水性树脂分散体是稳定的分散体。
2.根据权利要求1所述的分散体,其中所述含有活性氢、含有阳离子盐基的聚合物包括未凝胶的聚环氧化物-聚氧化烯聚胺树脂。
3.根据权利要求2所述的弹性体,其中所述含有活性氢、含有阳离子盐基的聚合物进一步包括聚环氧化物-胺加和物,其中至少部分与所述聚环氧化物反应的胺是聚胺的酮亚胺。
4.根据权利要求1所述的分散体,其中所述锌(II)脒配合物包括脒和羧化物配体。
5.根据权利要求1所述的分散体,其中所述至少部分封端的多异氰酸酯包括具有结构(3)部分的含氨基甲酸酯物质:
其中,R是H、烷基、烯基或芳基,且X是氢、烷基、烯基、芳基或-N(R1)(R2),其中R1和R2彼此独立地是H、烷基、烯基或芳基。
6.根据权利要求1所述的分散体,其中所述水性树脂分散体在250°F至320°F的温度下固化。
7.根据权利要求6所述的分散体,其中所述水性树脂分散体在275°F至320°F的温度下固化。
8.一种方法,包括将权利要求1的分散体与导电阳极和导电阴极接触,其中要被涂覆的表面是阴极。
9.一种制造水性树脂分散体的方法,包括将第一水性树脂分散体与第二水性树脂分散体结合,其中:
(a)第一水性树脂分散体包括:
(i)含有活性氢、含有阳离子盐基的聚合物;和
(ii)锌(II)脒配合物;以及
(b)第二水性树脂分散体包括:
(i)含有活性氢、含有阳离子盐基的聚合物;和
(ii)至少部分封端的多异氰酸酯。
10.根据权利要求9所述的方法,其中第一水性树脂分散体和第二水性树脂分散体都是稳定的分散体。
11.根据权利要求9所述的方法,其中在第一水性树脂分散体中存在的所述含有活性氢、含有阳离子盐基的聚合物包括未凝胶的聚环氧化物-聚氧化烯聚胺树脂。
12.根据权利要求11所述的弹性体,其中在第二水性分散体中存在的所述含有活性氢、含有阳离子盐基的聚合物包括聚环氧化物-胺加和物,其中至少部分与所述聚环氧化物反应的胺是聚胺的酮亚胺。
13.根据权利要求9所述的方法,其中所述锌(II)脒配合物包括脒和羧化物配体。
14.根据权利要求9所述的方法,其中所述锌(II)脒配合物在第一水性树脂分散体中以10至30wt%的量存在,基于第一水性树脂分散体的总固体重量。
15.根据权利要求9所述的方法,其中第一水性树脂分散体本质上不含有任何至少部分封端的多异氰酸酯。
16.根据权利要求9所述的方法,其中第一水性树脂分散体本质上不含有含锡的金属催化剂。
17.根据权利要求9所述的方法,其中选择所述至少部分封端的多异氰酸酯,以便当与第一水性分散体结合时提供在320°F或以下的温度下固化的水性树脂分散体。
18.根据权利要求9所述的方法,其中所述至少部分封端的多异氰酸酯包括具有结构(3)部分的含氨基甲酸酯物质:
其中,R是H、烷基、烯基或芳基,且X是氢、烷基、烯基、芳基或-N(R1)(R2),其中R1和R2彼此独立地是H、烷基、烯基或芳基。
19.一种涂覆基材的方法,包括将通过权利要求9的方法生产的组合物与导电阳极和导电阴极接触,其中要被涂覆的表面是阴极。
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