CN105062181B - 次硝酸铋在电泳漆中的应用 - Google Patents
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Abstract
含有碱式硝酸铋的可阴极沉积的电泳漆,其含有至少一种具有反应性官能团的粘结剂和至少一种含有互补的反应性官能团的交联剂,所述官能团能发生热交联反应。
Description
本分案申请是基于申请号为200880103005.X、申请日为2008年8月13日、发明名称为“次硝酸铋在电泳漆中的应用”的中国专利申请的分案申请。
技术领域
本发明涉及含有铋化合物的可阴极沉积的电泳漆,这些电泳漆的制备方法,以及它们的用途。
背景技术
从专利文献中已知制备电泳漆的许多例子。在此,尤其是锡化合物和/或铋的化合物被用作交联催化剂。最近,优选采用铋化合物作为交联催化剂,因为它们除了它们的高活性之外,相比锡化合物还具有低毒性。铋化合物作为在由异氰酸酯基和羟基形成氨基甲酸酯结构中的催化剂的应用长久以来是已知的(J.H.Saunders and K.C.Frisch,Polyurethanes,Chemistry and Technology aus High Polymers,第XVI卷,部分1,Interscience Publishers,a division of John Wiley and Sons,纽约,第4次印刷,1967年7月,第167页)。但是,到目前为止,铋化合物作为在制备电泳漆过程中的催化剂的应用,是非常受限的。在EP 0 642 558中清楚地限制了可能用于电泳漆的铋化合物,因为可容易获得的、较长链的酸的盐,如辛酸铋和新癸酸铋,在应用于阳离子粘结剂中时,由于油状析出,会造成失效()。此外,由于被混入到粘结剂中或混入到颜料膏中,据说无机铋化合物很难分散,并且以这种形式仅仅具有非常低的催化活性。欧洲专利EP 0 739389描述了一种借助电泳涂漆,制备防腐涂漆的简化工艺,其中所述电泳漆含有乳酸铋或二甲基丙酸铋。提及了其他可能的铋化合物,但是在此缺少详细的说明,尤其是在实施例中仅采用了乳酸和二甲基丙酸的盐。没有提及次硝酸铋。基于氨基酸(EP 0 927 232)和链烷磺酸(EP 1 163 302)的其他铋络合物被描述为在电泳漆中的可良好使用的且稳定的催化剂体系。为了改进电泳漆的防腐性,DE 100 01 222A1提到了使用胶体铋。在该德国专利中采用了脂肪族羧酸的铋盐。有机羧酸的铋盐在电泳漆中的另一个应用描述在德国专利申请DE44 34 593A1中。在制备这种防腐漆的过程中,应当很大程度上避免毒性成分。德国专利申请DE 102 36 350A1描述了含有碱式水杨酸铋的电泳漆,其具有良好的流动性,不产生表面缺陷,并且确保良好的防腐性。但是,这些已知的电泳漆需要相对高的烘烤温度,以获得充分的交联。
发明内容
本发明的目的是寻找含有铋化合物的新的电泳漆,其中本发明的电泳漆中的交联反应,应在尽可能低的烘烤温度下进行。
令人惊讶地发现,在使用碱式硝酸铋(也被称为次硝酸铋)作为交联催化剂时,可以在相对低的温度下进行烘烤在基材上沉积的薄膜。
因此,本发明提供了一种开头所述类型的电泳漆,其特征在于,所述铋化合物是碱式硝酸铋。
鉴于现有技术,令人惊讶地且对于本领域技术人员难以预见的是,本发明的目的可以借助碱式硝酸铋而实现。特别令人惊讶的是,本发明的电泳漆可简单地制备,是储存稳定的,具有在分散的成分的最佳粒子尺寸,并且可非常好地过滤。它们可以以非常简单的方式毫无问题地以电泳方式沉积在导电性基材上。得到的电沉积涂漆具有良好的流动性,无表面缺陷和斑点,并且提供优异的防腐性和边角防护性(Kantenschutz)。
欧洲专利申请EP 151 0558 B1和EP 1 518 906采用了大量用于制备电泳漆的不同金属盐,其中一种是硝酸的铋盐。但是,这两个专利没有描述碱式硝酸铋的应用。所述欧洲专利也没有公开通过加入硝酸的铋盐作为交联催化剂而降低烘烤温度。此外,与本申请中所用的水不溶性的次硝酸铋相比,硝酸铋具有良好的水溶性。溶解的Bi盐在所述电泳漆中,可能会表现出一些缺点。可溶性盐会在超滤液中被吸收,并因此以这种方式被持续地从所述电泳漆中除去。而且,在车身的预处理之后,外来离子可能会被带入电泳漆浴中。这些外来离子可能会使可溶性Bi催化剂失活(EP 1 342 757)。
本发明的电泳漆优选具有5~50重量%,优选地5~35重量%的固含量。此处的固体是指电泳漆的份额,其构成由此制备的电沉积涂漆。本发明的电泳漆含有至少一种粘结剂。
所述粘结剂含有反应性官能团,所述官能团能能够与存在于交联剂中的互补反应官能团发生热交联反应。
所述粘结剂含有阳离子和/或潜在的阳离子基团。这类粘结剂可被用于可阳离子沉积的电泳漆中。
可通过中和剂和/或季铵化剂转化为阳离子的、适当的潜在的阳离子基团的例子为伯、仲或叔氨基,仲硫醚基或叔膦基,尤其是叔氨基或仲硫醚基。
适当的阳离子基团的例子为伯、仲、叔或季铵基、叔锍基或季鏻基,优选为季铵基或叔锍基,但尤其是季铵基。
用于所述潜在的阳离子基团的适当的中和剂的例子为无机和有机酸,如硫酸、盐酸、磷酸、甲酸、乙酸、乳酸、二羟甲基丙酸、柠檬酸或磺酸,如氨基磺酸和链烷磺酸,例如甲磺酸,尤其是甲酸、乙酸或乳酸。
用于电泳漆的适当的粘结剂的例子可由如下公开文献获知:EP 0 082 291A1、EP0 234 395A1、EP 0 227 975 A1、EP 0 178 531A1、EP 0 333 327、EP 0 310 971A1、EP0456 270A1、US3,922,253A、EP 0 261 385A1、EP 0 245 786A1、EP 0 414 199A1、EP 0 476514A1、EP 0 817 684A1、EP0 639 660A1、EP 0 595 186A1、DE 41 26 476A1、WO98/33835、DE 33 00 570A1、DE 37 38 220A1、DE 35 18 732A1或DE 196 18 379A1。优选地,所述粘结剂是含有伯、仲、叔或季氨基或铵基和/或叔锍基的树脂,并具有优选为20~250mgKOH/g的胺值,和300~10 000道尔顿的重均分子量。尤其是采用氨基(甲基)丙烯酸酯树脂、氨基-环氧树脂、具有末端双键的氨基-环氧树脂、具有伯和/或仲羟基的氨基-环氧树脂、氨基-聚氨酯树脂、含氨基的聚丁二烯树脂或改性的环氧树脂-二氧化碳-胺的反应产物。
适当的反应性官能团的例子为羟基、巯基、和伯和仲氨基,尤其是羟基。
适当的互补反应官能团的例子为封闭的异氰酸酯基。
作为适当的交联剂,考虑所有常规的且已知的交联剂,所述交联剂含有适当的互补反应性官能团。所述交联剂优选选自如下组:封闭的多异氰酸酯、密胺-甲醛树脂、三(烷氧基羰基氨基)三嗪和聚环氧化物。优选地,所述交联剂选自由封闭的多异氰酸酯和高反应性密胺-甲醛树脂所组成的组。特别优选地,采用封闭的多异氰酸酯。
所述封闭的多异氰酸酯由常规的且是公知的、具有脂肪族、脂环族、芳脂族和/或芳族连接的异氰酸酯基的漆料多异氰酸酯制备。
适当的漆料多异氰酸酯的例子已描述在,例如“Methoden der organischenChemie”,Houben-Weyl,第14/2卷,第4版,Georg Thieme Verlag,Stuttgart 1963,第61~70页,以及W.Siefken,Liebigs Annalen der Chemie,第562卷,第75~136页。
适当的漆料多异氰酸酯的其他例子为具有异氰脲酸酯基团、缩二脲基团、脲基甲酸酯基团、亚氨基噁二嗪二酮基团、氨基甲酸酯基团、脲基团、碳二亚胺基团和/或脲二酮基团的多异氰酸酯,其可由常规的并且公知的二异氰酸酯获得。优选作为二异氰酸酯使用六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、2-异氰酸基丙基环己基异氰酸酯、二环己基甲烷-2,4’-二异氰酸酯、二环己基甲烷-4,4’-二异氰酸酯或1,3-双(异氰酸基甲基)环己烷(BIC)、衍生自二聚脂肪酸的二异氰酸酯、1,8-二异氰酸基-4-异氰酸基甲基辛烷、1,7-二异氰酸基-4-异氰酸基甲基庚烷,1-异氰酸基-2-(3-异氰酸基丙基)环己烷、2,4-和/或2,6-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、萘二异氰酸酯或者由这些多异氰酸酯组成的混合物。
用于制备所述封闭的多异氰酸酯的适当的封闭剂的例子为:
i)酚,如苯酚,甲酚、二甲苯酚、硝基苯酚、氯代苯酚、乙基苯酚、叔丁基苯酚、羟基苯甲酸、这种酸的酯或者2,5-二叔丁基-4-羟基甲苯;
ii)内酰胺,如ε-己内酰胺、δ-戊内酰胺、γ-丁内酰胺或β-丙内酰胺;
iii)活性次甲基化合物,如二乙基丙二酸、二甲基丙二酸、乙酰乙酸乙酯或甲酯或者乙酰丙酮;
iv)醇如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇、叔戊醇、月桂醇、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、二乙二醇单甲醚、二乙二醇单乙醚、丙二醇单甲醚、甲氧基甲醇、乙醇酸、乙醇酸酯、乳酸、乳酸酯、羟甲基脲、羟甲基密胺、双丙酮醇、氯乙醇、溴乙醇、1,3-二氯-2-丙醇、1,4-环己基-二甲醇或乙酰基氰醇;
v)硫醇如丁硫醇、己硫醇、叔丁基硫醇、叔十二烷基硫醇、2-巯基苯并噻唑、噻吩、甲基噻吩或乙基噻吩;
vi)酰胺如乙酰替苯胺(Acetoanilid)、乙酰茴香酰胺、丙烯酰胺、甲基丙烯酰胺、乙酰胺、硬脂酰胺或苯甲酰胺;
vii)酰亚胺如琥珀酰亚胺、邻苯二甲酰亚胺或马来酰亚胺;
viii)胺如二苯胺、苯基萘胺、二甲代苯胺、N-苯基二甲代苯胺、咔唑、苯胺、萘胺、丁胺、二丁胺或丁基苯胺;
ix)咪唑如咪唑或2-乙基咪唑;
x)脲如脲、硫脲、亚乙基脲、亚乙基硫脲或1,3-二苯脲;
xi)氨基甲酸酯如苯基N-苯基氨基甲酸酯或2-噁唑烷酮;
xii)亚胺如乙撑亚胺;
xiii)肟如丙酮肟、甲醛肟、乙醛肟、丙酮肟、甲乙酮肟、二异丁酮肟、二乙酰基单肟、二苯甲酮肟或氯代己酮肟;
xiv)亚硫酸的盐,如亚硫酸氢钠或亚硫酸氢钾;
xv)羟氨基酯如苄基甲基丙烯酸羟氨酯(BMH)或烯丙基甲基丙烯酸羟氨酯;或者
xvi)取代的吡唑、咪唑或三唑;以及
xvii)1,2-多元醇如乙二醇、丙二醇、以及1,2-丁二醇;
xviii)2-羟基酯如2-羟乙基丙烯酸酯、2-羟乙基甲基丙烯酸酯;
xix)这些封闭剂的混合物。
根据本发明,本发明的电泳漆含有总式为4(BiNO3(OH)2)BiO(OH)的次硝酸铋。根据DAB7铋含量为71~74重量%。次硝酸铋是一种商品化合物,例如由MCP HEK GmbH公司,Lübeck,德国,出售。本发明的电泳漆,基于他们的固体计,含有优选为0.05~5,优选为0.1~4,尤其是0.2~3重量%的次硝酸铋。
此外,本发明的电泳漆还可含有有效量的至少一种典型的且是公知的添加剂,选自如下组:不同于次硝酸铋的催化剂、颜料、防凹坑添加剂(Antikrateradditiven)、聚乙烯醇、可热固化的反应性稀释剂、分子分散的可溶性染料、光稳定剂如UV吸收剂和可逆的自由基清除剂(HALS)、抗氧化剂、低沸点和高沸点(“长”)有机溶剂,脱气剂、润湿剂、乳化剂、增滑剂、聚合抑制剂、耐热的自由基引发剂、增粘剂、流动调节剂、成膜助剂、阻燃剂、防腐剂、流动助剂、蜡、干燥剂、杀生剂和消光剂。
适当的添加剂的其他例子已描述在教科书《Lackadditive》,Johan Bieleman,Wiley-VCH,Weinheim,纽约,1998,以及D.Stoye和W.Freitag(编者),“Paints,Coatingsand Solvents”,第二次完全修正版,Wiley-VCH,Weinheim,纽约,1998,《14.9.SolventGroups》,第327~373页。
优选将颜料用作添加剂。优选地,所述颜料选自如下组:常规的且公知的赋予色彩的、赋予效果的、导电的、磁屏蔽的、荧光的、填充的和防腐的有机和无机颜料。
本发明的电泳漆是通过将上文所述的成分混合并均化而制备的,并且任选地,借助常规的和公知的混合方法和设备,如搅拌槽、搅拌磨、挤出机、捏合机、Ultraturrax、直列式高速分散机(In-line-Dissolver)、静态混合器、微混合器、齿轮分散机、释压喷嘴(Druckentspannungsdüsen)和/或微射流均质机(Mikrofluidizern)。在这种情况下,颜料优选以颜料膏或颜料制剂的形式,被混入到所述电泳漆中(参见,Lexikon Lacke undDruckfarben,Georg Thieme Verlag,Stuttgart,纽约,1998,“”,第452页)。本发明所采用的次硝酸铋的另一个特别的优点是,其能被出色地混入到所述颜料膏中,以及混入到本发明的电泳漆中。
本发明的电泳漆可通常在导电性基材,例如导电性基材或者使其变为导电性的基材,例如通过金属化使之具有导电性的塑料基材,或者尤其是金属基材上进行阴极沉积。因此,本发明还涉及将本发明的电泳漆在相应的基材上阴极沉积的方法。作为金属基材可使用由全部常规金属构成的部件,例如在汽车工业中的产规的金属部件,尤其是汽车车身及其部件。
下文将参照本发明的实施例和对比实施例,对本发明进行详细说明。
具体实施方式
实施例1:
1.1交联剂V1的制备(=DE 197 03 869的实施例1)
在装有回流冷凝器、内温度计和惰性气体入口的反应器中,在氮气气氛下,预置1084份基于4,4-二苯基甲烷二异氰酸酯的异构体和更高官能度的齐聚物,其NCO当量为135(A270,BASF AG)。加入0.6份二月桂酸二丁基锡并以这样的速率滴加1314份丁基二甘醇醚,使得产物温度保持低于70℃。任选地必须进行冷却。将温度在70℃下再保持120分钟。当随后进行检测时,无法再检测出NCO基团。冷却至70℃。固含量>97%。
1.2水性粘结剂分散体D1的制备(=DE 197 03 869的实施例2.3)
在装有回流冷凝器、内温度计和惰性气体入口的反应器中预置1128份基于双酚A的环氧当量(EEW)为188的商品环氧树脂,94份苯酚和228份双酚A,并在氮气下加热至130℃。在搅拌下,加入1.5g三苯基膦,此时发生放热反应,温度升至160℃。再次冷却至130℃,随后检测EEW。目标数值为478。然后,在冷却的同时,加入15.7份Plastilit 3060(BASFAG)。在95℃下,加入115.5份二乙醇胺,此时发生放热反应。40分钟后,加入61.2份N,N-二甲氨基丙胺。在短时间的放热反应(140℃)之后,将装料在130℃下继续反应2小时,直至粘度保持恒定。
将97.6份丁基乙二醇和812份70℃的交联剂V2的热溶液快速在搅拌下加入到得到的反应混合物中,并在105℃下出料。
将2400份得到的混合物立即分散到预置的混合物中,所述混合物由2173份软化水和49.3份冰醋酸组成。在加入额外的751份软化水之后,得到具有如下参数的稳定的分散体:
固含量(60分钟/130℃):45.1%
pH值:5.9
平均离子尺寸:145nm
1.3研磨树脂溶液R1的制备
按照EP 505 445B1,实施例1.3,制备研磨树脂,出于更号的操作的目的,还用2.82份冰醋酸和13.84份完全软化的水对所述树脂进行中和和稀释。由此,将初始固含量降至60%。
1.4水性颜料膏的制备
1.4.1颜料膏P1(本发明的颜料膏)
将下列组分顺序加入高速运转的溶解搅拌机中,并混合30分钟:
随后将混合物在实验室搅拌磨中,在1-2h期间将其分散至12μm的Hegman细度,并且任选地再用水调节至所期望的加工粘度。
1.4.2颜料膏P2(对比实施例)
按照1.4.1所述的方法,制备颜料膏2,但是,用6.0份的碱式水杨酸铋(Bi含量56~59%,HEK-Lübeck)代替次硝酸铋。
1.5电泳漆的制备
为了测试可阴极沉积的电泳漆,相应于下表,将所述水性粘结剂分散体与颜料膏混合。此处如此进行:预置粘结剂分散体,并用去离子水将其稀释。随后,在搅拌下,加入颜料膏。所给出的值相应于重量份。
2.电泳漆的测试
将本发明的电涂浴在室温下,在搅拌下陈化24h。将所述电泳漆沉积在阴极连接的磷酸锌化的钢板上。在32℃的浴温下,沉积时间为120s。如此选择沉积电压,使得能获得20μm的经烘烤的漆膜的厚度。
将沉积的漆膜用去离子水洗涤,并在给定的温度下烘烤15分钟。
为了测试经烘烤的漆膜的交联状态,按照DIN EN13523-11(摩擦测试)测定对作为溶剂的丁酮(甲乙酮)的耐受性。为此测定这样的双摩擦次数,在该次数时可漆膜的明显损坏变得可以辨认。在100次双摩擦的最大值的情况下,漆膜被评价为i.O.。
下面的表1和图1给出了在各种烘烤温度下,本发明的电泳漆(ETL1)和对比实施例(ETL2)的结果。
从数据明显可以看出,在低出5~10℃的烘烤温度下,本发明的电泳漆中的交联反应已经是充分的。
表1
耐溶剂性(DIN EN 13523-11,用MEK进行的摩擦测试)
Claims (1)
1.水不溶性的碱式硝酸铋在可阴极沉积的电泳漆中作为交联催化剂用于降低电泳漆的烘烤温度的用途,
其中所述电泳漆含有至少一种粘结剂、至少一种交联剂和至少一种颜料,
其中在电泳漆的制备中不使用水溶性的硝酸铋,和
其中水不溶性的碱式硝酸铋以包含至少一种颜料的颜料膏的形式被混入到所述电泳漆中。
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2008
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- 2008-08-13 BR BRPI0815169-5A patent/BRPI0815169A2/pt not_active IP Right Cessation
- 2008-08-13 EP EP08785518.5A patent/EP2190936B1/de active Active
- 2008-08-13 RU RU2010109453/05A patent/RU2010109453A/ru not_active Application Discontinuation
- 2008-08-13 MX MX2010000877A patent/MX2010000877A/es unknown
- 2008-08-13 CA CA2695954A patent/CA2695954A1/en not_active Abandoned
- 2008-08-13 JP JP2010520484A patent/JP5579061B2/ja active Active
- 2008-08-13 ES ES08785518.5T patent/ES2684802T3/es active Active
- 2008-08-13 WO PCT/EP2008/006642 patent/WO2009021719A2/de active Application Filing
- 2008-08-13 CN CN200880103005A patent/CN101835852A/zh active Pending
- 2008-08-13 KR KR1020107004869A patent/KR101488692B1/ko active IP Right Grant
- 2008-08-13 US US12/673,202 patent/US9493660B2/en active Active
-
2016
- 2016-09-27 US US15/277,095 patent/US10975252B2/en active Active
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Also Published As
Publication number | Publication date |
---|---|
CN101835852A (zh) | 2010-09-15 |
WO2009021719A2 (de) | 2009-02-19 |
ES2684802T3 (es) | 2018-10-04 |
MX2010000877A (es) | 2010-04-30 |
JP2010536943A (ja) | 2010-12-02 |
DE102007038824A1 (de) | 2009-02-19 |
RU2010109453A (ru) | 2011-09-27 |
CA2695954A1 (en) | 2009-02-19 |
US20110094890A1 (en) | 2011-04-28 |
EP2190936B1 (de) | 2018-05-23 |
BRPI0815169A2 (pt) | 2015-03-31 |
US10975252B2 (en) | 2021-04-13 |
KR20100066483A (ko) | 2010-06-17 |
JP5579061B2 (ja) | 2014-08-27 |
EP2190936A2 (de) | 2010-06-02 |
KR101488692B1 (ko) | 2015-02-03 |
US9493660B2 (en) | 2016-11-15 |
US20170015845A1 (en) | 2017-01-19 |
CN105062181A (zh) | 2015-11-18 |
WO2009021719A3 (de) | 2009-11-12 |
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