CN1466603A - 低温干燥的水性涂料 - Google Patents
低温干燥的水性涂料 Download PDFInfo
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Abstract
本发明涉及含水、单组分可加工的粘合剂组合物，用于在100℃以下干燥制备可砂磨并且同时耐碎石和风蚀稳定的涂层。
Description
本发明涉及水性、单组分可加工的(einkomponentigverarbeitbare)粘合剂组合物及其制备和应用，该组合物用于制备在100℃以下干燥、可砂磨(schleifbaren)和同时抗碎石和风蚀稳定的涂料，优选用于汽车系列涂漆。
在汽车系列涂漆中已开创了表面层的多层结构，该结构也越来越多地在应用水性涂料组合物的情况下实现。对此，这些现代的涂料也遇到对经济性的要求。本发明的目的在于在尽可能少和尽可能低成本的一步中应用该涂料。
在汽车系列涂漆的常规漆结构中，首先在基于通过阴极电浸渍涂敷(KTL)的金属表面施加一碎石保护层和填充层(Füllerschicht)或者二者的组合(“碎石保护填料”)，然后在这些层上涂敷基漆，然后涂敷清漆或颜料着色的面漆。
碎石保护层和/或填充层用于补偿表面的不均匀性并由于高弹性和变形性而提供良好的抗碎石性。对此，以前将柔性聚酯或聚醚-聚氨酯以及多异氰酸酯或蜜胺交联剂用于这些层。在施用基漆和清漆或面漆之前烘烤碎石保护填料，这对于改善面漆状态和在施用上面的漆层前磨蚀填料层是必要的。在涂敷清漆或面漆之后再次进行烘烤。这一方法的缺点是，必须进行两次昂贵的＞120℃的烘烤过程。在低温下干燥的涂料，如可由聚丙烯酸酯配制的那些，不具有需要的抗碎石性，因为它们交联成脆性膜。
本发明的目的是发现储存稳定的单组分可加工的涂料配制物，它除了良好的抗碎石强度外还具有良好的耐磨性能和表面硬度。此外，该涂料应是经晒的，以在适度覆盖的面漆或基漆的情况下，或者在完全不用颜料着色的面漆或基漆的位置也形成风蚀稳定的涂层。此外，在本质上需要该涂层对各种基材的粘附，所述基材为例如在汽车制造中常用的塑料(预处理的聚丙烯或聚乙烯、预处理的聚丙烯/EPDM共混物、聚氨酯-RIM、ABS、聚对苯二甲酸丁二醇酯、聚碳酸酯、聚酰胺、SMC、BMC等，以及所述塑料的共混物)以及铁和非铁金属和基于不同粘合剂的硬化的漆层。考虑到在汽车制造中常用的热塑性材料(见上述)小的热变形稳定性，所述涂层必须可以在低于100℃的温度下硬化/交联。
建议用于抗碎石的涂层和/或基于水性粘合剂的填充层的解决方案描述于例如EP-A 0 330 139中。它要求保护可将聚丙烯酸酯加到OH-和COOH-官能的聚酯中。但没有相应的实施例，同样没有描述聚丙烯酸酯接枝到聚酯作为接枝基质上的接枝共聚。已知所要求保护的酸官能聚酯的分散体具有差的储存稳定性，因为它们通过酯键的裂解而快速化学降解(例如Jones，T.E.；McCarthy，J.M.，J.CoatingsTechnol.76(844)，第57页(1995))。
例如EP-A 0 024 727描述了基于环氧树脂-磷酸酯、可水稀释的聚酯以及水溶性蜜胺树脂的结合的烤漆。在DE-A 4 000 748的实施例中描述了基于可水稀释的羟基官能的聚酯-聚氨酯树脂，任选其它粘合剂和水溶性氨基树脂的水性汽车填料。
这些涂料还不能完全满足特别是汽车工业对填料层的高要求。通过进一步开发的多异氰酸酯交联的填料层得到了改进(M.Bock，H.Casselmann，H.Blum“用于汽车工业的水性PUR底漆进展”，Proc.Waterborne，Higher Solids and Powder Coatings Symp.NewOrleans 1994)。但所有提到的体系都有不足，即如果用反应性氨基-和/或多异氰酸酯树脂在较低烘烤温度下交联，所用的可水稀释的聚酯或聚酯-聚氨酯树脂具有有限的储存稳定性。
EP-A 0 980 880描述了抗碎石的物理干燥的涂料，该涂料在应用聚丙烯酸酯分散体与聚氨酯分散体组合的情况下制备，但该涂料的可砂磨性能不足。
WO PCT/00/01205描述了用聚丙烯酸酯分散体制备的抗碎石的物理干燥的涂层。但是这些组合在低于0℃的温度下具有弱的抗碎石强度。
因此，本发明目的也提供储存稳定的水性、低助溶剂含量、单组分、耐光的涂料体系，其在低于100℃的烘烤温度下具有改进的可砂磨性能和良好的抗碎石稳定性。此外，该涂料体系应提供在汽车制造中应用的不同基质上粘附。
令人惊奇地发现，这一目的可通过应用由特别硬和高弹性的几乎不含有OH-基团的水性聚氨酯分散体和高反应性的可水稀释的蜜胺树脂的组合达到。硬和软分散体界限的划分可根据通过物理干燥得到的膜的摆杆硬度进行。硬PUR-分散体A按照Knig(DIN 53157)摆杆硬度＞90s表征，而软PUR-分散体B通过摆杆硬度＜90s表征。
在含有用于汽车填料常用的颜料和添加剂的涂料组合物中，按下述合并粘结剂组分：
加入20-90重量％，优选40-70重量％的分散体A，10-80重量％，优选30-60重量％的分散体B，此外，加入0-30重量％，优选5-20重量％反应性的蜜胺树脂用于交联，所述三种树脂组分的份数之和为100％粘合剂组分。
特别适合于这种组合的是类似于WO PCT/00/01205的聚氨酯分散体作为高弹性组分和类似于EP-A 0 269 972的聚氨酯分散体作为硬组分。这些引用的专利文献描述了在所谓的丙酮法中制备聚氨酯分散体。在所谓的熔体分散方法中制备的类似组成的分散体同样适合于该应用。优选所述分散体用叔胺，例如三乙胺、二异丙基乙基胺、吗啉中和，所述粘合剂任选与可水稀释的氨基树脂组合，该氨基树脂具有与烘烤温度适应的反应活性(例如Cymel327，328-Cytec IndustriesB.V.，Rotterdam，Niederlande，MaprenalVMF 3921 W-VianovaResins GmbH und Co.KG，Frankfurt，Germany)。
实施例
实施例1
可水稀释的含有OH的、脂肪酸改性的聚酯-聚氨酯分散体与反应性蜜胺树脂组合((BayhydrolFT 145(Bayer AG，Leverkusen，Germany)/Cymel328(Cytec Industries B.V.，Rotterdam，Netherlands))
将35.8g下述的颜料糊与50.8g45％的脂肪酸改性的聚酯-聚氨酯分散体(BayhydrolFT145)和3.0g85％的商购水性蜜胺树脂(Cymel328)一起搅拌并用10.4g蒸馏水稀释到约17s ISO-Cup 5mm的喷雾粘度。实施例2
可水稀释的、低OH含量的硬聚氨酯分散体(BayhydrolPR 135，Bayer AG，Leverkusen，Germany)与按照EP-A 0 330 139的弹性聚氨酯分散体组合。
所述弹性聚氨酯分散体由272g脂肪族聚碳酸酯二醇(Desmophen2020，Bayer AG，Leverkusen，Germany，分子量2000)、272g基于己二酸、己二醇、新戊二醇的聚酯二醇(分子量1700)和26.8g二羟甲基丙酸组成，它们在氮气氛下称量并加热到65℃。然后加入11.3g三羟甲基丙烷、250g丙酮、106.6g异佛尔酮二异氰酸酯、75.9g六亚甲基二异氰酸酯和0.025％的二月桂酸二丁基锡并加热回流直至达到理论的NCO值或略微低于该值。冷却到45℃后，加入17.2g三乙胺(中和度85％)和1150g蒸馏水并于40℃-50℃搅拌该混合物直至不再能检测到游离的NCO基团。然后蒸馏除去丙酮，得到的很细颗粒的弹性聚氨酯分散体具有约40％的固体含量，pH约7.7和粘度约7800mPa.s/23℃。
用搅拌器将34.5g实施例1中所用的颜料糊与34.9g 35％的聚氨酯分散体(BayhydrolPR 135)和30.6g 40％的上述按EP-A 0 330139的弹性聚氨酯分散体混合。实施例3
具有低OH基团含量的可水稀释的硬聚氨酯分散体(BayhydrolPR135)与反应性的蜜胺树脂(Cymel328)组合。
将34.4g用于实施例1的颜料糊与62.7g 35％的聚氨酯分散体(BayhydrolPR 135)和2.9g 85％的商购水性蜜胺树脂(Cymel328)一起搅拌。实施例4
按照EP-A 0 330 139的具有低OH基团含量的可水稀释的弹性聚氨酯分散体与反应性的蜜胺树脂(Cymel328)组合。
将37.3g上述颜料糊与59.5g 40％的按EP-A 0 330 139的聚氨酯分散体(参见上述实施例2)和3.1g 85％的商购水性蜜胺树脂(Cymel328)一起搅拌。实施例5
具有低OH基团含量的可水稀释的硬分散体(BayhydrolPR 135)和按照EP-A 0 330 139的弹性聚氨酯分散体以1∶1的比例与反应性的蜜胺树脂(Cymel328)组合。
用搅拌器将35.8g实施例1所用的颜料糊与32.6g 35％的聚氨酯分散体(BayhydrolPR 135)、28.6g 40％的EP-A 0 330 139的弹性聚氨酯分散体(参见上述实施例2)和3.0g 85％的商购水性蜜胺树脂(Cymel328)充分混合。用于涂料实施例1-5的颜料糊
将由10.8g 70％可水稀释的聚酯树脂(BayhydrolD 270)、21.1g蒸馏水、1.5g 10％的存在于水中的二甲基乙醇胺和2.8g商购润湿剂、27.7g二氧化钛(TronoxR-FD-I，Kerr McGee Pigments GmbH和Co.KG，Krefeld，Germany)、0.3g氧化铁黑(Bayferrox303 TBayer AG，Leverkusen，Germany)、27.9g硫酸钡(Blanc fixe Micro，Sachtleben Chemie GmbH，Duisburg，Germany)、6.8g滑石(MicroTalc IT Extra，Norwegian Talc，Frankfurt，Germany)和1.0g抗沉降剂(AerosilR 972，Degussa-Hüls AG，Frankfurt，Germany)组成的预分散的浆状物于冷却下在市售珍珠磨(Perlmühle)中研磨30分钟成糊。
由此得到的涂料体系具有粘合剂-颜料/填料比为约1∶1)和下述粘合剂的组合，固体含量用重量份数(重量份)表示，在ISO-5mm杯中的流动时间立即和在40℃下储存7天后测定。
| 涂料实施例 | 1 | 2 | 3 | 4 | 5 |
粘合剂-固体树脂(重量份)
| OH-聚酯 | 90.0 | - | - | - | - |
| PUD，硬，低OH含量 | - | 50.0 | 90.0 | - | 45.0 |
| PUD，弹性，低OH含量 | - | 50.0 | - | 90.0 | 45.0 |
| 蜜胺 | 10.0 | - | 10.0 | 10.0 | 10.0 |
| 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |
| - | |||||
| 固体含量 | 50.9％ | 49.1％ | 48.9％ | 53.1％ | 50.9％ |
| ISO 5mm流动时间 | 17s | 12s | 15s | 13s | 12s |
| 在40℃下7天后的流动时间 | 24s | 12s | 13s | 13s | 12s |
通过喷嘴直径为1.5mm和雾化压力为5巴的流动杯(Fliessbecher)喷枪将这些涂料喷涂到下述基材上，所得的干膜厚度为25-35μm。将所述湿涂料膜在23℃通空气5分钟，然后在循环空气炉中烘烤。在测试摆杆硬度和光泽的情况下用玻璃板作为基材，在测定粘附/交叉切割(Gitterschnitt)、Erichsen-深冲(Tiefung)和耐磨性时用去脂钢板作基材以及在碎石测试中用在汽车产品中用的涂KTL的钢板作基材。
得到了下述测试结果：
| 涂料实施例 | 1 | 2 | 3 | 4 | 5 |
烘烤条件填料：10分钟室温和30分钟90℃
碎石测试组成：KTL-板，填料(10min RT和30min 90℃)，水基涂层“黑金属的”(15μm，10min 80℃)，2-组分丙烯酸系清漆(40μm，30min，90℃)
| 摆杆硬度 | 21s | 54s | 108s | 30s | 65s |
| 光泽60° | 93％ | 51％ | 51％ | 56％ | 53％ |
| Erichsen深拉 | 10mm | 10mm | 10mm | 10mm | 10mm |
| 交叉切割(0-5) | 0 | 1 | 0 | 0 | 0 |
| 耐磨性能，湿(1-4) | 3 | 2-3 | 1 | 2-3 | 1-2 |
A)VDA[德国汽车工业协会]撞击：2次500g；1.5巴
| 涂层间粘附KTL/填料(1-3) | 2 | 2-3 | 2 | 1 | 1 |
| 涂层间粘附填料/面漆(1-3) | 1 | 1 | 1 | 1 | 1 |
| 碎石测试结果(1-10) | 1 | 2 | 2-3 | 1 | 1 |
B)在室温和-30℃的BMW楔
摆杆硬度：Knig摆动试验，DIN 53 157光泽测定60°按照DIN EN ISO 2813Erichsen深拉，按照DIN EN ISO 1520交叉切割，按照DIN EN ISO 2409
| 从金属板上剥落室温/-30℃ | 0/1mm | 0/0 | 0/2mm | 0/0 | 0/0 |
耐磨性按照VW的说明书，用手弄湿，用标准化的颗粒320-400的砂纸，指数1-4(1＝通过水柱将沙尘从砂纸上完全除去；4＝不可砂磨)
VDA碎石试验按照VW的说明书用2×500g钢屑在1.5巴的空气压力下轰击。指数1-10(1＝没有穿透，10＝板上有很大和很多的剥落)
涂层间粘附，指数1-3(1＝良好，3＝无粘附)
碎石试验按照BMW的说明书，用Byk的ESP10单击测试仪在3巴测试压力下进行。测定从钢板上的平面分离，用mm表示。
结果表明，象预计的那样，通过含OH聚酯分散体和高反应性的蜜胺树脂的存在不能保证在实施例1中有足够的稳定性。在实施例3-5中，如果应用具有低OH含量的聚氨酯分散体，用蜜胺树脂的稳定性更有利。涂料膜所希望的硬度可通过配制物中具有低OH含量的硬和软分散体的比例进行调整。本发明的实施例5在稳定性、耐磨性和抗冲击性能方面表现出良好的结果。没有蜜胺树脂所述混合物同样稳定和可应用。
Claims (6)
1.一种储存稳定的含水单组分、可加工、耐碎石和可砂磨涂料组合物，这种涂料可以在低于100℃下硬化，由用于汽车系列填料常用的颜料和添加剂以及由聚氨酯分散体A和B组成的粘合剂和市售高反应性蜜胺树脂组成，其特征在于，所述聚氨酯分散体A物理干燥后按DIN53157的摆杆硬度＞90s，聚氨酯分散体B物理干燥后(按DIN 53157的)摆杆硬度＜90s。
2.按照权利要求1的涂料组合物，其特征在于，所述聚氨酯分散体的羟基含量为0-1.0重量％，优选0-0.5重量％，基于固体树脂计。
3.按照权利要求1和2的涂料组合物，其特征在于，所述涂料组合物的粘合剂固体树脂组分具有下述组成
聚氨酯分散体A固体含量：20-90重量％，优选40-70重量％，
聚氨酯分散体B固体含量：10-80重量％，优选30-60重量％，
以及
反应性氨基树脂交联剂：0-30重量％，优选5-20重量％，
其中在涂料配方中三种组分的含量加和为100重量％。
4.按照权利要求1-3的涂料组合物作为由金属和塑料制成的汽车部件的可砂磨、耐碎石涂料的用途。
5.按照权利要求4的用途，用于在汽车工业中对基材的常规预处理。
6.按照权利要求4和5的用途，其中所得涂层在≤100℃，优选在60-100℃下硬化20-40分钟。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702940A (zh) * | 2012-06-12 | 2012-10-03 | 天长市巨龙车船涂料有限公司 | 一种汽车中涂漆 |
| CN111647343A (zh) * | 2020-06-12 | 2020-09-11 | 安徽东顺汽车研发有限公司 | 一种环保卡车喷漆的生产配方及其制备工艺 |
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| AT411831B (de) * | 2002-07-19 | 2004-06-25 | Surface Specialties Austria | Wässrige bindemittel |
| US7473442B2 (en) * | 2005-09-14 | 2009-01-06 | Ppg Industries Ohio, Inc. | Multi-component, waterborne coating compositions, related coatings and methods |
| US20080167431A1 (en) * | 2005-09-14 | 2008-07-10 | Ppg Industries Ohio, Inc. | Multi-component, waterborne coating compositions, related coatings and methods |
| US20090298989A1 (en) * | 2008-05-28 | 2009-12-03 | Funston Sr Randall A | 2K Waterborne Polyurethane Coating System and Methods Thereof |
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| EP0024727B1 (en) | 1979-09-01 | 1982-05-26 | FARMITALIA CARLO ERBA S.p.A. | Anthracycline glycosides, processes for their preparation and pharmaceutical composition containing them |
| DE3313236A1 (de) * | 1983-04-13 | 1984-10-18 | Bayer Ag, 5090 Leverkusen | Loesungsmittelhaltige, vernetzerhaltige beschichtungszubereitungen und ihre verwendung zur thermoaktiven einstrich-umkehrbeschichtung |
| US4791168A (en) * | 1987-04-15 | 1988-12-13 | Basf Corporation, Inmont Division | Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics |
| DE3936288A1 (de) * | 1989-11-01 | 1991-05-02 | Bayer Ag | In wasser dispergierbare bindemittelkombinationen, ein verfahren zur herstellung eines einbrennfuellers und dessen verwendung |
| DE4000748A1 (de) | 1990-01-12 | 1991-07-18 | Hoechst Ag | Waessrige ueberzugsmasse, deren herstellung und verwendung |
| JP3287605B2 (ja) * | 1991-05-17 | 2002-06-04 | 日本カーバイド工業株式会社 | 水性被覆用組成物 |
| DE4406159A1 (de) * | 1994-02-25 | 1995-08-31 | Bayer Ag | Wäßrige Polyester-Polyurethan-Dispersionen und ihre Verwendung in Beschichtungsmitteln |
| JPH08209060A (ja) * | 1995-02-02 | 1996-08-13 | Asahi Corp | 常乾型水性エマルジョン系塗料 |
| JPH1060311A (ja) * | 1996-08-12 | 1998-03-03 | Cosmo Sogo Kenkyusho:Kk | 水系制振塗料 |
| DE19654296A1 (de) * | 1996-12-27 | 1998-07-02 | Bollig & Kemper Gmbh & Co Kg | Beschichtung für ein elektrisch leitfähiges Substrat |
| ATE282652T1 (de) | 1998-08-17 | 2004-12-15 | Bayer Materialscience Ag | Wässriges beschichtungsmittel, dessen herstellung und verwendung für einbrennlacke |
| DE19858818A1 (de) * | 1998-12-21 | 2000-06-29 | Bayer Ag | Wäßrige reaktive Spachtelmassen (II) |
| DE10004723A1 (de) | 2000-02-03 | 2001-08-09 | Bayer Ag | Wässrige Sperrschicht auf Basis von Polyurethan-Disperionen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702940A (zh) * | 2012-06-12 | 2012-10-03 | 天长市巨龙车船涂料有限公司 | 一种汽车中涂漆 |
| CN111647343A (zh) * | 2020-06-12 | 2020-09-11 | 安徽东顺汽车研发有限公司 | 一种环保卡车喷漆的生产配方及其制备工艺 |
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| US20020107336A1 (en) | 2002-08-08 |
| EP1325048A1 (de) | 2003-07-09 |
| KR100842603B1 (ko) | 2008-07-01 |
| CN1205243C (zh) | 2005-06-08 |
| WO2002024779A1 (de) | 2002-03-28 |
| TW584657B (en) | 2004-04-21 |
| CZ2003860A3 (cs) | 2003-06-18 |
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| US6827983B2 (en) | 2004-12-07 |
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