CN111020549A - 一种锌铝镁镀层板的无铬钝化液 - Google Patents
一种锌铝镁镀层板的无铬钝化液 Download PDFInfo
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Abstract
本发明提供了一种锌铝镁镀层板的无铬钝化液，包括水性介质和以溶解/分散状态存在于水性介质中的至少以下成分：铝离子、磷酸盐、氟代酸、氧化剂和树脂。本发明通过氧化剂，磷酸盐和氟代酸的组合，引入铝离子作为成膜离子，通过磷化和氧化过程的协同作用，提高了锌镁铝镀层的耐腐蚀性和耐水性，并有效抑制了镁铝金属的黑变倾向，树脂的引入大大提高了涂层的附着力。由于不使用硅烷等不稳定组分，钝化液的稳定性可以提高到一年以上。且，本组合的主要成分为无机成分，从而可以在薄膜层的条件下实现对于镁铝金属或镀层的保护作用，烘干条件仅需50‑60度，从而大幅度降低了无铬钝化的使用成本，并扩展了镁铝金属或合金镀层的应用范围。
Description
技术领域
本发明涉及金属材料的表面处理防腐的钝化液，具体涉及一种锌铝镁镀层板的无铬钝化液。
背景技术
(1)锌铝镁是一种合金金属，主要是用作钢及钢制品的表面防腐蚀处理，包括各种锌系列的镀层和大量的钢制件整件浸镀防腐；一开始用作钢制品表面防腐处理的金属是纯锌，随着技术的发展的改进，陆续出现了铝锌合金和锌铝镁合金等合金金属，增加了金属层耐腐蚀的效果。
最开始是由日本的日新制钢公司在21世纪初研发并且量产，开发的目的是为了代替某些不锈钢的应用场景。国内的钢厂目前酒钢、唐钢和宝钢均有生产，后期随着产业升级，这将是一种逐渐被广泛应用的材料。
锌铝镁镀层钢板是指在现有的热镀锌镀层中添加了一定量的Al、Mg或者在热镀铝锌镀层中添加了一定量的Mg元素的镀层钢板，具有高耐蚀性、高切边保护性能的特点。锌铝镁镀层，是一种综合性能非常优秀的合金金属，制造成本只比铝锌镀层略高，其镀层的耐蚀性远高于纯锌和铝锌合金，同时对钢板切口的保护性能非常好，焊接性能与纯锌钢板相当。目前市场上锌铝镁钢板已经有了直接应用的案例，同时作为彩基板应用的锌铝镁彩涂板也由实现了量产并且大量应用，直接裸用的锌铝镁钢板属于高铝锌铝镁，作为彩基板的锌铝镁钢板属于低铝锌铝镁。未来随着建筑和各行业对于材料的要求逐步提高，锌铝镁镀层钢板有可能会逐渐取代镀铝锌钢板在市场上的应用。
(2)目前常规的无铬钝化分为两类，一类为以水解硅烷作为基础的弱酸性体系，例如：
1)发明名称--一种用于镀锌层表面的无铬钝化液，公开(公告)号-CN102337532A申请(专利权)人武汉迪赛高科技研究发展有限公司；
2)发明名称-一种无铬钝化液及热镀锌金属材料公开(公告)号-CN102373453A申请(专利权)攀钢集团钢铁钒钛股份有限公司；
3)发明名称-金属材料表面处理用组合物和处理方法公开(公告)号-CN1814860A申请(专利权)人日本帕卡濑精株式会社；
该类体系的共同特点是以一种或几种硅烷水解物作为主要成膜物质，PH在4-6，且基材基本以镀锌为主。
另一个体系为以树脂作为基础的弱碱性体系，例如：
美国专利-Composition and process for treating metal surfaces,PCTPub.No.:WO00/52226,Assignee:Henkel corporation,Gulph mills,PA。该类体系的共同特点是采用一种或几种树脂作为主要成膜物质，PH在8-10，基材以镀铝锌为主。
由于镀锌铝镁板的活性很强，原有的产品体系不能适应新基材的需求，例如：
硅烷配方在湿热试验中非常容易出现发黑现象，锌铝镁板具有很强的发黑倾向，在没有涂覆钝化膜的情况下极易出现不均匀黑斑以及整板发黑的现象，涂上硅烷体系钝化液后无法改变发黑倾向，特别是长期存放后板面出现严重黑变，无法满足下游客户需求。
树脂配方对于锌铝镁板的防护通常不足，盐雾试验较短，通常小于120小时甚至72小时，难以满足下游客户对于耐腐蚀性的需求。同时，树脂配方也存在长期存放板面的发黑问题。
本提案的目的的是在现有的生产线引入新的化学品，保护锌铝镁基板在运输和储存过程中无白锈和黑斑出现，提供合格的钝化板。
为此，本发明应运而生。
发明内容
有鉴于上，本发明旨在于提供一种可以应用于锌铝镁镀层板的钝化液，来克服使用硅烷配方钝化液应用于锌铝镁镀层板时的发黑现象和树脂配方类钝化液应用于锌铝镁镀层板的耐盐雾性差的弊端，为此，本发明提供了一种锌铝镁镀层板的无铬钝化液，其特征在于，包括水性介质和以溶解/分散状态存在于水性介质中的至少以下成分：铝离子、磷酸盐、氟代酸、氧化剂和树脂。
本发明的有益效果为：
本发明通过氧化剂，磷酸盐和氟代酸的组合，引入铝离子作为成膜离子，通过磷化和氧化过程的协同作用，提高了锌镁铝镀层的耐腐蚀性和耐水性，并有效抑制了镁铝金属的黑变倾向，树脂的引入大大提高了涂层的附着力。由于不使用硅烷等不稳定组分，钝化液的稳定性可以提高到一年以上。且，本组合的主要成分为无机成分，从而可以在薄膜层的条件下实现对于镁铝金属或镀层的保护作用，烘干条件仅需50-60度，从而大幅度降低了无铬钝化的使用成本，并扩展了镁铝金属或合金镀层的应用范围。
较佳的，所述铝离子和磷酸盐为含铝的磷酸盐或有机膦酸盐，选自以下组分中的一种或者多种的组合：三聚磷酸铝，磷酸二氢铝，PA80胶，有机次磷酸铝。
较佳的，所述含铝的磷酸盐或有机膦酸盐占以溶解/分散状态存在于水性介质中的总成分的5％-45％。
较佳的，所述氟代酸为过渡金属氟代酸，选自以下组分中的一种或者多种的组合：氟锆酸，氟钛酸，氟铪酸。
较佳的，所述过渡金属氟代酸占以溶解/分散状态存在于水性介质中的总成分的0.5％-5.5％。
较佳的，所述氧化剂为氧化性盐，选自以下组分中的一种或者多种的组合：硝酸锌，硝酸锰，硝酸铈，硝酸铝，硝酸镍，硝酸铜，硝酸铁，硝酸镁，硝酸氧锆，硝酸锆，硝酸钛。
较佳的，所述氧化性盐占以溶解/分散状态存在于水性介质中的总成分的3-30％。
较佳的，所述树脂选自以下组分中的一种或者多种的组合：阳离子或非离子树脂，种类为丙烯酸树脂，聚氨酯树脂，环氧树脂。
较佳的，所述树脂占以溶解/分散状态存在于水性介质中的总成分的20-80％。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
对比实施例1：以水解氨基硅烷和环氧硅烷作为主体，PH值在4-6，其他组分由过渡金属氟代酸，磷酸，丙烯酸树脂等，在镀锌基板上具有良好的耐腐蚀性，耐湿热性和重涂性，但在锌铝镁基板上湿热性能极差，120小时湿热实验(49摄氏度，98％相对湿度)后表面色差Delta E≥5，无法满足客户需求。
对比实施例2：树脂含量为55％，PH在8-9，其他组分由锆盐，磷酸盐组成，在镀锌基板上可以提供较好的耐腐蚀性和湿热性，但在锌铝镁基板上盐雾性能很差，72小时盐雾试验腐蚀面积大于10％，无法满足客户需求。
下述实施例中，将以溶解/分散状态存在于水性介质中的铝离子、磷酸盐、氟代酸、氧化剂和树脂等除水以外的成分称为总成分。
实施例1：磷酸二氢铝2％，硝酸锌4％，水性丙烯酸树脂24％，氟铪酸0.2％；余量为水，混合后搅拌乳化成型得钝化液。具体的，磷酸二氢铝占总成分的6.62％，硝酸锌占总成分的13.25％，水性丙烯酸树脂占总成分的79.47％，氟铪酸占总成分的0.66％。
实施例2：磷酸二氢铝10％，硝酸锌6％，水性丙烯酸树脂12％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，磷酸二氢铝占总成分的33.9％，硝酸锌占总成分的20.34％，水性丙烯酸树脂占总成分的40.68％，氟钛酸占总成分的5.08％。
实施例3：磷酸二氢铝8％，硝酸锌6％，水性环氧树脂15％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，磷酸二氢铝占总成分的26.23％，硝酸锌占总成分的19.67％，水性环氧树脂占总成分的49.18％，氟钛酸占总成分的4.92％。
实施例4：磷酸二氢铝8％，硝酸镁6％，水性聚氨酯树脂12％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，磷酸二氢铝占总成分的29.09％，硝酸镁占总成分的21.82％，水性聚氨酯树脂占总成分的43.64％，氟钛酸占总成分的5.45％。
实施例5：有机磷酸铝10％，硝酸铈1％，水性聚氨酯树脂18％，氟锆酸1％；余量为水，混合后搅拌乳化成型得钝化液。具体的，有机磷酸铝占总成分的33.33％，硝酸铈占总成分的3.33％，水性聚氨酯树脂占总成分的60％，氟锆酸占总成分的3.33％。值得一提的是，实际投料中误差在0.01％，但不会影响实际产品效果。
实施例6：磷酸二氢铝8％，硝酸铝6％，水性丙烯酸树脂15％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，磷酸二氢铝占总成分的26.23％，硝酸铝占总成分的19.67％，水性丙烯酸树脂占总成分的49.18％，氟钛酸占总成分的4.92％。
实施例7：PA80 10％，硝酸锌6％，水性丙烯酸树脂13％，氟锆酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，PA80占总成分的32.79％，硝酸锌占总成分的19.67％，水性丙烯酸树脂占总成分的42.63％，氟锆酸占总成分的4.92％。值得一提的是，实际投料中误差在0.01％，但不会影响实际产品效果。
实施例8：磷酸二氢铝10％，硝酸锰3％，水性丙烯酸树脂17％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，磷酸二氢铝占总成分的31.75％，硝酸锰占总成分的9.52％，水性丙烯酸树脂占总成分的53.97％，氟钛酸占总成分的4.76％。
实施例9：有机磷酸铝10％，硝酸锆2％，水性丙烯酸树脂16％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，有机磷酸铝占总成分的33.90％，硝酸锆占总成分的6.78％，水性丙烯酸树脂占总成分的54.24％，氟钛酸占总成分的5.08％。
实施例10：有机磷酸铝10％，硝酸氧锆2％，水性丙烯酸树脂16％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，有机磷酸铝占总成分的33.90％，硝酸氧锆占总成分的6.78％，水性丙烯酸树脂占总成分的54.24％，氟钛酸占总成分的5.08％。
实施例11：有机磷酸铝10％，硝酸铁2％，水性丙烯酸树脂16％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，有机磷酸铝总成分的33.90％，硝酸铁总成分的6.78％，水性丙烯酸树脂总成分的54.24％，氟钛酸总成分的5.08％。
实施例12：有机磷酸铝10％，硝酸铜2％，水性丙烯酸树脂16％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，有机磷酸铝总成分的33.90％，硝酸铜总成分的6.78％，水性丙烯酸树脂总成分的54.24％，氟钛酸总成分的5.08％。
实施例13：有机磷酸铝10％，硝酸镍6％，水性丙烯酸树脂12％，氟钛酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，有机磷酸铝占总成分的33.90％，硝酸镍占总成分的20.34％，水性丙烯酸树脂占总成分的40.68％，氟钛酸占总成分的5.08％。
实施例14：有机磷酸铝10％，硝酸钛1％，水性聚氨酯树脂16％，氟锆酸0.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，有机磷酸铝占总成分的36.36％，硝酸钛占总成分的3.64％，水性聚氨酯树脂占总成分的58.18％，氟锆酸占总成分的1.82％。
实施例15：磷酸二氢铝13％，硝酸锌8％，水性聚氨酯树脂8％，氟锆酸1.5％；余量为水，混合后搅拌乳化成型得钝化液。具体的，磷酸二氢铝占总成分的47.46％，硝酸锌占总成分的30.51％，水性聚氨酯树脂占总成分的16.95％，氟锆酸占总成分的5.08％。
将实施例1～15的铝离子、磷酸盐、氟代酸、氧化剂和树脂与总成分比例汇集如下表：
将实施例1～15进行理化指标测试，并与对比实施例1～2对比如下：
| 烘干温度 | 存储时间 | 耐黑变 | 重涂性 | 耐盐雾 | |
| 对比实施例1 | 80 | 3个月 | ≥5 | 良好 | 72小时 |
| 对比实施例2 | 80 | 3个月 | ≤3 | 良好 | 48小时 |
| 实施例1 | 60 | 12个月 | ≤3 | 良好 | ≥72小时 |
| 实施例2 | 60 | 12个月 | ≤3 | 良好 | ≥96小时 |
| 实施例3 | 60 | 12个月 | ≤3 | 良好 | ≥168小时 |
| 实施例4 | 60 | 12个月 | ≤3 | 良好 | ≥120小时 |
| 实施例5 | 60 | 12个月 | ≤3 | 良好 | ≥96小时 |
| 实施例6 | 60 | 12个月 | ≤3 | 良好 | ≥168小时 |
| 实施例7 | 60 | 12个月 | ≤3 | 良好 | ≥96小时 |
| 实施例8 | 60 | 12个月 | ≤3 | 良好 | ≥96小时 |
| 实施例9 | 60 | 12个月 | ≤3 | 良好 | ≥168小时 |
| 实施例10 | 60 | 12个月 | ≤3 | 良好 | ≥168小时 |
| 实施例11 | 60 | 12个月 | ≤3 | 良好 | ≥120小时 |
| 实施例12 | 60 | 12个月 | ≤3 | 良好 | ≥96小时 |
| 实施例13 | 60 | 12个月 | ≤3 | 良好 | ≥96小时 |
| 实施例14 | 60 | 12个月 | ≤3 | 良好 | ≥96小时 |
| 实施例15 | 50 | 12个月 | ≤3 | 良好 | ≥72小时 |
本领域中普通技术人员可根据上述说明对本发明做出多种变化。因而，在不违反本发明的权利要求宗旨的前提下，实施例中的某些细节不应构成对本发明的限定，本发明将以所附权利要求书界定的范围作为保护范围。
Claims (9)
1.一种锌铝镁镀层板的无铬钝化液，其特征在于，包括水性介质和以溶解/分散状态存在于水性介质中的至少以下成分：铝离子、磷酸盐、氟代酸、氧化剂和树脂。
2.根据权利要求1所述的无铬钝化液，其特征在于：所述铝离子和磷酸盐为含铝的磷酸盐或有机膦酸盐，选自以下组分中的一种或者多种的组合：三聚磷酸铝，磷酸二氢铝，PA80胶，有机次磷酸铝。
3.根据权利要求2所述的无铬钝化液，其特征在于：所述含铝的磷酸盐或有机膦酸盐占以溶解/分散状态存在于水性介质中的总成分的5％-45％。
4.根据权利要求1所述的无铬钝化液，其特征在于：所述氟代酸为过渡金属氟代酸，选自以下组分中的一种或者多种的组合：氟锆酸，氟钛酸，氟铪酸等。
5.根据权利要求4所述的无铬钝化液，其特征在于：所述过渡金属氟代酸占以溶解/分散状态存在于水性介质中的总成分的0.5％-5.5％。
6.根据权利要求1所述的无铬钝化液，其特征在于：所述氧化剂为氧化性盐，选自以下组分中的一种或者多种的组合：硝酸锌，硝酸锰，硝酸铈，硝酸铝，硝酸镍，硝酸铜，硝酸铁，硝酸镁，硝酸氧锆，硝酸锆，硝酸钛。
7.根据权利要求6所述的无铬钝化液，其特征在于：所述氧化性盐占以溶解/分散状态存在于水性介质中的总成分的3-30％。
8.根据权利要求1所述的无铬钝化液，其特征在于：所述树脂选自以下组分中的一种或者多种的组合：阳离子或非离子树脂，种类为丙烯酸树脂，聚氨酯树脂，环氧树脂。
9.根据权利要求8所述的无铬钝化液，其特征在于：所述树脂占以溶解/分散状态存在于水性介质中的总成分的20-80％。
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