CN107400883B - 镀锌板涂装前硅烷/锆复合处理剂及其制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
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Abstract
本发明公开了一种镀锌板涂装前硅烷/锆复合处理剂及其制备方法，该复合处理剂主要由硅烷、锆氟络合物、锆酸酯、稀土铈盐、醇和去离子水等组成，该复合处理剂采用化学复配的方法制备而成，制成的复合处理剂可应用于镀锌板涂装前的化学转化表面处理。该复合处理剂具有无磷无铬的环保特点，可常温处理镀锌板，无需加热节能能耗，获得的硅烷复合膜层致密，耐蚀防护性能好等优点，与有机涂料结合性能优异，可替代磷化处理工艺技术。
Description
技术领域
本发明涉及镀锌板涂装前的表面处理技术领域，特别是一种镀锌板涂装前硅烷/锆复合处理剂及其制备方法。
技术背景
镀锌板是为防止钢板表面遭受腐蚀，延长其使用寿命，在钢板表面镀涂以一层金属锌，这种镀涂锌的薄钢板称为镀锌板，为了防止在使用、储运过程中其表面出现锈蚀情况，镀锌板表面需进行钝化处理，传统的铬酸盐钝化由于水溶性六价铬可以自由从钝化膜中溶出起到再钝化作用，保证了钝化膜的自修复能力，使其具有优越的耐腐蚀性，可由于六价铬极强的致癌性和环境危害性，其使用越来越受到严格限制。开发无铬钝化工艺技术也越来越受到人们的关注。目前虽然有各种无铬钝化技术，可无铬钝化技术仍存在不少缺陷，或(无自修复功能)耐蚀性差，或处理工艺适用性有限(多为喷淋工艺)，或成本高昂很难达到应用要求。
发明内容
针对以上技术问题，本发明的目的在于提供一种镀锌板涂装前硅烷/锆复合处理剂及其制备方法。使硅烷和无机锆、有机锆在镀锌板表面进行协同转化成膜，形成强交联、高性能的复合膜，并藉由稀土铈改性复合膜，使膜层具有自修复性能，提高裸膜耐蚀性。本发明技术方案具体如下：
本发明首先公开了一种镀锌板涂装前硅烷/锆复合处理剂的制备方法，所述镀锌板涂装前硅烷/锆复合处理剂的组成原料各组分的质量百分数为：
所述的镀锌板涂装前硅烷/锆复合处理剂的制备方法包括如下步骤：
(1)往反应釜内加入所需水总量的80-90％，开启反应釜进行搅拌；
(2)往反应釜内加入锆氟络合物，搅拌均匀使其彻底混合；
(3)往反应釜内缓慢加入硅烷和醇的混合物，搅拌使其彻底溶解；
(4)往反应釜内缓慢加入锆酸酯和醇的混合物，搅拌均匀使其彻底混合；
(5)停止搅拌，循环过滤除去反应釜内的悬浮物、颗粒物后静置24小时以上直至溶液澄清稳定；
(6)往反应釜内加入铈盐，搅拌均匀使其彻底混合；
(7)最后补足余量水，搅拌均匀使其彻底混合后即得复合处理剂。
优选的，所述的硅烷其单体通式表示为：
R(4-n)-Si-(OR’)n，其中n＝1，2，3；
R表示的基团为氢、烷基、氨基、环氧基、乙烯基、脲基或异氰酸基；OR’表示的基团为甲氧基，乙氧基或乙酰氧基；
所述的硅烷为单体或其低聚物中的一种或多种，所述低聚物的聚合度为2-20。
优选的，所述的锆氟络合物选自氟锆酸及其盐中的一种或多种。
优选的，所述的锆酸酯选自双(柠檬酸二乙酯)二丙氧基锆螯合物、锆酸盐乳酸盐螯合物、三乙醇胺锆螯合物、三乙醇胺多元醇锆螯合物、乙酰丙酮锆中的一种或多种。
优选的，所述的铈盐选自硝酸高铈、硝酸亚铈、硝酸铈铵、硫酸高铈、醋酸铈中的一种或多种。
优选的，所述的醇选自乙醇、异丙醇、丙二醇、丙三醇中的一种或多种。
优选的，所述的步骤(3)所加入的醇占醇总量的60-80％；所述的步骤(4)所加入的醇为步骤(3)后余量的醇。
本发明还公开了一种上述方法制备得到的镀锌板涂装前硅烷/锆复合处理剂。
与现有镀锌板涂装前处理技术相比，镀锌板涂装前硅烷/锆复合处理剂及制备方法具有以下几个优点：(1)无磷无铬无有害物质，环保可靠；(2)常温操作，无需加热，节约能源；(3)处理方式兼容性强，适用喷淋或浸渍工艺；(4)本发明制备方法得到的镀锌板涂装前硅烷/锆复合处理剂性能优越，获得的复合膜层致密耐蚀性好，与有机涂料结合好，涂层耐中性盐雾试验优异。
具体实施方式
本发明公开了一种镀锌板涂装前硅烷/锆复合处理剂的制备方法，所述镀锌板涂装前硅烷/锆复合处理剂的组成原料各组分的质量百分数为：
所述的镀锌板涂装前硅烷/锆复合处理剂的制备方法包括如下步骤：
(1)往反应釜内加入所需水总量的80-90％，开启反应釜进行搅拌；
(2)往反应釜内加入锆氟络合物，搅拌均匀使其彻底混合；
(3)往反应釜内缓慢加入硅烷和醇的混合物，搅拌使其彻底溶解；
(4)往反应釜内缓慢加入锆酸酯和醇的混合物，搅拌均匀使其彻底混合；
(5)停止搅拌，循环过滤除去反应釜内的悬浮物、颗粒物后静置24小时以上直至溶液澄清稳定；
(6)往反应釜内加入铈盐，搅拌均匀使其彻底混合；
(7)最后补足余量水，搅拌均匀使其彻底混合后即得复合处理剂。
优选的，所述的硅烷其单体通式表示为：
R(4-n)-Si-(OR’)n，其中n＝1，2，3；
R表示的基团为氢、烷基、氨基、环氧基、乙烯基、脲基或异氰酸基；OR’表示的基团为甲氧基，乙氧基或乙酰氧基；
所述的硅烷为单体或其低聚物中的一种或多种，所述低聚物的聚合度为2-20。
优选的，所述的锆氟络合物选自氟锆酸及其盐中的一种或多种。
优选的，所述的锆酸酯选自双(柠檬酸二乙酯)二丙氧基锆螯合物、锆酸盐乳酸盐螯合物、三乙醇胺锆螯合物、三乙醇胺多元醇锆螯合物、乙酰丙酮锆中的一种或多种。
优选的，所述的铈盐选自硝酸高铈、硝酸亚铈、硝酸铈铵、硫酸高铈、醋酸铈中的一种或多种。
优选的，所述的醇选自乙醇、异丙醇、丙二醇、丙三醇中的一种或多种。
优选的，所述的步骤(3)所加入的醇占醇总量的60-80％；所述的步骤(4)所加入的醇为步骤(3)后余量的醇。
下面结合实施例对本发明做进一步说明。
实施例1：
本实施例的镀锌板涂装前硅烷/锆复合处理剂组成原料各组分的质量百分数为：
制备方法包括如下步骤：
(1)往反应釜内加入所需水总量的80％，开启反应釜进行搅拌；
(2)往反应釜内加入氟锆酸，搅拌均匀使其彻底混合；
(3)往反应釜内缓慢加入丙基三甲氧基硅烷和异丙醇混合物(70％异丙醇)，搅拌使其彻底溶解；
(4)往反应釜内缓慢加入双(柠檬酸二乙酯)二丙氧基锆螯合物和异丙醇混合物(30％异丙醇)，搅拌使其彻底溶解；
(5)停止搅拌，循环过滤除去反应釜内的悬浮物、颗粒物后静置24小时以上直至溶液澄清稳定；
(6)往反应釜内加入硝酸亚铈，搅拌均匀使其彻底混合；
(7)最后补足余量水，搅拌均匀使其彻底混合后即得复合处理剂。
将所述的复合处理剂对镀锌板进行浸渍处理5分钟，烘干后进行环氧粉末喷涂，并进行性能测试。
实施例2：
本实施例的镀锌板涂装前硅烷/锆复合处理剂组成原料各组分的质量百分数为：
所述的镀锌板复合处理剂的制备方法同实施例1。
将所述的复合处理剂对镀锌板进行喷淋处理2分钟，烘干后喷涂水性丙烯酸树脂，并进行性能测试。
实施例3：
本实施例的镀锌板涂装前硅烷/锆复合处理剂组成原料各组分的质量百分数为：
所述的镀锌板硅烷复合处理剂的制备方法同实施例1。
将所述的复合处理剂对镀锌板进行喷淋处理1.5分钟，烘干后进行阴极电泳涂装，并进行性能测试。
对比例1：
将实施例3所述的复合处理剂组成原料中去除硝酸亚铈和三乙醇胺多元醇锆螯合物后，对镀锌板进行喷淋处理1.5分钟，烘干后进行阴极电泳涂装，并进行性能测试。
对比例2：
将某三元锌系磷化处理剂对镀锌板进行喷淋处理1.5分钟，烘干后进行涂料涂装，并进行性能测试。
对镀锌板表面的复合膜及其涂装性能试验结果表明，所述的复合膜的各项理化性能都有了明显的提高，各检测指标相当于甚至优于三元锌系磷化处理。
对镀锌板表面的复合膜及其涂装性能试验结果见表1。
表1：本发明制备的镀锌板表面的复合膜及其涂装性能试验结果
*浸泡试验后涂层面上无起皮鼓泡及锈蚀等现象；盐雾试验后涂层面上无起皮鼓泡等现象且划叉沿线的单边腐蚀扩散宽度≤2mm为通过的最大试验小时数。
实施例和对比例综合证明本发明技术制备的复合处理剂及其在镀锌板表面形成的复合转化膜有良好的致密性耐腐蚀性能，与有机涂料结合号，各项性能优异，可替代磷化处理工艺技术，应用于镀锌板涂装前处理的规模生产。
Claims (6)
1.一种镀锌板涂装前硅烷/锆复合处理剂的制备方法，其特征在于：所述镀锌板涂装前硅烷/锆复合处理剂的组成原料各组分的质量百分数为：
所述的锆酸酯选自双(柠檬酸二乙酯)二丙氧基锆螯合物、锆酸盐乳酸盐螯合物、三乙醇胺锆螯合物、三乙醇胺多元醇锆螯合物、乙酰丙酮锆中的一种或多种；
所述的铈盐选自硝酸高铈、硝酸亚铈、硝酸铈铵、硫酸高铈、醋酸铈中的一种或多种；
所述的镀锌板涂装前硅烷/锆复合处理剂的制备方法包括如下步骤：
(1)往反应釜内加入所需水总量的80-90％，开启反应釜进行搅拌；
(2)往反应釜内加入锆氟络合物，搅拌均匀使其彻底混合；
(3)往反应釜内缓慢加入硅烷和醇的混合物，搅拌使其彻底溶解；
(4)往反应釜内缓慢加入锆酸酯和醇的混合物，搅拌均匀使其彻底混合；
(5)停止搅拌，循环过滤除去反应釜内的悬浮物、颗粒物后静置24小时以上直至溶液澄清稳定；
(6)往反应釜内加入铈盐，搅拌均匀使其彻底混合；
(7)最后补足余量水，搅拌均匀使其彻底混合后即得复合处理剂。
2.如权利要求1所述的镀锌板涂装前硅烷/锆复合处理剂的制备方法，其特征在于所述的硅烷其单体通式表示为：
R(4-n)-Si-(OR’)n，其中n＝1，2，3；
R表示的基团为氢、烷基、氨基、环氧基、乙烯基、脲基或异氰酸基；OR’表示的基团为甲氧基，乙氧基或乙酰氧基；
所述的硅烷为单体或其低聚物中的一种或多种，所述低聚物的聚合度为2-20。
3.如权利要求1所述的镀锌板涂装前硅烷/锆复合处理剂的制备方法，其特征在于所述的锆氟络合物选自氟锆酸及其盐中的一种或多种。
4.如权利要求1所述的镀锌板涂装前硅烷/锆复合处理剂的制备方法，其特征在于所述的醇选自乙醇、异丙醇、丙二醇、丙三醇中的一种或多种。
5.如权利要求1所述的镀锌板涂装前硅烷/锆复合处理剂的制备方法，其特征在于所述的步骤(3)所加入的醇占醇总量的60-80％；所述的步骤(4)所加入的醇为步骤(3)后余量的醇。
6.一种如权利要求1所述方法制备得到的镀锌板涂装前硅烷/锆复合处理剂。
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| EP1887105A1 (en) * | 2006-08-08 | 2008-02-13 | The Boeing Company | Chromium-free conversion coating |
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