CN101760736B - 一种镀锌钢板表面处理剂和一种镀锌钢板及其制备方法 - Google Patents
一种镀锌钢板表面处理剂和一种镀锌钢板及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种镀锌钢板表面处理剂,其含有:A、含环氧基的硅烷衍生物,B、含烷基的硅烷衍生物,C、烷氧基硅烷衍生物,以及D、下述三种中的一种或多种:阳离子聚合物水分散体、非离子聚合物水分散体和水溶性聚合物。本发明还公开了其制备方法:5~70℃下,将所述的各成分均匀混合0.5~8小时,即可制得。本发明还公开了表面涂覆了该表面处理剂的镀锌钢板及其制备方法。本发明的镀锌钢板表面处理剂具有优异的抗腐蚀性、耐碱性、耐溶剂性、再涂装性、耐高温性和导电性。
Description
技术领域
本发明涉及一种镀锌钢板表面处理剂及其制备方法,和一种镀锌钢板及其制备方法。
背景技术
为防止钢板表面遭受腐蚀,延长其使用寿命,通常在钢板表面涂覆一层金属锌。这种涂锌的钢板称为镀锌钢板。
对于刚刚制得的镀锌钢板,有时需要立即对其作“镀后表面处理”,为后续成型或涂敷涂料等工艺作表面准备,同时也为后续操作、储存和运输过程中为镀锌钢板提供短期保护。目前,许多表面处理工艺已应用于工业中,如磷化、铬酸盐化、涂油以及它们的变种和组合。
铬酸盐化从上世纪30年代开始应用于工业界,一度成为镀锌钢板后表面处理使用最广泛的工艺。铬酸盐化可提供短期防锈和防蚀保护,其过程为,铬酸、铬盐和无机酸的水溶液在金属表面上产生薄的转化层,金属与溶液之间的化学反应引起金属溶解,并形成含有复杂的铬和金属化合物的保护膜。该方法的工艺简单,成本低,抗蚀性能好。但是涂膜中的含铬化合物,特别是六价铬元素,对人体及环境都有严重危害。
为了寻求对环境友好的工艺,近年来多种无铬有机或无机表面处理技术得到发展,如含金属钼、钒或锆的无机化学转化膜体系、聚合物水分散体-二氧化硅体系和聚合物水分散体-硅酸盐体系等等。
目前,将含硅有机-无机纳米杂化材料引入到镀锌板的表面处理工艺是研究的热点之一。硅烷被用来作为金属表面的防腐蚀的处理剂的研究由来已久,如:U.S.Patent No.20030049486A1,US20050058843A1与EP 1153089B1通过引入一种含有乙烯基硅烷与含有烷基的硅烷组合物处理金属(主要是锌)的表面,US6955728B1则通过用一种含有酰氧基硅烷的处理剂来处理锌的表面。CN 1887449A与CN 1887451A则将硅烷、水溶性聚合物以及含钒化合物的组合物作为镀锌钢板的表面处理剂,使钢板表面有耐碱性和耐溶剂性。但这些表面处理剂或者防腐蚀效果不理想,或者含有有毒重金属元素,因此,亟待寻求具有同样优异的防腐蚀性能和更加符合环保要求的镀锌钢板表面处理剂。
发明内容
本发明所要解决的技术问题是为了克服现有的镀锌钢板表面处理剂防腐蚀效果不理想,含有有毒重金属的缺陷,而提供一种具有各种优异性能、且不含有毒重金属元素的镀锌钢板表面处理剂及其制备方法,以及一种涂覆该表面处理剂的镀锌钢板及其制备方法。
本发明的镀锌钢板表面处理剂含有:A、含环氧基的硅烷衍生物,B、含烷基的硅烷衍生物,C、烷氧基硅烷衍生物,以及D、下述三种中的一种或多种:阳离子聚合物水分散体、非离子聚合物水分散体和水溶性聚合物。
成分A:所述的含环氧基的硅烷衍生物是指分子结构中含至少一个环氧基的硅烷类化合物,较佳的为如式I所示的化合物,最优选缩水甘油醚丙基甲基二甲氧基硅烷、缩水甘油醚丙基三甲氧基硅烷和缩水甘油醚乙基三乙酰基硅烷中的一种或多种,所述的含环氧基的硅烷衍生物的含量较佳的为20~45%,更佳的为20~35%,最佳的为20~25%;百分比为其质量占A、B、C和D总质量的百分比。
式I
其中,Y为C1-C6的亚烷基;R为C1-C6烷基;X为C1-C4烷氧基或C2-C4酰氧基;n为0或1。
成分B:所述的含烷基的硅烷衍生物指分子结构中含至少一个烷基的硅烷类化合物,较佳的为如式II和/或式III所示的化合物,优选甲基三甲氧基硅烷、二甲基二甲氧基硅烷、甲基三乙氧基硅烷、1,2-二-三乙氧基硅基乙烷。所述的含烷基的硅烷衍生物的含量较佳的为15~45%,更佳的为15~35%,最佳的为15~25%;百分比为其质量占A、B、C和D总质量的百分比。
式II 式III
其中,R和Z独立的为C1-C6烷基;M为C1-C6亚烷基;X为C1-C4烷氧基或C2-C4酰氧基;n为0或1。
成分C:所述的烷氧基硅烷衍生物是指分子结构中含至少一个烷氧基的硅烷类化合物,较佳的如式IV所示的化合物,优选四甲氧基硅烷、四乙氧基硅烷和四丙氧基硅烷中的一种或多种。所述的烷氧基硅烷衍生物的含量较佳的为5~30%,更佳的为5~20%,最佳的为5~10%;百分比为其质量占A、B、C和D总质量的百分比。
HnSiX4-n
其中,X为C1-C4烷氧基;n为0或1。
成分D:所述的阳离子聚合物水分散体较佳的为阳离子聚氨酯水分散体、阳离子丙烯酸酯水分散体、阳离子环氧水分散体和阳离子醇酸水分散体中的一种或多种。所述的非离子聚合物水分散体较佳的为非离子聚氨酯水分散体、非离子丙烯酸酯水分散体、非离子环氧水分散体和非离子醇酸水分散体重的一种或多种。所述的水溶性聚合物较佳的为水溶性聚乙二醇、水溶性聚丙烯酰胺、水溶性聚氨酯和水溶性聚丙烯酸中的一种或多种。
所述的阳离子聚合物水分散体、非离子聚合物水分散体或水溶性聚合物的分子量对本发明的表面处理剂的应用效果没有影响,可选用现有的各种分子量的阳离子聚合物水分散体、非离子聚合物水分散体或水溶性聚合物使用。
所述的成分D的含量较佳的为30~60%,更佳的为30~50%,最佳的为30~40%;百分比为其质量占A、B、C和D总质量的百分比。
本发明中,在反应物中还可加入酸性化合物和/或水。
其中,所述的酸性化合物较佳的为有机酸或无机酸。所述的无机酸较佳的为盐酸、硫酸、硝酸、磷酸、氟钛酸、氟锆酸、氟硅酸或氢氟酸;所述的有机酸较佳的为醋酸或羟基磺酸。所述的酸性化合物的含量较佳的为前述A、B、C和D四种成分总质量的5~35%,更佳的为5~20%,最佳的为5~10%。
其中,所述的水的含量较佳的为前述A、B、C和D四种成分总质量的50~200%,更佳的为100~200%,最佳的为150~200%。
本发明的镀锌钢板表面处理剂为均一的半透明状物质,其pH值一般为2~7。也可使用pH调节剂调节pH至合适值。
本发明还涉及本发明的组合物的制备方法:将上述各成分均匀混合,即可制得。混合的温度和时间可为本领域常规条件,优选条件为:混合的温度较佳的为5~70℃,通常在自然室温下进行即可;混合的时间较佳的为0.5~8小时,更佳的为1~3小时。较佳的,在搅拌条件下进行混合使其混合均匀。
本发明还进一步的涉及一种镀锌钢板,其表面涂覆了本发明的镀锌钢板表面处理剂。该镀锌钢板表面涂覆的本发明的镀锌钢板表面处理剂的量较佳的为0.5~2mg/m2。本发明中,所述的镀锌钢板可为本领域各种类型的镀锌钢板,如电镀锌钢板或热镀锌钢板等。
本发明进一步的涉及所述的镀锌钢板的制备方法,其本发明的镀锌钢板表面处理剂涂覆镀锌钢板上,成膜温度为60~120℃。
本发明所用试剂及原料均市售可得。
本发明的积极进步效果在于:本发明的镀锌钢板表面处理剂不含有毒重金属元素,且具有优异的抗腐蚀性、耐碱性、耐溶剂性、耐高温性、导电性以及再涂装性。
具体实施方式
下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在所述的实施例范围之中。
实施例1~12的镀锌钢板表面处理剂配方中各组分依次为A、含环氧基的硅烷衍生物,B、含烷基的硅烷衍生物,C、烷氧基硅烷衍生物,以及D、下述三种中的一种或多种:阳离子聚合物水分散体、非离子聚合物水分散体和水溶性聚合物。各组分的含量如表1所示。
实施例1
将上述成分按表1中配比5℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至7,8小时后即可制得热镀锌钢板表面处理剂。
实施例2
非离子聚氨酯水分散体,醋酸。
将上述成分按表1中配比10℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至6,3小时后即可制得镀锌钢板表面处理剂。
实施例3
将上述成分按表1中配比20℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至5,2小时后即可制得镀锌钢板表面处理剂。
实施例4
将上述成分按表1中配比40℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至3,1小时后即可制得镀锌钢板表面处理剂。
实施例5
将上述成分按表1中配比25℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至2,0.5小时后即可制得镀锌钢板表面处理剂。
实施例6
将上述成分按表1中配比50℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至4,2小时后即可制得镀锌钢板表面处理剂。
实施例7
将上述成分按表1中配比15℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至3,1.5小时后即可制得镀锌钢板表面处理剂。
实施例8
将上述成分按表1中配比70℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至6,2小时后即可制得镀锌钢板表面处理剂。
实施例9
将上述成分按表1中配比60℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至5,2小时后即可制得镀锌钢板表面处理剂。
实施例10
水溶性聚氨酯,氢氟酸,水。
将上述成分按表1中配比25℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至3,1小时后即可制得镀锌钢板表面处理剂。
实施例11
将上述成分按表1中配比30℃下均匀混合,用pH调节剂(KOH水溶液或硝酸)调节pH至4,3小时后即可制得镀锌钢板表面处理剂。
实施例12
将上述成分按表1中配比25℃下均匀混合,用pH调节剂(KOH水溶液或盐酸)调节pH至4,3小时后即可制得镀锌钢板表面处理剂。
表1实施例1~12各组分含量
实施例 | A含环氧基的硅烷衍生物/g | B含烷基的硅烷衍生物/g | C烷氧基硅烷衍生物/g | D阳离子或非离子的聚合物水分散体或水溶性聚合物/g | 酸性化合物/g | 水/g |
1 | 20 | 45 | 5 | 30 | \ | \ |
2 | 45 | 15 | 10 | 30 | 5 | \ |
3 | 30 | 30 | 5 | 35 | \ | 50 |
4 | 20 | 20 | 15 | 45 | 20 | 150 |
5 | 25 | 15 | 30 | 30 | 30 | 200 |
6 | 40 | 15 | 5 | 40 | 35 | 120 |
7 | 35 | 25 | 10 | 30 | 15 | 80 |
8 | 20 | 30 | 20 | 30 | 25 | 60 |
9 | 20 | 15 | 15 | 50 | 20 | 180 |
10 | 20 | 20 | 5 | 55 | 8 | 100 |
11 | 25 | 20 | 25 | 30 | 12 | 120 |
12 | 15 | 15 | 5 | 65 | 5 | 100 |
实施例13
将市售镀锌钢板用汉高Ridoline 1559弱碱性脱脂清洗剂浸渍或喷淋处理浓度:10~20%;温度:室温;清洗时间:1~2分钟)。用自来水对清洗过的镀锌钢板漂洗。对镀锌钢板表面残留水份空气吹干备用。用涂敷机将实施例10制得的表面处理剂均匀涂敷在已处理过的钢板表面。涂覆量为0.5mg/m2,成膜温度为60℃。
实施例14
将市售镀锌钢板用汉高Ridoline 1559弱碱性脱脂清洗剂浸渍或喷淋处理浓度:10~20%;温度:室温;清洗时间:1~2分钟)。用自来水对清洗过的镀锌钢板漂洗。对镀锌钢板表面残留水份空气挤干备用。用涂敷机将实施例11制得的表面处理剂均匀涂敷在已处理过的钢板表面。涂覆量为1.5mg/m2,成膜温度为90℃。
实施例15
将市售镀锌钢板用汉高Ridoline 1559弱碱性脱脂清洗剂浸渍或喷淋处理浓度:10~20%;温度:室温;清洗时间:1~2分钟)。用自来水对清洗过的镀锌钢板漂洗。对镀锌钢板表面残留水份空气吹干备用。用涂敷机将实施例12制得的表面处理剂均匀涂敷在已处理过的钢板表面。涂覆量为2mg/m2,成膜温度为120℃。
效果实施例
一、基材:市售镀锌钢板(未经前处理,或者仅涂油处理)
二、基材清洗:
1.用汉高Ridoline 1559弱碱性脱脂清洗剂浸渍或喷淋处理。(浓度:10~20%wt);温度:室温;清洗时间:1~2分钟。)
2.用自来水对清洗过的镀锌钢板漂洗。
3.对镀锌钢板表面残留水份空气吹干或挤干备用。
三、涂敷:用涂敷线棒或涂敷机将由下表配方制得的对比表面处理剂1~4以及本发明的表面处理剂分别均匀涂敷在已处理过的钢板表面。下述百分比为质量百分比。
将上述反应物质混合均匀后,在25℃条件下搅拌30分钟后得到均一物质。
四、固化:钢板峰值温度(Peak Metal Temperature,PMT)控制在80~120℃),干膜膜厚为0.5~2mg/m2。
五、测试:
(1)耐腐蚀性:根据美国材料学会标准方法ASTM B117-03,测腐蚀面积。
(2)耐碱性:汉高Ridoline 336、50℃,浸没2分钟,水洗后目测板面。
(3)耐溶剂性:用棉球蘸80%酒精/丁酮(MEK),负重约1公斤在样板表面来回擦30次,测定擦试前后的ΔE值。
(4)导电性:依照IBM标准,使用三菱Loresta MP-T360电导仪,并采用BSP探头进行测试样板的导电性。
(5)耐高温性:将样板放入220℃烘箱中烘烤20分钟后取出,测定烘烤前后的ΔE值。
(6)再涂装性:经粉末喷涂(膜厚20μm)后,样板经划格加杯突等力学测试。
七、测试结果:
如上表所示:与对比表面处理剂1~4相比,本发明的镀锌钢板表面处理剂具有优异的抗腐蚀性、耐溶剂性、耐高温性、导电性以及再涂装性。
Claims (18)
3.如权利要求1所述的表面处理剂,其特征在于:所述的含环氧基的硅烷衍生物为缩水甘油醚丙基甲基二甲氧基硅烷、缩水甘油醚丙基三甲氧基硅烷和缩水甘油醚乙基三乙酰基硅烷中的一种或多种。
4.如权利要求1所述的表面处理剂,其特征在于:所述的含环氧基的硅烷衍生物的含量为20~45%;百分比为其质量占A、B、C和D总质量的百分比。
5.如权利要求1所述的表面处理剂,其特征在于:所述的含烷基的硅烷衍生物为甲基三甲氧基硅烷、二甲基二甲氧基硅烷和甲基三乙氧基硅烷中的一种或多种。
6.如权利要求1所述的表面处理剂,其特征在于:所述的含烷基的硅烷衍生物的含量为15~45%;百分比为其质量占A、B、C和D总质量的百分比。
7.如权利要求1所述的表面处理剂,其特征在于:所述的烷氧基硅烷衍生物为四甲氧基硅烷、四乙氧基硅烷和四丙氧基硅烷中的一种或多种。
8.如权利要求1所述的表面处理剂,其特征在于:所述的烷氧基硅烷衍生物的含量为5~30%;百分比为其质量占A、B、C和D总质量的百分比。
9.如权利要求1所述的表面处理剂,其特征在于:
所述的阳离子聚合物水分散体为阳离子聚氨酯水分散体、阳离子丙烯酸酯水分散体、阳离子环氧水分散体和阳离子醇酸水分散体中的一种或多种;
所述的非离子聚合物水分散体为非离子聚氨酯水分散体、非离子丙烯酸酯水分散体、非离子环氧水分散体和非离子醇酸水分散体中的一种或多种;
所述的水溶性聚合物为水溶性聚乙二醇、水溶性聚丙烯酰胺、水溶性聚氨酯和水溶性聚丙烯酸中的一种或多种。
10.如权利要求1所述的表面处理剂,其特征在于:所述的D的含量为30~60%;百分比为其质量占A、B、C和D总质量的百分比。
11.如权利要求1所述的表面处理剂,其特征在于:所述的表面处理剂还含有酸性化合物和/或水。
12.如权利要求11所述的表面处理剂,其特征在于:所述的酸性化合物含量为A、B、C和D四种成分总质量的5~35%;所述的水的含量为A、B、C和D四种成分总质量的50~200%。
13.如权利要求11所述的表面处理剂,其特征在于:所述的酸性化合物为盐酸、硫酸、硝酸、磷酸、氟钛酸、氟锆酸、氟硅酸、氢氟酸、醋酸和羟基磺酸中的一种或多种。
14.如权利要求1所述的表面处理剂,其特征在于:所述的表面处理剂的pH值为2~7。
15.如权利要求1~14任一项所述的表面处理剂的制备方法,其特征在于其包括如下步骤:5~70℃下,将所述的各成分均匀混合0.5~8小时,即可制得。
16.一种镀锌钢板,其特征在于:其表面涂覆了如权利要求1~14任一项所述的镀锌钢板表面处理剂。
17.如权利要求16所述的镀锌钢板,其特征在于:所述的镀锌钢板表面涂覆的镀锌钢板表面处理剂的量为0.5~2mg/m2。
18.如权利要求16所述的镀锌钢板的制备方法,其特征在于:将如权利要求1~14任一项所述的镀锌钢板表面处理剂涂覆镀锌钢板上,成膜温度为60~120℃。
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CN100391623C (zh) | 2005-06-27 | 2008-06-04 | 宝山钢铁股份有限公司 | 具有耐碱性和耐溶剂性的用于镀锌钢板的表面处理剂 |
JP4776458B2 (ja) * | 2005-07-22 | 2011-09-21 | 新日本製鐵株式会社 | 耐食性、耐熱性、耐指紋性、導電性、塗装性および加工時の耐黒カス性に優れたクロメートフリー表面処理金属材 |
FR2914631B1 (fr) * | 2007-04-06 | 2009-07-03 | Eads Europ Aeronautic Defence | Materiau nanostructure particulier, comme revetement protecteur de surfaces metalliques. |
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- 2009-12-23 KR KR1020117015177A patent/KR101641484B1/ko active IP Right Grant
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CN1360644A (zh) * | 1999-07-19 | 2002-07-24 | 辛辛那提大学 | 以乙烯基硅烷与双甲硅烷基氨基硅烷的水性混合物对金属表面的保护性处理 |
US6955728B1 (en) * | 1999-07-19 | 2005-10-18 | University Of Cincinnati | Acyloxy silane treatments for metals |
CN1814860A (zh) * | 2005-02-02 | 2006-08-09 | 日本帕卡濑精株式会社 | 金属材料表面处理用组合物和处理方法 |
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EP2383370B1 (en) | 2016-09-28 |
US8906990B2 (en) | 2014-12-09 |
EP2383370A1 (en) | 2011-11-02 |
KR101641484B1 (ko) | 2016-07-22 |
AU2009329626A1 (en) | 2011-08-18 |
KR20110117070A (ko) | 2011-10-26 |
CN101760736A (zh) | 2010-06-30 |
EP2383370A4 (en) | 2015-04-08 |
US20110281118A1 (en) | 2011-11-17 |
CA2748285A1 (en) | 2010-07-01 |
MX2011006887A (es) | 2011-10-06 |
CA2748285C (en) | 2018-05-01 |
AU2009329626B2 (en) | 2016-03-03 |
BRPI0923695B1 (pt) | 2019-04-24 |
WO2010072152A1 (zh) | 2010-07-01 |
BRPI0923695A2 (pt) | 2016-09-06 |
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