CN112930419A - 含有三价铬和无机化合物的表面处理溶液组合物、制造利用该组合物进行表面处理的热浸镀锌钢板的方法 - Google Patents

含有三价铬和无机化合物的表面处理溶液组合物、制造利用该组合物进行表面处理的热浸镀锌钢板的方法 Download PDF

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CN112930419A
CN112930419A CN201980070901.9A CN201980070901A CN112930419A CN 112930419 A CN112930419 A CN 112930419A CN 201980070901 A CN201980070901 A CN 201980070901A CN 112930419 A CN112930419 A CN 112930419A
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steel sheet
dip galvanized
hot
galvanized steel
vanadium
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CN112930419B (zh
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曺秀铉
李康慜
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Posco Holdings Inc
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Posco Co Ltd
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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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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    • B05D3/0272—After-treatment with ovens
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract

本发明提供一种表面处理溶液组合物、利用该表面处理溶液组合物进行表面处理的热浸镀锌钢板及其制造方法，所述表面处理溶液组合物包含：30‑51重量％的三价铬化合物，所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，且其含量比A/(A+B)满足0.3‑0.6；5‑15重量％的硅烷偶联剂；0.2‑3重量％的钒系防锈耐蚀剂；3‑12重量％的胶态二氧化硅；0.5‑5重量％的聚硅氧烷共聚物；和14‑61.3重量％的水，用含有三价铬的所述表面处理溶液组合物进行处理的热浸镀锌钢板具有耐蚀性、耐黑变性、制管油反应性和耐碱性优异的效果。

Description

含有三价铬和无机化合物的表面处理溶液组合物、制造利用 该组合物进行表面处理的热浸镀锌钢板的方法
技术领域
本发明涉及一种高耐蚀性的含有三价铬和无机化合物的表面处理溶液组合物、制造利用所述组合物进行表面处理的热浸镀锌钢板的方法。
背景技术
形成镀锌(Zn)层的热浸镀材料由于基材铁的牺牲防腐蚀带来的保护效果而具有优异的耐蚀性，因此被广泛地用作建筑材料。但是，所述热浸镀材料的暴露面由Zn形成，因此，当暴露在一般的腐蚀环境，特别是暴露在湿润气氛时，表面上容易产生作为锌氧化物的白锈，使得材料的质量特性变差。此外，当镀锌材料暴露在高温高湿环境时，容易发生表面颜色变为黑色的黑变现象。
为了解决这种问题，以往利用六价铬或铬酸盐对经镀覆处理的钢板进行处理，以此确保耐蚀性和耐黑变性。但是，由于这种六价铬被指定为对环境有害的物质，目前正在加强对于六价铬的使用的管制。此外，使用六价铬作为热浸镀锌钢板的表面处理剂时，存在钢板表面变为黑色或产生黑点等的问题。
因此，近年来，为了解决六价铬对环境有害的问题，正在应用通过将含有三价铬的表面处理溶液组合物涂覆在钢板上来确保镀锌钢板的耐蚀性和耐黑变性的方法。例如，韩国公开专利第2006-0123628号、第2005-0052215号和第2009-0024450号中，通过将钢板浸入含有三价铬的组合物中进行化学转化处理的方式确保耐蚀性和耐黑变性，但是浸入时间长，因此无法应用于钢铁公司的连续工艺，并且化学转化处理方法具有耐指纹性降低等问题。
此外，韩国公开专利第2004-0046347号和日本的特开2002-069660号中，将含有三价铬的组合物以喷涂或辊涂的方式涂覆在镀覆钢板上，从而可以应用于钢铁公司的连续工艺，并且可以确保耐指纹性。但是，所述组合物中包含多孔二氧化硅成分，因此不适于在湿润的气氛中发生严重的变色的Mg、Al合金。所述多孔二氧化硅具有强吸湿性质，因此存在在Mg、Al、Zn合金钢板上引发急剧的变色的问题。
发明内容
要解决的技术问题
本发明的一个方面提供一种表面处理溶液组合物，所述表面处理溶液组合物不含对环境有害的物质六价铬，并且以对人体无害的三价铬和无机化合物为主要成分。
本发明的另一个方面提供一种利用三价铬和无机化合物进行表面处理的热浸镀锌钢板，其中，通过将本发明的表面处理溶液组合物应用于热浸镀锌钢板的表面，所述热浸镀锌钢板具有优异的耐蚀性、耐黑变性、制管油反应性和耐碱性。
本发明的又一个方面提供一种制造利用本发明的表面处理溶液组合物进行表面处理的热浸镀锌钢板的方法。
技术方案
本发明的一个方面提供一种表面处理溶液组合物，所述表面处理溶液组合物包含：30-51重量％的三价铬化合物，所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，且其含量比A/(A+B)满足0.3-0.6；5-15重量％的硅烷偶联剂；0.2-3重量％的钒系防锈耐蚀剂；3-12重量％的胶态二氧化硅；0.5-5重量％的聚硅氧烷共聚物；和14-61.3重量％的水。
本发明的另一个方面提供一种经表面处理的热浸镀锌钢板，所述热浸镀锌钢板包括：钢板；热浸镀锌层，形成在所述钢板的至少一面上；和三价铬酸盐薄膜层，形成在所述热浸镀锌层上，其中，所述三价铬酸盐薄膜层包含：37.7-58.1重量％的三价铬化合物，所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，并且其含量比A/(A+B)满足0.89-0.95；34.6-40.7重量％的硅烷偶联剂；1.4-8.2重量％的钒系防锈耐蚀剂；4.2-6.6重量％的胶态二氧化硅；和1.7-6.8重量％的聚硅氧烷共聚物。
本发明的另一个方面提供一种制造经表面处理的热浸镀锌钢板的方法，所述方法包括以下步骤：将所述表面处理溶液组合物涂覆在形成有热浸镀锌层的热浸镀锌钢板上；以及将涂覆的所述表面处理溶液组合物进行干燥，以形成三价铬酸盐薄膜层。
有益效果
利用本发明的含有三价铬和无机化合物的表面处理溶液组合物进行处理的热浸镀锌钢板具有耐蚀性、耐黑变性、焊接性和耐碱性优异的效果。
具体实施方式
以下，参考附图，对本发明的优选的实施方案进行说明。但是，本发明的实施方案可以变形为各种其它实施方案，本发明的范围并不限定于以下说明的实施方案。
本发明涉及一种含有三价铬的表面处理溶液组合物、利用所述组合物进行表面处理的热浸镀锌钢板和制造所述热浸镀锌钢板的方法。
本发明的一个实施方案的表面处理溶液组合物中，以溶液组合物的总重量为基准，包含：30-51重量％的三价铬化合物、5-15重量％的硅烷偶联剂、0.2-3重量％的钒系防锈耐蚀剂、3-12重量％的胶态二氧化硅、0.5-5重量％的聚硅氧烷共聚物和14-61.3重量％的水，所述三价铬化合物是磷酸铬(A)和硝酸铬(B)，并且其含量比A/(A+B)满足0.3-0.6。
利用本发明的含有三价铬的表面处理溶液组合物进行表面处理的热浸镀锌钢板具有耐蚀性、耐黑变性、焊接性和耐碱性优异的效果。此外，所述组合物包含对人体无害的三价铬作为主要成分，而不含有对环境有害的物质六价铬，因此具有防止对人体的伤害和环境污染的问题的效果。
所述三价铬化合物是作为主要成分包含在本发明的表面处理溶液组合物中的成分，其具有与六价铬相似的自修复效果(self-healing effect)和自润滑性，并且起到确保耐蚀性和耐黑变性的作用。包含在本发明的组合物中的所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)。
随着所述磷酸铬的比例增加，显示出耐蚀性提高的效果，但是耐黑变性可能会变差。另外，随着硝酸铬的比例增加，耐黑变性提高，但是耐蚀性可能会变差。具体地，利用所述磷酸铬形成薄膜时，由于磷酸成分不挥发，在薄膜表面上形成磷酸铬薄膜，因此提高耐蚀性，但由于所述磷酸铬的吸湿性，耐黑变性可能会降低。另一方面，利用所述硝酸铬形成薄膜时，大部分硝酸成分挥发，因此不会影响耐黑变性，但是硝酸铬的含量增加时，相对难以在薄膜表面上形成磷酸铬薄膜，因此耐蚀性可能会变差。
因此，根据本发明的一个实施方案，控制各成分的含量，使得所述磷酸铬(A)和硝酸铬(B)的含量比A/(A+B)满足0.3-0.6。当所述含量比小于0.3时，加工后的耐蚀性可能会降低，当所述含量比超过0.6时，耐黑变性可能会降低。
包含磷酸铬(A)和硝酸铬(B)的所述三价铬化合物的总含量为30-51重量％，优选为35-45重量％。当所述三价铬化合物的含量小于30重量％时，坚固的不溶性薄膜层变薄，因此在需要耐蚀性的镀覆钢板的表面上不能有效地阻断水分的渗透，从而引起黑变，并且还存在降低耐蚀性的问题。另外，当所述三价铬化合物的含量超过51重量％时，为了提高耐蚀性而添加的钒系防锈耐蚀剂、胶态二氧化硅和起到粘合剂作用的硅烷偶联剂的含量相对减少，因此存在难以确保充分的耐蚀性和耐黑变性的问题。
所述硅烷偶联剂通过使无机成分和有机成分交联的作用来促进干燥并确保高耐蚀性。对所述硅烷偶联剂的种类不作特别限定，例如，优选为选自2-(3,4-环氧环己基)-乙基三甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-脲基丙基三甲氧基硅烷和正硅酸四乙酯中的一种以上。
所述硅烷偶联剂的含量为5-15重量％，优选为7-12重量％。当所述硅烷偶联剂的含量小于5重量％时，耐碱性和耐燃料性变差，当所述硅烷偶联剂的含量超过15重量％时，薄膜的干燥度变高，形成过硬的薄膜，因此加工部耐蚀性变差。
包含所述钒系防锈耐蚀剂是为了在利用本发明的表面处理溶液组合物进行表面处理的热浸镀锌钢板的表面上形成钝化薄膜以提高镀覆钢板的耐蚀性。由此，所述热浸镀锌钢板的薄膜发生损坏时，邻近薄膜的四价钒溶出并还原成三价并在暴露的镀覆表面上形成钝化薄膜，因此可以具有抑制腐蚀的效果。此外，在腐蚀环境下，钒优先溶出，抑制因镀覆成分的溶解而引起的pH的上升，因此可以具有提高热浸镀锌钢板的耐蚀性的效果。并且，所述钒系防锈耐蚀剂防止因奇数个锌的电子离子的形成而引起的镀层表面的黑变现象，因此可以具有提高镀层的耐黑变性的效果。
所述钒系防锈耐蚀剂优选可以是选自五氧化二钒(V2O5)、偏钒酸(HVO3)、偏钒酸铵、偏钒酸钠、三氯氧化钒(VOCl3)、三氧化二钒(V2O3)、二氧化钒(VO2)、硫酸氧钒(VOSO4)、草酸氧钒[VO(COO)2]、乙酰丙酮氧钒[VO(OC(CH3)＝CHCOCH3))2]、乙酰丙酮钒[V(OC(CH3)＝CHCOCH3))3]、三氯化钒(VCl3)、硫酸钒(VSO4·8H2O)、二氯化钒(VCl2)和一氧化钒(VO)中的一种以上。
所述钒系防锈耐蚀剂的含量为0.2-3重量％，优选为0.5-2重量％。当所述防锈耐蚀剂的含量小于0.2重量％时，存在难以确保耐蚀性的问题，当所述防锈耐蚀剂的含量超过3重量％时，存在难以确保耐黑变性和耐碱性的问题。
所述胶态二氧化硅通过与三价铬化合物形成无机系二氧化硅结合来增强薄膜的致密性，以防止腐蚀因子的渗透，从而有效地提高利用本发明的表面处理溶液组合物进行表面处理的热浸镀锌钢板的耐蚀性。所述胶态二氧化硅的粒度可以为5-15nm，并且所述胶态二氧化硅可以水分散在pH为3-5的酸性水溶液中。此时，当所述胶态二氧化硅的粒度超过15nm时，在水分散过程中可能会发生溶液的稳定性降低的问题，并且在镀覆钢板上形成薄膜后，在用于产品加工的冲压工艺等中，由于与冲压表面的摩擦，可能会引起加工性降低的问题。此外，当所述胶态二氧化硅的粒度小于5nm时，通过阻断腐蚀因子来确保耐蚀性方面可能存在问题。此外，当将所述胶态二氧化硅进行水分散的酸性溶液的pH不在3-5的范围时，由于分散的二氧化硅颗粒的沉淀，也存在溶液稳定性降低的问题。
所述胶态二氧化硅为固态的二氧化硅颗粒以不发生沉淀和凝聚的状态稳定地分散在诸如水或有机溶剂的液体中，所述胶态二氧化硅的种类不受限制，但优选可以使用Ludox HAS(snowtex-O)。
所述胶态二氧化硅的含量为3-12重量％，优选为5-10重量％。当所述胶态二氧化硅的含量小于3重量％时，加工部耐蚀性差，当所述胶态二氧化硅的含量超过12重量％时，由于薄膜的吸湿性增加，存在耐黑变性降低的问题。
所述聚硅氧烷共聚物通过有机系结合和无机系结合在利用本发明的表面处理溶液组合物进行表面处理的热浸镀锌钢板的表面上形成致密的薄膜，并且通过向薄膜赋予柔韧性，起到提高平板和加工部的耐蚀性的作用。此外，通过防止腐蚀因子的渗透，提高所述热浸镀锌钢板的耐黑变性，并且通过赋予柔韧的薄膜性质，有效地提高加工性。
所述聚硅氧烷共聚物可以包含硅氧烷化合物和硅烷化合物中的至少一种成分，所述硅氧烷化合物是选自聚二甲基硅氧烷、聚乙烯基硅氧烷、聚苯基甲基硅氧烷、六甲基硅氧烷等中的一种以上，所述硅烷化合物是选自甲基三甲氧基硅烷、乙基三甲氧基硅烷、六甲基二硅烷、乙氧基三乙基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、γ-环氧丙氧基三乙基硅烷和γ-环氧丙氧基三甲基硅烷等中的一种以上。
此外，所述聚硅氧烷共聚物优选在选自磷酸、有机磷酸、草酸、柠檬酸、甲酸中的一种以上的酸催化剂的存在下通过合成所述硅氧烷化合物和/或硅烷化合物而获得，所述聚硅氧烷共聚物是重均分子量为300-1500之间的共聚物，更优选地，可以是重均分子量为650-750之间的共聚物。当所述聚硅氧烷共聚物的重均分子量小于300时，在薄膜的干燥过程中无法稳定地形成薄膜，因此耐蚀性可能会降低，当所述聚硅氧烷共聚物的重均分子量超过1500时，所述聚硅氧烷共聚物的稳定性可能会发生问题。
所述聚硅氧烷共聚物的含量为0.5-5重量％，优选为1.0-4.5重量％。当所述聚硅氧烷共聚物的含量小于0.5重量％时，加工部耐蚀性、耐黑变性和加工性变差，当所述聚硅氧烷共聚物的含量超过5重量％时，存在耐碱性降低的问题。
所述水是本发明的表面处理溶液组合物的溶剂，使用所述水是为了稀释表面处理溶液组合物的成分。所述水可以使用例如去离子水或蒸馏水。除了本发明的各组成成分之外，作为余量包含所述溶剂，优选地，所述溶剂的含量例如为14-61.3重量％。
根据本发明的另一个实施方案，提供一种利用上述含有三价铬的表面处理溶液组合物进行表面处理的热浸镀锌钢板及其制造方法。
具体地，所述经表面处理的热浸镀锌钢板包括：钢板；镀锌层，形成在所述钢板的至少一面上；和三价铬酸盐薄膜层，形成在所述镀锌层上。此时，所述三价铬酸盐薄膜层可以使用上述本发明的表面处理溶液组合物，更详细地，所述三价铬酸盐薄膜层包含：37.7-58.1重量％的三价铬化合物、34.6-40.7重量％的硅烷偶联剂、1.4-8.2重量％的钒系防锈耐蚀剂、4.2-6.6重量％的胶态二氧化硅、1.7-6.8重量％的聚硅氧烷共聚物。此外，所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，且其含量比A/(A+B)满足0.89-0.95。
所述三价铬酸盐薄膜层是通过对上述表面处理溶液组合物进行干燥而获得的涂层，相当于所述三价铬酸盐薄膜层中包含的挥发性物质全部挥发后残留的成分。由此，所述三价铬酸盐薄膜层中不包含作为溶剂的水，并且也不包含三价铬酸盐化合物和硅烷偶联剂中所包含的水。因此，三价铬酸盐薄膜层中包含的成分对应于以100重量％的三价铬酸盐薄膜层的总固含量为基准的含量。
所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，其含量比A/(A+B)满足0.89-0.95，以镀覆钢板上干燥的薄膜层为基准，所述三价铬化合物的含量为37.7-58.1重量％，优选为44-51重量％。当所述三价铬化合物的含量小于37.7重量％时，坚固的不溶性薄膜层变薄，因此在需要耐蚀性的镀覆钢板的表面上不能有效地阻断水分的渗透，从而引起黑变，并且还存在耐蚀性降低的问题。另外，当所述三价铬化合物的含量超过58.1重量％时，为了提高耐蚀性而添加的钒系防锈耐蚀剂、胶态二氧化硅、聚硅氧烷和起到粘合剂作用的硅烷偶联剂的含量相对减少，因此存在难以确保充分的耐蚀性和耐黑变性的问题。
此外，所述磷酸铬(A)和硝酸铬(B)的含量比A/(A+B)满足0.89-0.95，当上述含量比小于0.89时，加工后的耐蚀性可能会降低，当上述含量比超过0.95时，耐黑变性可能会降低。
在所述表面处理溶液组合物中，磷酸铬(A)和硝酸铬(B)的含量比A/(A+B)为0.3-0.6。但是，由于所述磷酸铬和硝酸铬中包含大量的水，在将所述表面处理溶液组合物涂覆在合金化镀锌钢板上并进行干燥以形成薄膜层的工艺中，去除所述水，因此所述薄膜层中包含的磷酸铬(A)和硝酸铬(B)的含量比A/(A+B)为0.89-0.95。
以镀覆钢板上干燥的薄膜层为基准，所述硅烷偶联剂的含量为34.6-40.7重量％，优选为38.7-40.7重量％。当所述硅烷偶联剂的含量小于34.6重量％时，耐碱性和制管油侵蚀性变差，当所述硅烷偶联剂的含量超过40.7重量％时，薄膜的干燥度变高，形成过硬的薄膜，因此加工部的耐蚀性变差，并且耐燃料性变差。
以镀覆钢板上干燥的薄膜层为基准，所述钒系防锈耐蚀剂的含量为1.4-8.2重量％，优选为1.4-4.7重量％。当所述防锈耐蚀剂的含量小于1.4重量％时，存在难以确保耐蚀性的问题，当所述防锈耐蚀剂的含量超过8.2重量％时，存在难以确保耐黑变性和耐碱性的问题。
以镀覆钢板上干燥的薄膜层为基准，所述胶态二氧化硅的含量为4.2-6.6重量％，优选为5.8-6.6重量％。当所述胶态二氧化硅的含量小于4.2重量％时，存在加工部耐蚀性差的问题，当所述胶态二氧化硅的含量超过6.6重量％时，由于薄膜的吸湿性增加，存在耐黑变性降低的问题。
另外，以镀覆钢板上干燥的薄膜层为基准，所述聚硅氧烷共聚物的含量为1.7-6.8重量％，优选为3.3-6.8重量％。当所述聚硅氧烷共聚物的含量小于1.7重量％时，存在加工部耐蚀性、耐黑变性和加工性差的问题，当所述聚硅氧烷共聚物的含量超过6.8重量％时，存在耐碱性差的问题。
根据本发明的一个实施方案，提供一种制造热浸镀锌钢板的方法，所述方法包括以下步骤：准备形成有热浸镀锌层的热浸镀锌钢板；将本发明的表面处理溶液组合物涂覆在所述热浸镀锌层上；以及将涂覆的所述表面处理溶液组合物进行干燥，以形成三价铬酸盐薄膜层。
所述表面处理溶液组合物包含：30-51重量％的三价铬化合物，所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，且其含量比A/(A+B)满足0.3-0.6；5-15重量％的硅烷偶联剂；0.2-3重量％的钒系防锈耐蚀剂；3-12重量％的胶态二氧化硅；0.5-5重量％的聚硅氧烷共聚物；和14-61.3重量％的水。所述表面处理溶液组合物中包含的各成分的含量范围的技术意义如上所述。
根据本发明的一个实施方案，可以将表面处理溶液组合物以2.14-3.57μm的厚度涂覆在所述镀覆钢板上。通过干燥工艺将以上述厚度进行涂覆的表面处理溶液组合物进行干燥后的薄膜层的厚度可以为0.3-0.5μm，优选可以为0.3-0.4μm。当所述表面处理溶液组合物的涂覆厚度小于2.14μm时，涂覆在钢板粗糙度的峰部分的表面处理溶液组合物薄，因此可能会发生耐蚀性降低的问题，当所述表面处理溶液组合物的涂覆厚度超过3.57μm时，形成厚的薄膜层，因此可能会发生焊接性和加工性等降低的问题。
对涂覆所述表面处理溶液组合物的方法不作特别限制，只要是通常进行的涂覆方法即可，例如，优选可以通过选自辊涂、喷涂、浸涂、喷射挤压和浸渍挤压中的任一种涂覆方法进行。
以原材料钢板的最终达到温度(PMT)为基准，将涂覆在所述热浸镀锌钢板上的表面处理溶液组合物进行干燥的工艺优选在40-60℃的温度下进行。以原材料钢板的最终达到温度(PMT)为基准，当所述干燥温度低于40℃时，无法完全干燥，因此耐碱性和制管油侵蚀性会变差，当所述干燥温度超过60℃时，在空气中的冷却过程(空冷)中钢板未能充分冷却并进行包装，从而发生结露现象，因此钢板的耐黑变性可能会变差。
另外，所述干燥优选在热风干燥炉或感应加热炉中进行。利用所述热风干燥炉对表面处理涂覆组合物进行干燥时，所述热风干燥炉的内部温度优选为100-200℃。另外，利用所述感应加热炉对表面处理涂覆组合物进行干燥时，向所述感应加热炉施加的电流优选为1000-3500A，更优选为1500-3000A。当所述热风干燥炉的内部温度低于100℃或向感应加热炉施加的电流小于1000A时，表面处理涂覆组合物无法完全干燥，因此耐碱性和制管油侵蚀性可能会变差。此外，当所述热风干燥炉的内部温度超过200℃或向感应加热炉施加的电流超过3500A时，在空气中的冷却过程(空冷)中钢板未能充分冷却并进行包装，从而发生结露现象，因此钢板的耐黑变性可能会变差。
此外，将所述表面处理溶液组合物进行干燥以形成三价铬酸盐薄膜层后，将所述三价铬酸盐薄膜层进行空冷，从而最终可以提供经表面处理的热浸镀锌钢板。
本发明的一个实施方案的制造所述热浸镀锌钢板的方法可以通过连续工艺进行，所述连续工艺的速度优选为80-100米/分钟(mpm)。当所述连续工艺的速度小于80米/分钟时，可能会发生生产性降低的问题，当所述连续工艺的速度超过100米/分钟时，在将表面处理溶液组合物进行干燥的工艺中溶液会飞散，从而可能会产生表面缺陷。
以下，通过具体的实施例对本发明进行更详细的说明。下述实施例仅仅是有助于理解本发明的示例，本发明的范围并不限定于此。
实施例
1.根据三价铬化合物的含量的物理性能的变化
为了测试根据本发明的表面处理溶液组合物的各成分含量的物理性能的变化，制备如下的表面处理溶液组合物：该表面处理溶液组合物包含三价铬化合物、钒系防锈耐蚀剂、胶态二氧化硅、硅烷偶联剂、聚硅氧烷共聚物和水，其中，所述三价铬化合物是硝酸铬和磷酸铬，所述钒系防锈耐蚀剂是乙酰丙酮钒，所述胶态二氧化硅是Ludox HAS(snowtex-O)，所述硅烷偶联剂是重量比为1:1的正硅酸四乙酯和3-环氧丙氧基丙基三甲氧基硅烷的混合物，所述聚硅氧烷共聚物是通过使用聚乙烯基硅氧烷、乙烯基三甲氧基硅烷和作为酸催化剂的磷酸进行合成的重均分子量为650的聚硅氧烷共聚物。
另外，在以下实施例中，将本发明的表面处理溶液组合物满足下表1的含量范围的情况记载为实施例，并且将一种以上的成分不满足下表1的含量范围的情况记载为比较例。
[表1]
Figure BDA0003039923420000111
以下实验是利用具有根据表2至表8的各成分含量的表面处理溶液组合物来进行，以下表2至表8中记载的各成分的含量是“以固含量为基准”记载。更详细地，所述“以固含量为基准”是指在干燥薄膜状态下去除水而显示出的100％的固含量为基准，其中，所述在干燥薄膜状态下去除水是指除了去除本发明的溶液组合物中包含的作为溶剂的水之外，还去除三价铬化合物和硅烷偶联剂中包含的水。以各实施例和比较例中制备的组合物中的固含量为14重量％的情况为基准，将所述固含量换算成100重量％的情况下测量的含量(重量％)示于下表2至表8中。
[表2]
Figure BDA0003039923420000121
为了测量根据各成分含量的物理性能的变化，将热浸镀锌钢板切割成7cm×15cm(宽度×长度)，并去除油分，然后通过棒式(BAR)涂覆将所述表2中制备的三价铬表面处理溶液组合物进行涂覆，并以PMT为60℃的条件进行干燥，使得干燥薄膜层的厚度为0.4μm，以制造试片。对制造的试片的平板耐蚀性、加工部耐蚀性和耐黑变性进行评价，并将评价结果记载于所述表2中。所述平板耐蚀性、加工部耐蚀性和耐黑变性的评价方法如下。
<平板耐蚀性>
根据ASTM B117中规定的方法，对试片进行处理后测量随着时间的经过的钢板的白锈产生率。此时，评价基准为如下所示。
◎：产生白锈的时间为144小时以上
○：产生白锈的时间为96小时以上且小于144小时
△：产生白锈的时间为小于55小时且小于96小时
×：产生白锈的时间为小于55小时
<加工部耐蚀性>
利用埃里克森试验机(Erichsen tester)将试片推到6mm的高度处，然后测量经过24小时时产生白锈的程度。此时，评价基准为如下所示。
◎：经过48小时后产生的白锈为小于5％
△：经过48小时后产生的白锈为5％以上且小于7％
×：经过48小时后产生的白锈为7％以上
<耐黑变性>
将试片放置在保持50℃和95％的相对湿度的恒温恒湿器中120小时，观察试验前/后的试片颜色变化(色差：ΔE)。此时，评价基准为如下所示。
◎：ΔE≤2
○：2<ΔE≤3
△：3<ΔE≤4
×：ΔE>4
如所述表2所示，三价铬化合物的含量满足本发明提出的含量时(实施例1至实施例4)，所有物理性能显示出良好以上的结果。
另一方面，添加过少的三价铬化合物时(比较例1)，平板耐蚀性、加工部耐蚀性和耐黑变性显示出不良的结果，添加过多的三价铬化合物时(比较例2)，除耐黑变性之外的所有物理性能显示出不良的结果。
2.根据三价铬化合物中包含的磷酸铬(Ⅲ)和硝酸铬(Ⅲ)的比例的物理性能的变化
使用所述实施例3的三价铬表面处理溶液组合物，但将磷酸铬(Ⅲ)和硝酸铬(Ⅲ)的比例控制为下表3中记载的磷酸铬和硝酸铬的比例。具体地，在蒸馏水中加入磷酸铬化合物和硝酸铬，并在80℃下反应1小时，然后冷却至常温以制备三价铬化合物(磷酸铬(Ⅲ)和硝酸铬(Ⅲ))。此时，控制各成分的含量，以使所述磷酸铬和硝酸铬的比例满足下表3的比例。
[表3]
Figure BDA0003039923420000131
Figure BDA0003039923420000141
将热浸镀锌钢板切割成7cm×15cm(宽度×长度)，并去除油分，然后通过棒式(BAR)涂覆将所述表3中制备的三价铬表面处理溶液组合物进行涂覆，并以PMT为60℃的条件进行干燥，使得干燥薄膜层的厚度为0.4μm，以制造试片。对制造的试片的平板耐蚀性和耐黑变性进行评价，并将评价结果记载于所述表3中。如所述表3所示，随着磷酸铬的比例增加，显示出耐蚀性提高的效果，另一方面，随着硝酸铬的比例增加，显示出耐黑变性提高的倾向。但是，磷酸铬和硝酸铬的比例为本发明提出的磷酸铬和硝酸铬的比例的以下或以上时，显示出耐蚀性或耐黑变性不良的倾向。
3.根据硅烷偶联剂的含量和种类的物理性能的变化
本发明的含有三价铬的表面处理溶液组合物包含三价铬化合物、钒系防锈耐蚀剂、胶态二氧化硅、硅烷偶联剂、聚硅氧烷共聚物，其中，所述三价铬化合物是硝酸铬和磷酸铬，所述钒系防锈耐蚀剂是乙酰丙酮钒，所述胶态二氧化硅是Ludox HAS(snowtex-O)，所述硅烷偶联剂是重量比为1:1的正硅酸四乙酯和3-环氧丙氧基丙基三甲氧基硅烷的混合物，所述聚硅氧烷共聚物是通过使用聚乙烯基硅氧烷、乙烯基三甲氧基硅烷和作为酸催化剂的磷酸进行合成的重均分子量为650的聚硅氧烷共聚物，并以所述组合物的固含量为基准，以下表4中记载的含量进行混合。
[表4]
Figure BDA0003039923420000142
Figure BDA0003039923420000151
将热浸镀锌钢板切割成7cm×15cm(宽度×长度)，并去除油分，然后通过棒式(BAR)涂覆将所述表4中制备的三价铬表面处理溶液组合物进行涂覆，并以PMT为60℃的条件进行干燥，使得干燥薄膜层的厚度为0.4μm，以制造试片。对制造的试片的平板耐蚀性、加工部耐蚀性、耐黑变性、耐碱性和焊接性进行评价，并将评价结果记载于所述表4中。平板耐蚀性、加工部耐蚀性、耐黑变性的评价方法如上所述，耐碱性和焊接性的评价方法如下。
<耐碱性>
将试片在碱性脱脂溶液中在60℃下浸渍2分钟后进行水洗和吹气(Air blowing)，然后测量前/后的色差(ΔE)。碱性脱脂溶液使用DAEHAN PARKERIZING公司的FinecleanerL 4460A：20g/2.4L+L 4460B12g/2.4L(pH＝12)。此时，评价基准为如下所示。
◎：ΔE≤2
○：2<ΔE≤3
△：3<ΔE≤4
×：ΔE>4
<焊接性>
如下评价焊接性：利用气动式交流(AC)点焊机，在250kg的电极压力、15个循环(Cycle)的焊接时间和7.5kA的通电电流下，没有飞溅(Spatter)，并且保持一定强度。此时，评价基准为如下的三种模式：可以焊接(○)、不能焊接(×)和焊接质量不良(△)。
如所述表4所示，当硅烷偶联剂的含量满足本发明提出的含量时(实施例8至实施例11)，所有物理性能显示出良好(○)以上的结果。
另一方面，添加过少的硅烷偶联剂时(比较例7)，耐碱性显示出不良的结果，添加过多的硅烷偶联剂时(比较例8)，薄膜的干燥度变高，形成坚硬的薄膜，从而显示出加工部耐蚀性差、耐黑变性不良且焊接质量不良的结果。
制备所述实施例11的三价铬表面处理溶液组合物，但硅烷偶联剂的种类使用下表5中记载的硅烷偶联剂。利用使用下表5中记载的硅烷偶联剂的三价铬表面处理溶液组合物进行如上所述的棒式(BAR)涂覆，并以PMT为60℃的条件进行干燥，以制造试片，对试片的平板耐蚀性进行评价，并将其结果记载于表5中。
[表5]
Figure BDA0003039923420000161
Figure BDA0003039923420000171
如所述表5所示，实施例12至实施例45显示出平板耐蚀性良好或优异的结果。特别是，利用根据实施例41的组成制备的三价铬表面处理溶液组合物进行处理的试验试片的情况下，在144小时以上后产生的白锈面积为0％，显示出最优异的结果。
4.根据钒系防锈耐蚀剂的含量的物理性能的变化
本发明的含有三价铬的表面处理溶液组合物包含三价铬化合物、钒系防锈耐蚀剂、胶态二氧化硅、硅烷偶联剂、聚硅氧烷共聚物，其中，所述三价铬化合物是硝酸铬和磷酸铬，所述钒系防锈耐蚀剂是乙酰丙酮钒，所述胶态二氧化硅是Ludox HAS(snowtex-O)，所述硅烷偶联剂是重量比为1:1的正硅酸四乙酯和3-环氧丙氧基丙基三甲氧基硅烷的混合物，所述聚硅氧烷共聚物是通过使用聚乙烯基硅氧烷、乙烯基三甲氧基硅烷和作为酸催化剂的磷酸进行合成的重均分子量为650的聚硅氧烷共聚物，并以下表6中记载的含量(以组合物的固含量为基准)进行混合。
[表6]
Figure BDA0003039923420000172
Figure BDA0003039923420000181
将热浸镀锌钢板切割成7cm×15cm(宽度×长度)，并去除油分，然后通过棒式(BAR)涂覆将所述表6中制备的三价铬表面处理溶液组合物进行涂覆，并以PMT为60℃的条件进行干燥，使得干燥薄膜层的厚度为0.4μm，以制造试片。对制造的试片的平板耐蚀性、加工部耐蚀性、耐黑变性、耐碱性进行评价，并将评价结果记载于所述表6中。所述平板耐蚀性、加工部耐蚀性、耐黑变性和耐碱性的评价方法如上所述。如所述表6所示，当防锈耐蚀剂的含量满足本发明提出的含量时(实施例46至实施例48)，所有物理性能显示出良好以上的结果。进行棒式(BAR)涂覆，并以PMT为60℃的条件进行干燥，以制造试片。对制造的试片的平板耐蚀性、加工部耐蚀性、耐黑变性、耐碱性进行评价，并将评价结果记载于所述表6中。所述平板耐蚀性、加工部耐蚀性、耐黑变性和耐碱性的评价方法如上所述。如所述表6所示，当防锈耐蚀剂的含量满足本发明提出的含量时(实施例46至实施例48)，所有物理性能显示出良好以上的结果。
另一方面，添加过少的防锈耐蚀剂时(比较例9)，除了耐黑变性和耐碱性之外的所有物理性能显示出不良的结果，添加过多的防锈耐蚀剂时(比较例10和比较例11)，除了耐蚀性之外的所有物理性能显示出不良的结果。
5.根据胶态二氧化硅的含量的物理性能的变化
本发明的含有三价铬的表面处理溶液组合物包含三价铬化合物、钒系防锈耐蚀剂、胶态二氧化硅、硅烷偶联剂、聚硅氧烷共聚物，其中，所述三价铬化合物是硝酸铬和磷酸铬，所述钒系防锈耐蚀剂是乙酰丙酮钒，所述胶态二氧化硅是Ludox HAS(snowtex-O)，所述硅烷偶联剂是重量比为1:1的正硅酸四乙酯和3-环氧丙氧基丙基三甲氧基硅烷的混合物，所述聚硅氧烷共聚物是通过使用聚乙烯基硅氧烷、乙烯基三甲氧基硅烷和作为酸催化剂的磷酸进行合成的重均分子量为650的聚硅氧烷共聚物，并以下表7中记载的含量(以组合物的固含量为基准)进行混合。
[表7]
Figure BDA0003039923420000191
将热浸镀锌钢板切割成7cm×15cm(宽度×长度)，并去除油分，然后通过棒式(BAR)涂覆将所述表7中制备的三价铬表面处理溶液组合物进行涂覆，并以PMT为60℃的条件进行干燥，使得干燥薄膜层的厚度为0.4μm，以制造试片。对制造的试片的平板耐蚀性、加工部耐蚀性、耐黑变性进行评价，并将评价结果记载于所述表7中。如所述表7所示，防锈耐蚀剂的含量满足本发明提出的含量时(实施例49至实施例52)，所有物理性能显示出良好以上的结果。
另一方面，添加过少的防锈耐蚀剂时(比较例12)，耐黑变性显示出不良的结果，添加过多的防锈耐蚀剂时(比较例13)，耐蚀性显示出不良的结果。
6.根据聚硅氧烷共聚物的含量的物理性能的变化
本发明的含有三价铬的表面处理溶液组合物包含三价铬化合物、钒系防锈耐蚀剂、胶态二氧化硅、硅烷偶联剂、聚硅氧烷共聚物，其中，所述三价铬化合物是硝酸铬和磷酸铬，所述钒系防锈耐蚀剂是乙酰丙酮钒，所述胶态二氧化硅是Ludox HAS(snowtex-O)，所述硅烷偶联剂是重量比为1:1的正硅酸四乙酯和3-环氧丙氧基丙基三甲氧基硅烷的混合物，所述聚硅氧烷共聚物是通过使用聚乙烯基硅氧烷、乙烯基三甲氧基硅烷和作为酸催化剂的磷酸进行合成的重均分子量为650的聚硅氧烷共聚物，并以下表8中记载的含量(以组合物的固含量为基准)进行混合。
[表8]
Figure BDA0003039923420000201
将热浸镀锌钢板切割成7cm×15cm(宽度×长度)，并去除油分，然后通过棒式(BAR)涂覆将所述表8中制备的三价铬表面处理溶液组合物进行涂覆，并以PMT为60℃的条件进行干燥，使得干燥薄膜层的厚度为0.4μm，以制造试片。如所述表8所示，聚硅氧烷共聚物的含量满足本发明提出的含量时(实施例53至实施例56)，所有物理性能显示出良好以上的结果。另一方面，当添加过少的防锈耐蚀剂时(比较例14)，平板耐蚀性、加工部耐蚀性、耐黑变性显示出不良的结果，当添加过多的防锈耐蚀剂时(比较例15)，耐碱性显示出不良的结果。
7.根据薄膜层的厚度和干燥温度的物理性能的变化
将热浸镀锌钢板切割成7cm×15cm(宽度×长度)，并去除油分，然后通过棒式(BAR)涂覆将所述实施例2的组合物(硅烷偶联剂的成分以实施例41为基准)进行涂覆，并利用热风干燥炉进行干燥以制造试片。将涂覆的薄膜层的厚度和PMT温度控制为下表9中记载的厚度。
对制造的试片的耐碱性、焊接性、平板耐蚀性、加工部耐蚀性和耐黑变性进行评价，并将评价结果整理在下表9中。
[表9]
Figure BDA0003039923420000202
Figure BDA0003039923420000211
如所述表8所示，以0.3-0.5μm形成薄膜层时(实施例57至实施例59)，所有物理性能显示出良好以上的结果。另一方面，所形成的薄膜过薄时(比较例16)，除了焊接性之外的所有物理性能显示出普通(△)的结果，并且加工部耐蚀性显示出不良的结果。另外，形成过厚的薄膜时(比较例17)，除了焊接性之外的所有物理性能显示出良好以上的结果，但与实施例59相比，没有提高的物理性能，因此在经济性方面不需要实施例59的薄膜厚度以上的薄膜厚度，并且存在焊接质量不良的问题。此外，如所述表9所示，以40-60℃的薄膜的干燥温度形成薄膜层时(实施例57至实施例59和实施例61)，所有物理性能显示出良好以上的结果。
另一方面，干燥温度过低时(实施例60)，未能充分干燥，因此耐碱性显示出普通(△)的结果。另外，干燥温度过高时(实施例62)，在空气中的冷却过程(空冷)中钢板未能充分冷却并进行包装，从而导致结露现象，因此耐黑变性显示出普通(△)的结果。
以上对本发明的实施例进行了详细的说明，但是本发明的权利范围并不限定于此，在不脱离权利要求书中记载的本发明的技术思想的范围内可以进行各种修改和变形，这对于本领域技术人员而言是显而易见的。

Claims (27)

1.一种表面处理溶液组合物，其包含：
30-51重量％的三价铬化合物，所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，且其含量比A/(A+B)满足0.3-0.6；
5-15重量％的硅烷偶联剂；
0.2-3重量％的钒系防锈耐蚀剂；
3-12重量％的胶态二氧化硅；
0.5-5重量％的聚硅氧烷共聚物；和
14-61.3重量％的水。
2.根据权利要求1所述的表面处理溶液组合物，其中，所述硅烷偶联剂是选自2-(3,4-环氧环己基)-乙基三甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-脲基丙基三甲氧基硅烷和正硅酸四乙酯中的一种以上。
3.根据权利要求1所述的表面处理溶液组合物，其中，所述钒系防锈耐蚀剂是选自五氧化二钒(V2O5)、偏钒酸(HVO3)、偏钒酸铵、偏钒酸钠、三氯氧化钒(VOCl3)、三氧化二钒(V2O3)、二氧化钒(VO2)、硫酸氧钒(VOSO4)、草酸氧钒[VO(COO)2]、乙酰丙酮氧钒[VO(OC(CH3)＝CHCOCH3))2]、乙酰丙酮钒[V(OC(CH3)＝CHCOCH3))3]、三氯化钒(VCl3)、硫酸钒(VSO4·8H2O)、二氯化钒(VCl2)和一氧化钒(VO)中的一种以上。
4.根据权利要求1所述的表面处理溶液组合物，其中，所述胶态二氧化硅的粒度为5-15nm，并且所述胶态二氧化硅水分散在pH为3-5的酸性水溶液中。
5.根据权利要求1所述的表面处理溶液组合物，其中，所述胶态二氧化硅是Ludox HAS(snowtex-O)。
6.根据权利要求1所述的表面处理溶液组合物，其中，所述聚硅氧烷共聚物包含硅氧烷化合物和硅烷化合物中的至少一种成分。
7.根据权利要求6所述的表面处理溶液组合物，其中，所述硅氧烷化合物是选自聚二甲基硅氧烷、聚乙烯基硅氧烷、聚苯基甲基硅氧烷和六甲基硅氧烷中的一种以上。
8.根据权利要求6所述的表面处理溶液组合物，其中，所述硅烷化合物是选自甲基三甲氧基硅烷、乙基三甲氧基硅烷、六甲基二硅烷、乙氧基三乙基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、γ-环氧丙氧基三乙基硅烷和γ-环氧丙氧基三甲基硅烷中的一种以上。
9.根据权利要求6所述的表面处理溶液组合物，其中，所述聚硅氧烷共聚物的重均分子量为300-1500。
10.一种经表面处理的热浸镀锌钢板，其包括：
钢板；
热浸镀锌层，形成在所述钢板的至少一面上；和
三价铬酸盐薄膜层，形成在所述热浸镀锌层上，
其中，所述三价铬酸盐薄膜层包含：
37.7-58.1重量％的三价铬化合物，所述三价铬化合物包含磷酸铬(A)和硝酸铬(B)，并且其含量比A/(A+B)满足0.89-0.95；
34.6-40.7重量％的硅烷偶联剂；
1.4-8.2重量％的钒系防锈耐蚀剂；
4.2-6.6重量％的胶态二氧化硅；和
1.7-6.8重量％的聚硅氧烷共聚物。
11.根据权利要求10所述的经表面处理的热浸镀锌钢板，其中，所述硅烷偶联剂是选自2-(3,4-环氧环己基)-乙基三甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-脲基丙基三甲氧基硅烷和正硅酸四乙酯中的一种以上。
12.根据权利要求10所述的经表面处理的热浸镀锌钢板，其中，所述钒系防锈耐蚀剂是选自五氧化二钒(V2O5)、偏钒酸(HVO3)、偏钒酸铵、偏钒酸钠、三氯氧化钒(VOCl3)、三氧化二钒(V2O3)、二氧化钒(VO2)、硫酸氧钒(VOSO4)、草酸氧钒[VO(COO)2]、乙酰丙酮氧钒[VO(OC(CH3)＝CHCOCH3))2]、乙酰丙酮钒[V(OC(CH3)＝CHCOCH3))3]、三氯化钒(VCl3)、硫酸钒(VSO4·8H2O)、二氯化钒(VCl2)和一氧化钒(VO)中的一种以上。
13.根据权利要求10所述的经表面处理的合金化热浸镀锌钢板，其中，所述胶态二氧化硅的粒度为5-15nm。
14.根据权利要求10所述的经表面处理的合金化热浸镀锌钢板，其中，所述胶态二氧化硅是Ludox HAS(snowtex-O)。
15.根据权利要求10所述的经表面处理的合金化热浸镀锌钢板，其中，所述聚硅氧烷共聚物包含硅氧烷化合物和硅烷化合物中的至少一种成分。
16.根据权利要求15所述的经表面处理的合金化热浸镀锌钢板，其中，所述硅氧烷化合物是选自聚二甲基硅氧烷、聚乙烯基硅氧烷、聚苯基甲基硅氧烷和六甲基硅氧烷中的一种以上。
17.根据权利要求15所述的经表面处理的合金化热浸镀锌钢板，其中，所述硅烷化合物是选自甲基三甲氧基硅烷、乙基三甲氧基硅烷、六甲基二硅烷、乙氧基三乙基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、γ-环氧丙氧基三乙基硅烷和γ-环氧丙氧基三甲基硅烷中的一种以上。
18.根据权利要求15所述的经表面处理的合金化热浸镀锌钢板，其中，所述聚硅氧烷共聚物的重均分子量为300-1500。
19.根据权利要求10所述的经表面处理的热浸镀锌钢板，其中，所述三价铬酸盐薄膜层的厚度为0.3-0.5μm。
20.一种制造经表面处理的热浸镀锌钢板的方法，其包括以下步骤：
将权利要求1至9中任一项所述的表面处理溶液组合物涂覆在形成有热浸镀锌层的热浸镀锌钢板上；以及
将涂覆的所述表面处理溶液组合物进行干燥，以形成三价铬酸盐薄膜层。
21.根据权利要求20所述的制造经表面处理的热浸镀锌钢板的方法，其中，涂覆所述表面处理溶液组合物的步骤是以2.14-3.57μm的厚度进行涂覆。
22.根据权利要求20所述的制造经表面处理的热浸镀锌钢板的方法，其中，以原材料钢板的最终达到温度(PMT)为基准，所述干燥在40-60℃的温度下进行。
23.根据权利要求20所述的制造经表面处理的热浸镀锌钢板的方法，其中，所述干燥在热风干燥炉或感应加热炉中进行。
24.根据权利要求23所述的制造经表面处理的热浸镀锌钢板的方法，其中，所述热风干燥炉的内部温度为100-200℃。
25.根据权利要求23所述的制造经表面处理的热浸镀锌钢板的方法，其中，向所述感应加热炉施加1000-3500A的电流。
26.根据权利要求20所述的制造经表面处理的热浸镀锌钢板的方法，其中，还包括将所述三价铬酸盐薄膜层进行空冷的步骤。
27.根据权利要求20所述的制造经表面处理的热浸镀锌钢板的方法，其中，制造所述热浸镀锌钢板的方法通过连续工艺进行，所述连续工艺的速度为80-100米/分钟。
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