WO2024149259A1 - 一种用于镀锡钢板的钝化处理液、镀锡钢板及其制造方法 - Google Patents

一种用于镀锡钢板的钝化处理液、镀锡钢板及其制造方法 Download PDF

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Publication number
WO2024149259A1
WO2024149259A1 PCT/CN2024/071411 CN2024071411W WO2024149259A1 WO 2024149259 A1 WO2024149259 A1 WO 2024149259A1 CN 2024071411 W CN2024071411 W CN 2024071411W WO 2024149259 A1 WO2024149259 A1 WO 2024149259A1
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Prior art keywords
tin
plated steel
steel sheet
passivation
passivation treatment
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PCT/CN2024/071411
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English (en)
French (fr)
Inventor
李鹏
魏军胜
陈红星
李秀军
徐清亮
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to AU2024208137A priority Critical patent/AU2024208137A1/en
Publication of WO2024149259A1 publication Critical patent/WO2024149259A1/zh
Priority to MX2025007494A priority patent/MX2025007494A/es
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • B05D3/10—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 by other chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • B05D3/10—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 by other chemical means
    • B05D3/102—Pretreatment of metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the invention relates to a surface treatment liquid and a process, in particular to a surface treatment liquid and a process for tin-plated steel plates.
  • tinplates In order to give the metal cans a beautiful appearance and good corrosion resistance, tinplates generally need to be surface-coated before they are made into metal cans, that is, one or more layers of organic coatings are coated on the surface of the tinplates and cured into a film, so as to give the metal cans a beautiful appearance and good corrosion resistance. Therefore, coating performance is a very important performance indicator of tinplates.
  • the surface tin layer of the tinplate sheet needs to be passivated to prevent the rapid oxidation of tin and improve the coating properties.
  • the traditional surface treatment technology of tinplate is to use chromate electrolytic passivation, that is, the tinplate is placed in a chromate solution and subjected to cathode electrolysis to form a passivation film containing chromium oxide on the surface of the tinplate.
  • the chromate used in this process is usually dichromate or chromic anhydride, but long-term use shows that this simple chromium oxide passivation film cannot give the tinplate completely satisfactory finishing performance, and defects such as paint shrinkage or poor paint film adhesion often occur, affecting the normal use of the tinplate.
  • the present invention aims to provide a passivation treatment liquid for tin-plated steel sheets.
  • the passivation treatment liquid to passivate the tin-plated steel sheets, the coating performance of the tin-plated steel sheets can be improved.
  • One of the purposes of the present invention is to provide a passivation treatment liquid for tin-plated steel sheets, which can give the surface of the tin-plated steel sheets better coating wettability and better paint film adhesion, so as to improve and solve the coating problems encountered by traditional tin-plated sheets.
  • the present invention provides a passivation treatment solution for tin-plated steel sheets, which comprises the following effective ingredients:
  • Chromic anhydride the content of which is 15-30g/L;
  • Metaphosphoric acid and/or metaphosphate the content of which is 5-15 g/L;
  • Ammonium bromide the content of which is 1-5g/L;
  • Nitrogen-containing organic matter the content of which is 0.2-2g/L.
  • chromic anhydride is the source of chromium in the passivation film on the surface of the tin-plated steel sheet
  • metaphosphoric acid and its salt are the source of phosphorus in the passivation film
  • ammonium bromide and nitrogen-containing organic matter increase the dispersibility and current efficiency of the passivation solution.
  • the addition of phosphorus can increase the bonding force between the tin-plated steel sheet and the paint film.
  • the content of chromic anhydride can also be 18-28g/L, or 20-25g/L, for example 22g/L;
  • the content of metaphosphoric acid and/or metaphosphate can also be 6-13g/L, or 8-11g/L, for example 9g/L, 10g/L;
  • the content of ammonium bromide can also be 2-4.5g/L, or 2.5-4g/L, or 3-4g/L, for example 3.5g/L; and/or the content of nitrogen-containing organic matter can also be 0.5-1.8g/L, or 0.8-1.5g/L, or 1-1.2g/L.
  • the nitrogen-containing organic matter includes at least one of thiourea, glycine and nicotinic acid.
  • the metaphosphate is an inorganic salt of metaphosphate, such as potassium salt, sodium salt, etc. of metaphosphate.
  • chromic acid and its salts such as chromic acid, potassium chromate, and sodium chromate, can also be used as the source of chromium.
  • the pH value of the passivation treatment solution of the present invention is 1.2-3.8.
  • This pH value range can be adjusted by using phosphoric acid and sodium hydroxide.
  • the pH value can also be 1.5-3.5, or 2-3.2, or 2.5-3.
  • Another object of the present invention is to provide a tinplate with excellent coating properties, whose surface has excellent coating wettability and better paint film adhesion, so as to improve and solve the coating problems encountered by traditional tinplate.
  • the present invention also provides a tin-plated steel sheet with excellent coating performance, comprising a steel substrate and a metal tin layer on the steel substrate, wherein the metal tin layer has a surface passivation film formed by the passivation treatment solution as described above.
  • the surface passivation film of the tin-plated steel sheet of the present invention contains metallic chromium, trivalent oxide of chromium, tin oxide and phosphorus, and does not contain hexavalent chromium.
  • the content of metallic chromium in the surface passivation film of the present invention is 0.5-2.5 mg/m 2 , and can also be 0.8-2.2 mg/m 2 , or 1.1-2 mg/m 2 , or 1.2-1.8 mg/m 2 ;
  • the content of trivalent chromium oxide is 2-7 mg/m 2 , and can also be 2.5-6.3 mg/m 2 , or 3.1-5.6 mg/m 2 , or 3.7-4.8 mg/m 2 , for example 4.5 mg/m 2 ;
  • the content of phosphorus is 0.3-5 mg/m 2 , and can also be 0.6-4.1 mg/m 2 , or 1.2-3 mg/m 2 , or 1.7-2.4 mg/m 2 , for example 1.9 mg/m 2 ;
  • the content of tin oxide is 0.5-2 mC/cm 2 , and can also be 0.9-1.9 mC/cm 2 , or 1.1-1.8 mC/cm 2 , or 1.3-1.7 mC/c
  • millicoulombs per square centimeter is usually used to represent the content of tin oxide, which specifically means the amount of reduction required for tin oxide to completely remove the oxide film by cathode electrolysis in a low concentration (eg 0.001 mol/L) hydrogen bromide solution.
  • the paint film adhesion grade of the tin-plated steel sheet of the present invention is grade 1.
  • the surface contact angle of the tin-plated steel sheet described in the present invention is ⁇ 76°.
  • Another object of the present invention is to provide a method for manufacturing a tin-plated steel sheet with excellent coating performance.
  • the tin-plated steel sheet manufactured by this method has excellent coating wettability and better paint film adhesion on its surface.
  • the present invention also provides a method for manufacturing tin-plated steel sheets, comprising the following steps: a) pre-treating the tin-plated steel substrate after soft melting to remove the tin oxide film on the surface of the tin-plated steel substrate; b) passivating the pre-treated tin-plated steel substrate, the passivation step comprising immersing the pre-treated tin-plated steel substrate in the above-mentioned passivation treatment solution, and using the tin-plated steel substrate as a cathode for cathodic electrolysis treatment.
  • the pretreatment step comprises immersing the tin-plated steel substrate after soft melting into a chromic anhydride solution, wherein the chromic anhydride content in the chromic anhydride solution is 10-20 g/L.
  • the tin-plated steel substrate of the present invention can be prepared by a common method known in the art, preferably by a method comprising the following steps performed in sequence: alkali washing (degreasing) of the steel substrate, pickling (surface activation), electroplating tin on the steel substrate to form a metal tin layer on the steel substrate, and soft melting (alloying) the tin-plated steel substrate.
  • the method of the present invention further comprises cleaning the surface of the tin-plated steel sheet with clean water after the passivation step until no chromate residue remains.
  • the tin-plated steel substrate is usually subjected to a soft melting alloying treatment, that is, the tin-plated steel substrate is quickly heated to a specific temperature above the melting point of metallic tin (e.g., 240-310°C) to form a tin-iron alloy layer between the steel substrate and the metallic tin layer. Since tin is easily oxidized, this process will generate a large amount of tin oxide on the surface of the tin-plated steel sheet.
  • a soft melting alloying treatment that is, the tin-plated steel substrate is quickly heated to a specific temperature above the melting point of metallic tin (e.g., 240-310°C) to form a tin-iron alloy layer between the steel substrate and the metallic tin layer. Since tin is easily oxidized, this process will generate a large amount of tin oxide on the surface of the tin-plated steel sheet.
  • the present invention pre-treats the tin-plated steel substrate after tin plating and reflowing by immersing it in a chromic anhydride solution.
  • the tin oxide film on the surface can be removed before the passivation step to control the content of tin oxide in the finished product.
  • the pretreatment is performed for 2-10 seconds.
  • the temperature of the chromic anhydride solution is 30-50°C.
  • the temperature of the passivation treatment solution is 40-65°C.
  • the charge density of the cathode electrolysis treatment is 15-60 C/dm 2 .
  • the method of the present invention further comprises squeezing the cleaned tin-plated steel sheet after passivation with a squeezing roller, and then drying the surface of the tin-plated steel sheet with hot air not less than 80°C; and the dried tin-plated steel sheet is conventionally coated with DOS oil (dioctyl sebacate) to obtain a finished product.
  • DOS oil dioctyl sebacate
  • the passivation treatment solution Compared with the prior art, the passivation treatment solution, the obtained tin-plated steel sheet and the manufacturing method thereof of the present invention have the following beneficial effects:
  • the chromic anhydride concentration used in the passivation treatment liquid of the present invention is low and does not contain fluorine, thereby reducing the corrosiveness to production equipment, reducing the environmental load and the environmental protection treatment cost of chromate wastewater.
  • the tin-plated steel sheet obtained by using the passivation treatment liquid and the manufacturing method described in the present invention has very excellent coating performance, is more conducive to the full spreading and wetting of the paint on the surface of the tin-plated steel sheet, and forms a strong bonding force between the paint film and the tin-plated steel sheet after the paint is cured, which can significantly reduce the quality risks of coating dewetting and poor paint film adhesion, and is more conducive to controlling the amount of tin oxide on the surface of the tin-plated steel sheet at a low level, prolonging the aging resistance of maintaining good coating performance, and will not cause a decrease in coating performance even after a long period of storage.
  • Pretreatment Immerse the tin-plated steel substrate after soft melting in a chromic anhydride solution, wherein the chromic anhydride content in the chromic anhydride solution is 10-20 g/L, the temperature of the chromic anhydride solution is 30-50° C., and the pretreatment time is 2-10 s;
  • the tin-plated steel sheet is used as a cathode for cathodic electrolysis treatment, and the cathode electrolysis charge density range is 15-60C/ dm2 ; after the passivation treatment, the surface of the tin-plated steel sheet is cleaned with clean water until no chromate residue is left; the cleaned tin-plated steel sheet after passivation is squeezed dry with a squeeze roller, and the surface of the tin-plated steel sheet is dried with hot air of not less than 80°C;
  • the comparative examples 1-3 do not undergo a pretreatment step, and the passivation step also adopts a conventional process
  • the passivation solution used is a 25 g/L sodium dichromate solution, and the passivation solution of the present invention is not used.
  • Table 1 lists the specific process parameters of the pretreatment process of Examples 1-9.
  • Table 2 lists the contents of the passivation treatment solutions of Examples 1-9 and Comparative Examples 1-3 of the present invention.
  • Table 3 lists the process parameters of the passivation step of Examples 1-9 of the present invention and Comparative Examples 1-3.
  • the inventors detected the components in the surface passivation films in Examples 1-9 and Comparative Examples 1-3, and listed them in Table 4.
  • the wettability of the surface of the tin-plated steel sheet of the embodiment and the comparative example was measured using a contact angle tester, and the test medium was water.
  • the surface wettability of each embodiment and the comparative example is listed in Table 4.
  • the evaluation method of the paint film adhesion performance refers to the paint film adhesion evaluation method adopted in QB/T 2763-2006 "Coating of Tin (or Chrome) Thin Steel Sheets".
  • the paint is a commercially available epoxy phenolic paint, which is coated on the surface of the tin-plated steel sheets involved in the examples and comparative examples, and the dry film weight of the paint film is 10g/ m2 .
  • the coating film adhesion performance is evaluated according to the paint film shedding area ratio, and the paint film adhesion performance of the tin-plated steel sheets of each example and comparative example is listed in Table 4.
  • the passivation film of the tin-plated steel sheet of the present invention contains metal chromium and phosphorus, while the comparative examples 1-3 do not contain them, and the contact angles of the embodiments 1-9 of the present invention are obviously smaller than those of the comparative examples 1-3, and the paint film adhesion grade is all grade 1. This shows that the present invention has better surface wetting performance and paint film adhesion performance.

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  • Engineering & Computer Science (AREA)
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Abstract

本发明公开了一种用于镀锡钢板的钝化处理液，包含：铬酐，其含量为15-30g/L；偏磷酸和/或偏磷酸盐，其含量为5-15g/L；溴化铵，其含量为1-5g/L；含氮有机物，其含量为0.2-2g/L。本发明还公开了采用该钝化处理液处理的镀锡钢板以及该镀锡钢板的制造方法。该镀锡钢板表面具有优异的涂料润湿性和更好的漆膜附着力。

Description

一种用于镀锡钢板的钝化处理液、镀锡钢板及其制造方法 技术领域
本发明涉及一种表面处理液及工艺，尤其涉及一种用于镀锡钢板的表面处理液及工艺。
背景技术
为了赋予金属罐精美的外观和良好的耐蚀性能，镀锡钢板在制成金属罐之前一般都需要进行表面涂饰，即在镀锡钢板表面涂覆一层或数层有机涂料并固化成膜，以便赋予金属罐精美的外观和良好的耐蚀性。因此，涂饰性能是镀锡钢板的一个非常重要的使用性能指标。
为了赋予镀锡钢板良好的涂装性能，需要对镀锡钢板的表面锡层进行钝化处理，以防止锡的快速氧化和提高涂装性能。
传统的镀锡钢板表面处理技术是采用铬酸盐电解钝化的方式，即，将镀锡钢板置于铬酸盐溶液中，进行阴极电解处理，在镀锡钢板表面形成一层含铬氧化物的钝化膜层。这种工艺使用的铬酸盐通常是重铬酸盐或铬酐，但长期的使用情况表明，这种单纯的铬氧化物钝化膜并不能赋予镀锡钢板完全令人满意的涂饰性能，经常会发生涂漆缩孔或是漆膜附着力不良等缺陷，影响镀锡钢板的正常使用。
此外，公开号为US3925171A的美国专利文献提到了一种在镀锡钢板表面沉积金属铬和铬氧化物的方法，其可以提高镀锡钢板的漆膜附着力。
基于此，本发明旨在提供一种用于镀锡钢板的钝化处理液，采用该钝化处理液对镀锡钢板进行钝化处理，可以提高镀锡钢板的涂饰性能。
发明内容
本发明的目的之一在于提供一种用于镀锡钢板的钝化处理液，其能够赋予镀锡钢板表面更好的涂料润湿性和更好的漆膜附着力，以改善和解决传统镀锡板遇到的涂饰性问题。
为了实现上述目的，本发明提出了一种用于镀锡钢板的钝化处理液，其包含如下有效成分：
铬酐，其含量为15-30g/L；
偏磷酸和/或偏磷酸盐，其含量为5-15g/L；
溴化铵，其含量为1-5g/L；
含氮有机物，其含量为0.2-2g/L。
在本发明的钝化处理液中，铬酐是镀锡钢板表面钝化膜中铬的来源，偏磷酸及其盐是钝化膜中磷的来源，溴化铵和含氮有机物则增加了钝化液的分散能力和电流效率。其中磷的添加可以增加镀锡钢板与漆膜的结合力。
优选地，铬酐的含量还可以为18-28g/L，或20-25g/L，例如22g/L；偏磷酸和/或偏磷酸盐的含量还可以为6-13g/L，或8-11g/L例如9g/L、10g/L；溴化铵的含量还可以为2-4.5g/L，或2.5-4g/L，或3-4g/L例如3.5g/L；和/或含氮有机物的含量还可以为0.5-1.8g/L，或0.8-1.5g/L，或1-1.2g/L。
优选地，在本发明所述的钝化处理液中，所述含氮有机物包括硫脲、甘氨酸、烟酸中的至少一种。
优选地，在本发明所述的钝化处理液中，所述偏磷酸盐为偏磷酸的无机盐，例如偏磷酸的钾盐、钠盐等。
优选地，在本发明所述的钝化处理液中，除了铬酐之外，也可使用铬酸及其盐作为铬的来源，例如铬酸、铬酸钾、铬酸钠。
优选地，本发明所述的钝化处理液的pH值为1.2-3.8。该pH值范围可以采用磷酸和氢氧化钠调节获得。pH值还可以为1.5-3.5，或2-3.2，或2.5-3。
本发明的另一目的在于提供一种涂饰性能优良的镀锡钢板，其表面具有优异的涂料润湿性和更好的漆膜附着力，以改善和解决传统镀锡钢板遇到的涂饰性问题。
基于此，本发明还提供了一种涂饰性能优良的镀锡钢板，包括钢基体和钢基体上的金属锡层其中，金属锡层上具有由如上文所述的钝化处理液形成的表面钝化膜。
优选地，本发明所述的镀锡钢板，其表面钝化膜含有金属铬、铬的三价氧化物、锡氧化物和磷，并且不含有六价铬。
优选地，本发明的表面钝化膜中，金属铬的含量为0.5-2.5mg/m2，还可以 为0.8-2.2mg/m2，或1.1-2mg/m2，或1.2-1.8mg/m2；铬的三价氧化物的含量为2-7mg/m2，还可以为2.5-6.3mg/m2，或3.1-5.6mg/m2，或3.7-4.8mg/m2，例如4.5mg/m2；磷的含量为0.3-5mg/m2，还可以为0.6-4.1mg/m2，或1.2-3mg/m2，或1.7-2.4mg/m2，例如1.9mg/m2；锡氧化物的含量为0.5-2mC/cm2，还可以为0.9-1.9mC/cm2，或1.1-1.8mC/cm2，或1.3-1.7mC/cm2，或1.4-1.5mC/cm2。
需要说明的是，本技术领域内通常采用毫库伦每平方厘米，即“mC/cm2”来表示锡氧化物的含量，具体含义为锡氧化物在低浓度(例如0.001mol/L)的溴化氢溶液、再阴极电解以完全去除氧化膜所需的还原电量。
优选地，本发明的镀锡钢板的漆膜附着力等级为1级。
优选地，本发明所述的镀锡钢板的表面接触角≤76°。
本发明的又一目的在于提供一种涂饰性能优良的镀锡钢板的制造方法，采用该方法制得的镀锡钢板，其表面具有优异的涂料润湿性和更好的漆膜附着力。
基于此，本发明还提供了一种制造镀锡钢板的方法，包括如下步骤；a)对软熔后的镀锡钢基体进行预处理，去除镀锡钢基体表面的锡氧化膜；b)对预处理后的镀锡钢基体进行钝化，所述钝化步骤包括将预处理后的镀锡钢基体浸入上述钝化处理液中，并将所述镀锡钢基体作为阴极进行阴极电解处理。
优选地，在本发明的方法中，预处理步骤包括将软熔后的镀锡钢基体浸入铬酐溶液中，所述铬酐溶液中的铬酐含量为10-20g/L。
本发明的镀锡钢基体可采用本领域已知的常用方法制备，优选采用包括依次进行的如下步骤的方法制备：对钢基体进行碱洗(除油)、酸洗(活化表面)、在钢基体上电镀锡，形成钢基体上的金属锡层、对镀锡钢基体进行软熔(合金化)。
优选地，本发明的方法还包括在钝化步骤后用清水清洗镀锡钢板表面至无铬酸盐残留。
由于镀锡钢板的单面镀锡量范围为0.3-15g/m2，故通常需对镀锡钢基体进行软熔合金化处理，即将镀锡钢基体快速加热到金属锡的熔点之上的特定温度(例如240-310℃)，在钢基体和金属锡层之间形成一层锡铁合金层。由于锡很容易被氧化，此工序会在镀锡钢板表面生成较多的锡氧化物。
本发明通过将镀锡和软熔后的镀锡钢基体浸入铬酐溶液中进行预处理的 步骤，可以在钝化步骤前，先去除表面的锡氧化膜，以控制成品中锡氧化物的含量。
优选地，在本发明所述的方法中，预处理进行2-10s的时间。
优选地，在本发明所述的方法中，所述铬酐溶液的温度为30-50℃。
优选地，在本发明所述的方法中，钝化处理液的温度为40-65℃。
优选地，在本发明所述的方法中，阴极电解处理的电量密度为15-60C/dm2。
优选地，本发明的方法还包括将钝化后经清洗的镀锡钢板用挤干辊挤干后，用不低于80℃热风将镀锡钢板表面烘干；烘干后的镀锡钢板进行常规涂DOS油(癸二酸二辛酯)后即获得成品。
相较于现有技术，本发明所述的钝化处理液、制得的镀锡钢板及其制造方法具有如下有益效果：
本发明所述的钝化处理液所采用的铬酐浓度较低，且不含氟，降低了对生产设备的腐蚀性，降低了环境负荷和铬酸盐废水的环保处理成本。
采用本发明所述的钝化处理液以及制造方法获得的镀锡钢板具有非常优异的涂饰性能，更有利于涂料在镀锡钢板表面充分铺展与润湿，并在涂料固化后的漆膜与镀锡钢板之间形成很强的结合力，可明显降低发生涂料反润湿和漆膜附着力不良的质量隐患，更有利于控制镀锡钢板表面的锡氧化物量在较低水平，延长保持良好涂饰性能的耐时效能力，即使经过较长时间储存，不会引起涂饰性能的降低。
具体实施方式
下面将结合具体的实施例对本发明所述的钝化处理液、镀锡钢板及其制造方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
实施例1-9以及对比例1-3
按照下述步骤制造本发明实施例1-9的镀锡钢板：
(1)对钢基体进行碱洗；
(2)酸洗；
(3)在钢基体上电镀锡，形成金属锡层，其中镀锡量为2.8g/m2；
(4)对镀锡钢基体进行软熔；
(5)预处理：将软熔后的镀锡钢基体浸入铬酐溶液中，铬酐溶液中的铬酐含量为10-20g/L，铬酐溶液的温度为30-50℃，预处理时间为2-10s；
(6)钝化：将经过预处理的镀锡钢基体浸入表2列出的钝化处理液中，用磷酸和氢氧化钠调节钝化处理液的pH值范围为1.2-3.8，钝化处理液温度为40-65℃，将镀锡钢板作为阴极进行阴极电解处理，阴极电解电量密度范围为15-60C/dm2；钝化处理后，用清水清洗镀锡钢板表面至无铬酸盐残留；将钝化后经清洗的镀锡钢板用挤干辊挤干后，用不低于80℃热风将镀锡钢板表面烘干；
(7)涂DOS油。
需要说明的是，为了显示本发明的实施效果，对比例1-3不进行预处理步骤，并且其钝化处理步骤也是采用传统工艺，所用钝化液为25g/L重铬酸钠溶液，并不采用本发明的钝化处理液。
表1列出了实施例1-9的预处理工艺的具体工艺参数。
表1.
表2列出了本发明的实施例1-9以及对比例1-3的钝化处理液成分含量。
表2.

表3列出了本发明的实施例1-9以及对比例1-3的钝化步骤工艺参数。
表3.
为了验证本发明的实施效果，发明人检测了实施例1-9和对比例1-3中的表面钝化膜中的成分，将其列于表4中。
此外，还对实施例1-9和对比例1-3进行了涂饰性能评价试验，其包括：
(1)表面润湿性能试验
使用接触角测试仪测量实施例和对比例镀锡钢板表面的润湿性能，测试介质为水。各实施例和对比例的表面润湿性能列于表4中。
(2)漆膜附着力性能
漆膜附着力性能评价方法参照QB/T 2763-2006《涂覆镀锡(或铬)薄钢板》所采用的漆膜附着力评价方法。涂料采用市售的某型环氧酚醛涂料，涂覆在实施例和对比例涉及的镀锡钢板表面，漆膜干膜重量为10g/m2。按漆膜脱落面积比评价涂膜附着力性能，将各实施例和对比例的镀锡钢板漆膜附着力性能列于表4中。
表4.
通过表4可以看出，由于未采用本发明的预处理步骤，对比例1-3的镀锡钢板的钝化膜中的锡氧化物全部高于本发明的上限2mC/cm2，而本发明各实施例的镀锡钢板的钝化膜中的锡氧化物含量均较低。
此外，由于采用了本发明所述的钝化处理液，本发明的镀锡钢板的钝化膜中含有金属铬和磷，而对比例1-3均不含有，并且本发明实施例1-9的接触角显然明显小于对比例1-3，且漆膜附着力等级均为1级。由此说明本发明具有更优的表面润湿性能和漆膜附着力性能。
需要说明的是，本发明的保护范围中现有技术部分并不局限于本申请文件所给出的实施例，所有不与本发明的方案相矛盾的现有技术，包括但不局限于在先专利文献、在先公开出版物，在先公开使用等等，都可纳入本发明的保护范围。
此外，本案中各技术特征的组合方式并不限本案权利要求中所记载的组合方式或是具体实施例所记载的组合方式，本案记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。
还需要注意的是，以上所列举的实施例仅为本发明的具体实施例。显然本发明不局限于以上实施例，随之做出的类似变化或变形是本领域技术人员能从本发明公开的内容直接得出或者很容易便联想到的，均应属于本发明的保护范围。

Claims (14)

  1. 一种用于镀锡钢板的钝化处理液，其特征在于，所述钝化处理液包含如下有效成分：
    铬酐，其含量为15-30g/L；
    偏磷酸和/或偏磷酸盐，其含量为5-15g/L；
    溴化铵，其含量为1-5g/L；
    含氮有机物，其含量为0.2-2g/L。
  2. 如权利要求1所述的钝化处理液，其特征在于，所述含氮有机物包括硫脲、甘氨酸、烟酸中的至少一种。
  3. 如权利要求1所述的钝化处理液，其特征在于，所述钝化处理液的pH值为1.2-3.8。
  4. 一种镀锡钢板，包括钢基体和钢基体上的金属锡层，其特征在于，所述金属锡层上具有表面钝化膜，所述表面钝化膜由权利要求1-3中任一项所述的钝化处理液形成。
  5. 如权利要求4所述的镀锡钢板，其特征在于，所述表面钝化膜含有金属铬、铬的三价氧化物、锡氧化物和磷，并且不含有六价铬。
  6. 如权利要求5所述的镀锡钢板，其特征在于，所述表面钝化膜中金属铬的含量为0.5-2.5mg/m2，铬的三价氧化物的含量为2-7mg/m2，磷的含量为0.3-5mg/m2，锡氧化物含量为0.5-2mC/cm2。
  7. 如权利要求4所述的镀锡钢板，其特征在于，所述镀锡钢板的漆膜附着力等级为1级。
  8. 如权利要求4所述的镀锡钢板，其特征在于，其所述镀锡钢板的表面接触角≤76°。
  9. 一种制造镀锡钢板的方法，其特征在于，所述方法包括如下步骤：
    a)对软熔后的镀锡钢基体进行预处理，去除镀锡钢基体表面的锡氧化膜；
    b)对预处理后的镀锡钢基体进行钝化，所述钝化步骤包括将预处理后的镀锡钢基体浸入如权利要求1-3中任一项所述的钝化处理液中，并将所述镀锡钢基体作为阴极进行阴极电解处理。
  10. 如权利要求9所述的方法，其特征在于，所述预处理包括将软熔后的镀锡钢基体浸入铬酐溶液中，所述铬酐溶液中的铬酐含量为10-20g/L。
  11. 如权利要求9所述的方法，其特征在于，所述预处理进行2-10s的时间。
  12. 如权利要求10所述的方法，其特征在于，所述铬酐溶液的温度为30-50℃。
  13. 如权利要求9所述的方法，其特征在于，在步骤b)中，钝化处理液的温度为40-65℃。
  14. 如权利要求9所述的方法，其特征在于，在步骤b)中，阴极电解处理的阴极电量密度为15-60C/dm2。
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