WO2017092648A1 - 一种无铬表面处理镀锡板、其生产方法及表面处理剂 - Google Patents

一种无铬表面处理镀锡板、其生产方法及表面处理剂 Download PDF

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Publication number
WO2017092648A1
WO2017092648A1 PCT/CN2016/107673 CN2016107673W WO2017092648A1 WO 2017092648 A1 WO2017092648 A1 WO 2017092648A1 CN 2016107673 W CN2016107673 W CN 2016107673W WO 2017092648 A1 WO2017092648 A1 WO 2017092648A1
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Prior art keywords
chromium
surface treatment
zinc
tin plate
treated
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PCT/CN2016/107673
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English (en)
French (fr)
Inventor
李鹏
晏人芸
魏军胜
李兵虎
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宝山钢铁股份有限公司
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Application filed by 宝山钢铁股份有限公司 filed Critical 宝山钢铁股份有限公司
Priority to MYPI2018701922A priority Critical patent/MY189387A/en
Priority to PL16869958.5T priority patent/PL3385405T3/pl
Priority to AU2016363456A priority patent/AU2016363456B2/en
Priority to EP16869958.5A priority patent/EP3385405B1/en
Priority to US15/779,246 priority patent/US11248298B2/en
Priority to ES16869958T priority patent/ES2912177T3/es
Priority to SG11201803648XA priority patent/SG11201803648XA/en
Publication of WO2017092648A1 publication Critical patent/WO2017092648A1/zh
Priority to ZA2018/02971A priority patent/ZA201802971B/en

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Classifications

    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • 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
    • C23C22/73—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 characterised by the process
    • C23C22/76—Applying the liquid by spraying
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the invention belongs to the technical field of tin plate, and particularly relates to a chromium-free surface treatment tin plate, a production method thereof and a surface treatment agent.
  • Tinplate also known as tinplate
  • Tinplate packaging has a beautiful appearance, good sealing and high strength. With the advantage of long shelf life, the packaged food or beverage can preserve the original flavor of the food for a long time.
  • tinplate applications are sometimes used in conjunction with electronic devices or home appliance components, and thus have a wide range of applications.
  • the tin on the surface of the tin plate is a metal that is easily oxidized by air, the oxide formed by the oxidation of tin reduces the processing property and performance of the tin plate, so tin plating is required in the production of the conventional tin plate.
  • the surface of the board is passivated.
  • the passivation method for tinplate production is usually an electrolytic passivation process immersed in a chromate solution.
  • the chromium in the solution is electrolytically reduced to a trivalent chromium compound or a metal chromium deposited on the surface of the tin plate to form a dense chromium blunt.
  • the film is treated with tin plate with excellent performance, environmental protection and non-toxic, and food contact safety.
  • chromate due to the use of chromate in the passivation process of tinplate, the use of chromate is increasingly limited in the increasingly strict environmental protection situation, so the chrome-free surface treatment for tinplate production is A major trend in the development of tinplate production technology.
  • the existing surface treatment method of tinplate is the production technology of chromate electrolytic passivation.
  • the surface of the tin plated steel plate is immersed in a chromium-containing treatment liquid for cathodic electrolysis treatment to form a layer on the surface of the tin plate.
  • a passivation film containing chromium which is composed of a trivalent chromium compound and a metallic chromium, has excellent properties, is environmentally friendly and non-toxic, and is safe for food contact.
  • the disadvantage of this tin plate passivation production method is that hexavalent chromate is used, and the production and use of chromate pose a threat to environmental safety, and the environmental protection treatment cost is high.
  • Cida Patent No. CN180606287.3 discloses a surface treatment liquid containing a phosphate ion, a tin ion and a silane coupling agent.
  • Chinese patent CN200880103264.2 discloses a chromium-free surface treatment method using a silane coupling agent as a main component and formed on the surface of the tin-plated layer, and the techniques of the above two patents can impart good stability to the surface of the tinplate. And paint film adhesion performance, but in terms of corrosion resistance compared with chromium passivation still has a clear gap.
  • Chinese patent CN01116679.7 discloses a surface treatment liquid containing a silane coupling agent and/or its hydrolytic condensation product, containing dispersed solid silica particles and zirconium and/or titanium ions, and further containing a water-soluble acrylic resin;
  • Chinese Patent No. CN200580028595.0 discloses a chromium-free treatment liquid containing an inorganic surface treatment layer containing at least one of Ti, Zr or Al and O, F and an organic surface treatment layer containing a silane coupling agent or a phenolic water-soluble compound.
  • Chinese patent CN201210445665.4 discloses a chromium-free passivation solution for treating a tin-plated steel plate, the composition mainly comprising: an inorganic compound containing at least one of silicon, titanium and zirconium, containing aluminum, vanadium, a metal compound of at least one of manganese, cobalt, nickel and molybdenum, further comprising a water-soluble resin;
  • Chinese Patent No. CN201280066604.5 discloses a tin-plating treatment using a chromium-free passivation agent coated with titanium and/or zirconium A passivation method for drying the film surface to form a film, and the passivation liquid contains a water-soluble resin.
  • Chinese patent CN201410650819.2 discloses a chromium-free surface treatment liquid for a tin plate containing titanium, silicon, aluminum, manganese, nickel plasma and phosphate.
  • the passivation liquid system has complex composition and is difficult to form on the surface of the tin plate.
  • the passivation film with uniform composition, excellent performance and stability, and fluorine in the passivation solution, the environmental performance is not ideal, and the technology is more difficult to implement successfully.
  • the object of the present invention is to provide a chromium-free surface-treated tin plate, a production method thereof and a surface treatment agent, and the tin layer on the surface of the tin plate forms a uniform and compact, stable and stable chromium-free passivation.
  • Membrane, the passivation film can impart excellent surface stability, corrosion resistance and paint adhesion property to the surface of the tin plate, and the food contact is safe, and the tin plate can achieve the performance comparable to the chromium passivation, and the production thereof
  • the process does not use chromate, which makes the tinplate production process truly green and meets increasingly stringent environmental regulations.
  • the zinc in the passivation film is derived from a zinc salt
  • the zirconium in the passivation film is derived from a zirconium salt
  • the molybdenum is derived from a molybdenum salt
  • the silicon in the passivation film is derived from an organosiloxane or a polysiloxane.
  • the zinc salt is at least one selected from the group consisting of zinc sulfate, zinc acetate, zinc nitrate, zinc gluconate, and zinc methionate;
  • the zirconium salt is selected from the group consisting of zirconyl sulfate, zirconyl nitrate, ammonium zirconium carbonate, zirconium acid.
  • the oxane is obtained by hydrolysis of an epoxy silane coupling agent.
  • a chromium-free surface treatment tinplate water-based surface treatment agent comprising: 0.1 to 5 wt% of a zinc salt, 0.1 to 5 wt% of a zirconium salt and/or a molybdenum salt, and 5 to 30 wt% of an organosiloxane or a poly
  • the silicone is the balance, and the aqueous surface treatment agent has a pH of 3-6.
  • the aqueous surface treatment agent further contains at least one of a reinforcing agent, a wetting agent and an organic acid modifier, the reinforcing agent content is 0.1 to 2% by weight; and the wetting agent content is 0.1 to 2wt%, the content of the organic acid regulator is 0.1 to 1% by weight;
  • the reinforcing agent is polyvinyl alcohol
  • the wetting agent is polyethylene glycol
  • the organic acid adjusting agent is selected from the group consisting of citric acid, acetic acid or fumaric acid.
  • the zinc salt is at least one selected from the group consisting of zinc sulfate, zinc acetate, zinc nitrate, zinc gluconate, and zinc methionate;
  • the zirconium salt is selected from the group consisting of zirconyl sulfate, zirconyl nitrate, ammonium zirconium carbonate, zirconium acid.
  • At least one of tetrabutyl ester and zirconium isopropoxide the molybdenum salt being selected from the group consisting of molybdic acid, ammonium molybdate, sodium molybdate, and potassium molybdate One less; the organosiloxane or polysiloxane is obtained by hydrolysis of an epoxy silane coupling agent.
  • the passivation film of the invention has good surface stability energy, and the surface tin oxide does not increase obviously even after long-time storage or hot air baking during processing; has good corrosion resistance and anti-sulfurization spot Performance and acid resistance; excellent adhesion of painted film after coating, even better than chromium passivation under certain conditions, and no heavy metal and organic components potentially harmful to human body, food contact is non-toxic , friendly to the environment.
  • the passivation film on the surface of the surface-treated tin plate according to the present invention contains zinc, zirconium and/or molybdenum, and further contains silicon, wherein zinc, zirconium and/or molybdenum, particularly zinc, and active in the passivation film
  • the functional group is combined and dispersed uniformly in the passivation film, which can significantly improve the corrosion resistance of the passivation film, and the combined use can achieve the effect equivalent to the chromium passivation.
  • the zirconium salt, the zinc salt and the molybdenum salt contained in the environmentally-friendly water-based surface treatment agent of the invention provide a passivation film-forming substance, and enhance the corrosion resistance of the passivation film against sulfur and acid; wherein the organosiloxane or The polysiloxane is obtained by hydrolysis of an epoxy silane coupling agent to provide a passivation film-forming substance, which acts as a skeleton of the passivation film, and its group can be well combined with zinc, zirconium and/or molybdenum.
  • the tin layer has a good sealing effect, and its epoxy-based organic functional group plays an important role in ensuring the adhesion property of the paint film after coating.
  • the polyvinyl alcohol in the aqueous surface treatment agent of the invention can enhance the toughness of the structure of the passivation film, can not easily generate microcracks, and improve the sealing effect;
  • the polyethylene glycol acts as a wetting agent and has a dispersion effect. It can improve the performance of the surface treatment agent, can better wet the surface of the tinplate and make the treatment agent spread more easily;
  • the role of the organic acid regulator is to adjust the pH of the surface treatment agent.
  • the surface treatment agent of the invention is an aqueous treatment agent, does not contain chromate, does not contain fluorine, does not contain phosphorus, has non-toxic composition, is environmentally friendly, has a pH value of 3-6, and the aqueous surface treatment agent is directly coated on the surface treatment agent.
  • the surface of the tin plate is coated on the surface of the tin plate after being immersed, and dried to form a film.
  • the surface of the tin plate treated by the surface treatment agent of the invention has excellent surface stability, paint adhesion property and corrosion resistance, and is safe for food contact, and can be used for food cans, beverage cans, chemical cans and electronic devices.
  • the invention also provides a method for producing a chromium-free surface treated tinplate, comprising the following steps:
  • the electroplating tin process is phenolsulfonic acid (PSA) tin or methanesulfonic acid (MSA) tin plating process, plating After the tin is completed, the tin layer is reflowed;
  • the surface of the reflowed tin plate is cleaned, the tin plate is immersed in distilled water or distilled water is sprayed onto the surface of the tin plate for cleaning, and then the excess moisture on the surface of the tin plate is removed by the squeeze roller;
  • the surface of the tin plate coated with the aqueous surface treatment agent is subjected to hot air drying, the hot air temperature is controlled at 80 to 120 ° C, the drying time is 0.2 to 2 seconds, and the surface treatment agent is dried to form a film to obtain a chromium-free surface treated tin plate. .
  • the impregnation step is: immersing the tin plate in the aqueous surface treatment agent, and the immersion time is 0.2 to 5 seconds.
  • the surface of the tinplate after reflow is cleaned, the cleaning is to remove impurities and dirt on the surface, and the surface of the tinplate is clean; the impregnation is performed before coating.
  • Pretreatment of the surface of the tin plate can activate the surface of the tin plate, making the passivation film easier to form a film and improving the uniformity of film distribution.
  • the surface treatment tin plate manufacturing method of the invention is simple, shortens the traditional process flow, the water surface treatment agent used does not contain chromate, and the chromate electrolytic treatment process is omitted, and the process of the invention is simpler and more reliable.
  • the waste liquid treatment involved is rare or not, and the comprehensive operation cost of the process including environmental protection treatment is low, and the conventional tinplate production line can be appropriately modified to realize the operation of the process.
  • the surface-treated tinplate of the invention has good surface stability, corrosion resistance, sulphide resistance and acid resistance, and the surface comprehensive performance can be equivalent to chromium passivation, and the surface is more clean and black-free. Ash; the coated film has excellent adhesion and performance, even better than chromium passivation under certain conditions. It does not contain heavy metals and organic components that are potentially toxic to humans. Food contact is non-toxic and environmentally friendly.
  • the surface treatment agent of the present invention does not contain environmentally unfriendly chromate, does not contain potentially toxic fluorine, does not contain phosphate which is liable to cause environmentally rich oxidation, and the treatment component is environmentally friendly, non-toxic, and biodegradable or Naturally degraded, the production waste liquid is simple to handle, environmentally friendly, and environmentally friendly treatment costs are low.
  • the surface treatment tinplate of the invention has simple production method, good process stability, low cost and environmental friendliness, and the surface tinplate production method realizes the complete green color of the tinplate from the production process to the final product.
  • the development trend of tinplate production technology meets the current strict environmental protection policies and regulations, has good economic benefits and significant social benefits, and has great commercialization and application value.
  • composition and treatment process of the aqueous surface treatment agent for the chromium-free passivation treatment tin plate in Examples 1-10 of the present invention are as shown in Table 1, and the content of each component in the surface treatment agent is expressed by mass percentage (wt%).
  • the remainder is water, wherein the treatment method refers to a method in which the aqueous surface treatment agent is directly coated or immersed and then coated, and the treatment time refers to the total time required from the immersion + coating or direct coating to the completion of drying.
  • the method for producing a chromium-free surface-treated tinplate according to the present invention comprises the following steps:
  • the tin-plated substrate is subjected to a tin plating process and a tin layer reflow treatment, wherein the tin plating process is performed by tin plating of phenolsulfonic acid or tin plating of methanesulfonic acid, and the tin layer is subjected to reflow treatment after tin plating is completed;
  • aqueous surface treatment agent of Examples 1-10 applying the aqueous surface treatment agent of Examples 1-10 to the surface of the tin plate which has been subjected to or not being impregnated by spraying or rolling, and extruding the excess aqueous surface treatment agent by using a squeeze roller.
  • the liquid film thickness of the aqueous surface treatment agent is made uniform, and the film thickness can be adjusted according to the spray amount or the coating amount, and the squeeze roll pressure;
  • the hot air temperature is controlled at 80-120 ° C, drying time 0.2 ⁇ 2 seconds, the aqueous surface treatment agent is dried to form a film, to obtain a chromium-free surface treatment tin plate.
  • the baking discoloration resistance, the paint film adhesion property and the corrosion resistance performance of the obtained chrome-free surface-treated tin plate were evaluated and evaluated.
  • the results are shown in Table 2, and compared with the chromium passivation comparison sample.
  • the comparison sample is a traditional chromate electrolytic passivation tin plate sample.
  • the chromium content of the passivation film of the comparison sample is 5 mg/m 2 . .
  • the evaluation content is as follows:
  • the surface of the tinplate was simulated by the hot air at 200 ° C for 60 minutes by the hot air at 200 ° C. Observe the surface of the tin plate, whether there is baking discoloration, and investigate its resistance to baking discoloration.
  • the coating film adhesion evaluation method refers to the coating method for evaluating the adhesion of the paint film used in QB/T 2763-2006 "coated tin (or chrome) steel sheet), and the coating is coated with a commercially available epoxy phenolic paint.
  • the dry film weight of the tin plating coating is 6-8 g/m 2 , and the surface of the paint film is peeled off after the ring and the tape is peeled off, and the degree of the paint film is separated from the surface of the sample, and the film is peeled off according to the paint film.
  • the area was evaluated for coating adhesion properties and compared to chromium passivated samples.
  • the anti-sulfurization performance evaluation method refers to the anti-sulfurization performance evaluation method of QB/T 2763-2006 "Coated tin-plated (or chromium) steel sheet", and according to the test results, the surface of the sample treated by the passivation agent of the present invention is formed to form a sulfide spot. The situation is compared with a chromium passivated sample.
  • the acid resistance evaluation method refers to the evaluation method of acid resistance of QB/T 2763-2006 "coated tin (or chrome) steel sheet", and the acidified spots formed on the surface of the sample treated by the passivation agent of the present invention are observed according to the test results. And compared with chromium passivated samples.
  • the tin plate obtained by using the chromium-free surface treatment method of the present invention is oxidized with chromium in terms of baking discoloration resistance, paint film adhesion, smear resistance and acid resistance.
  • the comparative samples achieved comparable performance and achieved better results in terms of paint adhesion and corrosion resistance.

Abstract

一种无铬表面处理镀锡板、其生产方法及表面处理剂，通过在镀锡板表面涂覆含有0.1～5wt％锌盐，0.1～5wt％锆盐和/或钼盐，5～30wt％硅氧烷或聚硅氧烷的环保型水性表面处理剂，在锡层表面形成一层成分均匀致密、性能良好且稳定的不含铬的钝化膜，该钝化膜含有0.1～20mg/m2的锌、0.1～20mg/m2的锆和/或钼、0.5～100mg/m2的硅，该钝化膜能够赋予镀锡板表面优良的表面稳定性、耐蚀性能和漆膜附着力性能，且食品接触安全，该镀锡板在性能上可实现与铬钝化媲美，其生产过程不使用铬酸盐，使镀锡板生产过程实现真正的绿色，符合日益严格的环保法规要求。

Description

一种无铬表面处理镀锡板、其生产方法及表面处理剂 技术领域
本发明属于镀锡板技术领域，具体涉及一种无铬表面处理镀锡板、其生产方法及表面处理剂。
背景技术
镀锡板又被称为马口铁，是一种常用的金属包装材料，被广泛用于食品、饮料、茶叶、糖果、化工用品等的包装，镀锡板包装具有外观精美，密封性好，强度高，保质期长等优点，包装食品或饮料能在长时间内最大程度的保存食品原有的风味。镀锡板用途除了作为包装材料外，有时也被用于与电子器件或家电部件，因此应用领域广泛。
由于镀锡板表面的锡是一种容易被空气氧化的金属，锡被氧化后形成的氧化物会降低镀锡板的加工性能和使用性能，因此在传统的镀锡板生产中会对镀锡板表面进行钝化处理。
镀锡板生产的钝化方式通常采用浸入铬酸盐溶液的电解钝化处理工艺，溶液中的铬被电解还原成三价铬化合物或金属铬沉积在镀锡板表面形成一层致密的铬钝化膜，经此方式处理的镀锡板性能优良，环保无毒，食品接触安全。但由于镀锡板的钝化生产过程使用了铬酸盐，在日益严格的环境保护形势下，铬酸盐的使用受到越来越多的限制，因此实现镀锡板生产的无铬表面处理是镀锡板生产技术发展的一大趋势。
现有的镀锡板表面处理方式是采用铬酸盐电解钝化的生产技术，是将表面镀锡后的钢板浸在含铬的处理液中进行阴极电解处理，使镀锡板表面形成一层含铬的钝化膜，此钝化膜由三价铬化合物及金属铬组成，性能优良，环保无毒，食品接触安全。但这种镀锡板钝化生产方法的缺点是要使用六价的铬酸盐，而铬酸盐的生产和使用会对环境安全造成威胁，且环保处理成本较高。
当前，铬酸盐的生产和使用在全球都受到越来越严格的限制，对镀锡板生产也提出了实现无铬化的要求。因此，有必要开发表面不含铬的镀锡板表面处理生产方法，且生产过程采用环保新型表面处理剂，经无铬表面处理的镀锡钢板仍要求保证优良的加工和使用性能。关于镀锡板生产的无铬表面处理，国内外已有不少相关研究成果发布，具体如下所述。
关于镀锡板无铬表面处理的相关技术，中国专利CN01806287.3公开了一种含有磷酸离子、锡离子和硅烷偶联剂的表面处理液。中国专利CN200880103264.2公开了以硅烷偶联剂作为主要组分并形成于所述镀锡层表面上的无铬表面处理方法，上述两项专利涉及的技术能够赋予镀锡板表面良好的稳定性和漆膜附着力性能，但在耐蚀性能方面跟铬钝化相比还是有较明显的差距。
中国专利CN01116679.7公开了含有硅烷偶联剂和/或其水解缩合产物，含有分散状固态二氧化硅颗粒以及锆和/或钛的离子或化合物，还含有水溶性丙烯酸树脂的表面处理液；中国专利CN200580028595.0公开了含有Ti、Zr或Al中的至少一种以及O、F的无机表面处理层和含有硅烷偶联剂或酚类水溶性化合物的有机表面处理层的无铬处理液和处理方法；中国专利CN201210445665.4公开了一种用于处理镀锡钢板的无铬钝化液，其成分主要包括：含有硅、钛和锆的至少其中之一的无机化合物，含有铝、钒、锰、钴、镍和钼的至少其中之一的金属化合物，还含有水溶性树脂；中国专利CN201280066604.5公开了一种使用涂覆含钛和/或锆的无铬钝化处理剂在镀锡板表面烘干成膜的钝化方法，钝化液中含有水溶性树脂。上述几种技术内容实质比较相近，被认为可以实现良好的漆膜附着力和耐蚀性能，但耐蚀性能仍难以达到铬钝化的水平，且这些表面处理剂某些成分具有一定的毒性或潜在的毒性，所生产的镀锡板食品接触安全存在一定风险，很难实现真正的商业化应用。
中国专利CN201410650819.2公开了含有一种含有钛、硅、铝、锰、镍等离子及磷酸根的镀锡板用无铬表面处理液，该钝化液体系成分复杂，难以在镀锡板表面形成成分均匀、性能优良且稳定的钝化膜，且钝化液中含有氟，环保性能不理想，此项技术实现成功应用的难度也较大。
发明内容
本发明的目的在于提供一种无铬表面处理镀锡板、其生产方法及表面处理剂，该镀锡板的锡层表面形成一层成分均匀致密、性能良好且稳定的不含铬的钝化膜，该钝化膜能够赋予镀锡板表面优良的表面稳定性、耐蚀性能和漆膜附着力性能，且食品接触安全，该镀锡板在性能上可实现与铬钝化媲美，其生产过程不使用铬酸盐，使镀锡板生产过程实现真正的绿色，符合日益严格的环保法规要求。
为达到上述目的，本发明的技术方案如下：
一种无铬表面处理镀锡板，其锡层表面覆盖无铬钝化膜，该无铬钝化膜含有：0.1～20mg/m2的锌、0.1～20mg/m2的锆和/或钼、0.5～100mg/m2的硅。
进一步，所述的钝化膜中的锌来自锌盐，钝化膜中的锆来自锆盐，钼来自钼盐，钝化膜中的硅来自有机硅氧烷或聚硅氧烷。
优选地，所述锌盐选自硫酸锌、醋酸锌、硝酸锌、葡萄糖酸锌、蛋氨酸锌中的至少一种；所述锆盐选自硫酸氧锆、硝酸氧锆、碳酸锆铵、锆酸四丁酯、异丙醇锆中的至少一种；所述钼盐选自钼酸、钼酸铵、钼酸钠、钼酸钾中的至少一种；所述的有机硅氧烷或聚硅氧烷由环氧基硅烷偶联剂水解而得到。
一种无铬表面处理镀锡板用水性表面处理剂，其包含：0.1～5wt％的锌盐，0.1～5wt％的锆盐和/或钼盐，5～30wt％的有机硅氧烷或聚硅氧烷，余量为水，所述的水性表面处理剂的pH为3-6。
进一步，所述的水性表面处理剂还含有增强剂、润湿剂和有机酸调节剂中的至少一种，所述的增强剂含量为0.1～2wt％；所述的润湿剂含量为0.1～2wt％，所述有机酸调节剂的含量为0.1～1wt％；
又进一步，所述的水性表面处理剂中，所述的增强剂为聚乙烯醇，所述的润湿剂为聚乙二醇，有机酸调节剂选自柠檬酸、醋酸或富马酸。
优选地，所述锌盐选自硫酸锌、醋酸锌、硝酸锌、葡萄糖酸锌、蛋氨酸锌中的至少一种；所述锆盐选自硫酸氧锆、硝酸氧锆、碳酸锆铵、锆酸四丁酯、异丙醇锆中的至少一种；所述钼盐选自钼酸、钼酸铵、钼酸钠、钼酸钾中的至 少一种；所述的有机硅氧烷或聚硅氧烷由环氧基硅烷偶联剂水解而得到。
本发明的钝化膜具有良好的表面稳定性能，即使经过长时间存储或在加工过程中经过热风烘烤，表面锡氧化物也不会有明显的增长；具有良好的耐蚀性能，抗硫化斑性能和抗酸性能；经涂装后的漆膜附着力性能优良，在某些条件下性能甚至优于铬钝化，而且，不含对人体有潜在毒性的重金属和有机物成分，食品接触无毒，对环境友好。
本发明所涉及的表面处理镀锡板表面的钝化膜中含有锌，锆和/或钼，还含有硅，其中的锌、锆和/或钼，特别是锌，与钝化膜中的活性官能团结合，在钝化膜中呈弥散状均匀分布，可显著提高钝化膜的耐蚀性能，组合使用可达到与铬钝化相当的效果。
本发明的环保水性表面处理剂中含有的锆盐、锌盐、钼盐，提供钝化膜成膜物质，增强钝化膜的抗硫、抗酸等耐蚀性能；其中的有机硅氧烷或聚硅氧烷由环氧基硅烷偶联剂水解得到，提供钝化膜成膜物质，起到钝化膜的骨架作用，其基团能与锌、锆和/或钼很好的结合，对锡层有良好的封闭效果，其具有的环氧基有机官能团对保证涂装后的漆膜附着力性能有重要作用。
本发明的水性表面处理剂中的聚乙烯醇作为增强剂，可增强钝化膜结构的强韧性，不容易产生微裂纹，提高封闭效果；聚乙二醇作为润湿剂，同时有分散作用，可改善表面处理剂的使用性能，可更好的润湿镀锡板表面和使处理剂更易均匀铺展；有机酸调节剂的作用为调节表面处理剂的pH值。
本发明的表面处理剂为水性处理剂，不含铬酸盐，不含氟，不含磷，组成物无毒，环保性好，pH值为3～6，该水性表面处理剂直接涂覆于镀锡板表面或经浸渍后再涂覆于镀锡板表面，烘干成膜。
经本发明的表面处理剂处理的镀锡板表面具有优良的表面稳定性、漆膜附着力性能和耐蚀性能，食品接触安全，可用于食品罐、饮料罐、化工罐及电子器件等。
本发明还提供一种无铬表面处理镀锡板的生产方法，包括如下步骤：
1)电镀锡工艺和软熔处理
电镀锡工艺采用苯酚磺酸镀(PSA)锡或甲基磺酸(MSA)镀锡工艺，镀 锡完成后对锡层进行软熔处理；
2)清洗
对软熔后的镀锡板表面进行清洗，将镀锡板浸渍在蒸馏水中或将蒸馏水喷淋至镀锡板表面进行清洗，然后通过挤干辊除去镀锡板表面多余水分；
3)涂覆
将所述水性表面处理剂通过喷淋或辊涂的方式涂覆到镀锡板表面上，用挤干辊挤掉多余的水性表面处理剂，使水性表面处理剂的液膜涂覆均匀；
4)烘干
对涂覆有水性表面处理剂的镀锡板表面进行热风烘干，热风温度控制在80～120℃，烘干时间0.2～2秒，表面处理剂干燥成膜，获得无铬表面处理镀锡板。
进一步，在步骤3)涂覆步骤前还包括浸渍步骤，所述的浸渍步骤为：将镀锡板浸渍在所述水性表面处理剂中，浸渍时间为0.2～5秒。
本发明的无铬表面处理镀锡板的生产方法中，对软熔后的镀锡板表面进行清洗，清洗是为了清除表面的杂质和污垢，保证镀锡板表面洁净；涂覆前进行浸渍，对镀锡板表面进行预处理，可活化镀锡板表面，使钝化膜更容易成膜并改善膜分布的均匀性。
传统工艺的镀锡板需要在电解槽中进行阴极电解处理，通常需要2个或更多的电解槽，还需要2～3个清洗槽，同时还需要阳极、导电辊和挤干辊等其他配套装备。
本发明涉及的表面处理镀锡板生产方法简单，缩短了传统的工艺流程，采用的水性表面处理剂中不含有铬酸盐，省掉了铬酸盐电解处理工艺，本发明工艺更简单可靠，涉及的废液处理少或无，包括环保处理在内的工艺运行综合成本低，对传统的镀锡板生产线进行适当改造就可以实现此工艺的投入运行。
与现有技术相比，本发明的有益效果：
1)本发明的表面处理镀锡板，具有良好的表面稳定性能、耐蚀性能、抗硫化斑性能和抗酸性能，表面综合性能可达到与铬钝化相当，且表面更为洁净，无黑灰；经涂装后的漆膜附着力性能优良，在某些条件下性能甚至优于铬钝化， 不含对人体有潜在毒性的重金属和有机物成分，食品接触无毒，对环境友好。
2)本发明的表面处理剂中不含有对环境不利的铬酸盐，不含有具有潜在毒性的氟，不含有易导致环境富氧化的磷酸盐，处理剂组分环保无毒，易生物降解或自然降解，生产废液处理简单，对环境友好，环保处理费用低。
3)本发明的表面处理镀锡板的生产方法简单，工艺稳定性好，成本低，对环境友好，该表面镀锡板生产方法实现了镀锡板从生产过程到最终产品的完全绿色，符合镀锡板的生产技术发展趋势，符合当前严格的环保政策和法规要求，具有良好的经济效益和显著的社会效益，具有很大的商业化推广应用价值。
具体实施方式
以下结合具体实施例对本发明作进一步说明。
本发明的实施例1-10中无铬钝化处理镀锡板的水性表面处理剂的成分及处理工艺如表1所示，表面处理剂中各组分含量以质量百分比(wt％)计，其余为水，其中，处理方法指将水性表面处理剂直接涂覆或浸渍后再涂覆的方式，处理时间指从浸渍+涂覆或直接涂覆到烘干完成所需的总时间。
本发明的无铬表面处理镀锡板的生产方法，包括如下步骤：
1)镀锡基板经过电镀锡工艺和锡层软熔处理，其中，电镀锡工艺采用苯酚磺酸镀锡或甲基磺酸镀锡工艺，镀锡完成后对锡层进行软熔处理；
2)对软熔后的镀锡板表面进行清洗，将镀锡板浸渍在蒸馏水中或将蒸馏水喷淋至镀锡板表面进行清洗，然后通过挤干辊除去镀锡板表面多余水分；
3)将实施例1-5、7、9-10的镀锡板浸渍在对应的水性表面处理剂中，浸渍时间为0.2～5秒；
4)将实施例1-10的水性表面处理剂通过喷淋或辊涂的方式涂覆到经过或未经浸渍的镀锡板表面上，采用挤干辊将多余的水性表面处理剂挤掉，使水性表面处理剂的液膜厚度均匀，膜厚可根据喷淋量或涂覆量、以及挤干辊压力调节；
5)对涂覆有表面处理剂的镀锡板表面进行热风烘干，热风温度控制在 80～120℃，烘干时间0.2～2秒，水性表面处理剂经干燥成膜，获得无铬表面处理镀锡板。
本发明实施例1-10制得无铬钝化处理镀锡样板后，对得到的无铬表面处理镀锡板的耐烘烤变色性、漆膜附着力性能和耐蚀性性能进行评价，评价结果如表2所示，并与铬钝化对比样进行对比，对比样为传统的铬酸盐电解钝化处理镀锡板试样，对比样的钝化膜中铬的含量为5mg/m2。
评价内容如下：
1)耐烘烤变色性
模拟镀锡板在涂装时的工况，使用200℃的热风烘烤通过实施例得到的表面处理镀锡板60分钟。观察镀锡板表面，是否存在烘烤变色情况，考察其耐烘烤变色性能。
2)漆膜附着力性能
漆膜附着力评价方法参照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，涂料采用市售的环氧酚醛涂料，涂覆在经本发明钝化剂处理的镀锡板表面，镀锡涂料干膜重量为6～8g/m2，漆膜表面经划圈和胶带剥离后，检验漆膜脱离试样表面的程度，按漆膜脱落面积评价涂膜附着力性能并与铬钝化试样进行比较。
3)抗硫化斑性能
抗硫化斑性能评价方法参照QB/T 2763-2006《涂覆镀锡(或铬)薄钢板》的抗硫化斑性能评价方法，根据试验结果观察经本发明钝化剂处理试样表面生成硫化斑的情况，并与铬钝化试样进行比较。
4)抗酸性能
抗酸性能评价方法参照QB/T 2763-2006《涂覆镀锡(或铬)薄钢板》的抗酸性能评价方法，根据试验结果观察经本发明钝化剂处理试样表面生成酸化斑的情况，并与铬钝化试样进行比较。
从表2可以看出，经过使用本发明所述无铬表面处理方法制得的镀锡板在耐烘烤变色性、漆膜附着力、抗硫化斑性能和抗酸性能等方面与铬钝化对比样相比都实现了相当的性能，在漆膜附着力和耐蚀性方面还取得了了更好的效果。
Figure PCTCN2016107673-appb-000001
表2
Figure PCTCN2016107673-appb-000002
备注：◎——性能优良，且优于铬钝化；○——性能与铬钝化相当；●——性能不如铬钝化。

Claims (17)

  1. 一种无铬表面处理镀锡板，其锡层表面形成无铬钝化膜，所述无铬钝化膜含有：0.1～20mg/m2的锌、0.1～20mg/m2的锆和/或钼、0.5～100mg/m2的硅。
  2. 根据权利要要求1所述的无铬表面处理镀锡板，其特征在于，所述的钝化膜中的锌来自锌盐。
  3. 根据权利要要求1所述的无铬表面处理镀锡板，其特征在于，所述的钝化膜中的锆来自锆盐，钝化膜中的钼来自钼盐；钝化膜中的硅来自有机硅氧烷或聚硅氧烷。
  4. 根据权利要要求2所述的无铬表面处理镀锡板，其特征在于，所述锌盐选自硫酸锌、醋酸锌、硝酸锌、葡萄糖酸锌、蛋氨酸锌中的至少一种。
  5. 根据权利要要求3所述的无铬表面处理镀锡板，其特征在于，所述锆盐选自硫酸氧锆、硝酸氧锆、碳酸锆铵、锆酸四丁酯、异丙醇锆中的至少一种。
  6. 根据权利要要求3所述的无铬表面处理镀锡板，其特征在于，所述钼盐选自钼酸、钼酸铵、钼酸钠、钼酸钾中的至少一种。
  7. 根据权利要要求3所述的无铬表面处理镀锡板，其特征在于，所述的有机硅氧烷或聚硅氧烷由环氧基硅烷偶联剂水解得到。
  8. 一种无铬表面处理镀锡板用水性表面处理剂，其包含：0.1～5wt％的锌盐，0.1～5wt％的锆盐和/或钼盐，5～30wt％的有机硅氧烷或聚硅氧烷，余量为水，所述的水性表面处理剂的pH为3-6。
  9. 根据权利要求8所述的无铬表面处理镀锡板用水性表面处理剂，其特征在于，还包括增强剂、润湿剂和有机酸调节剂中的至少一种，所述的增强剂含量为0.1～2wt％，所述的润湿剂含量为0.1～2wt％，所述有机酸调节剂的含量为0.1～1wt％。
  10. 根据权利要求9所述的无铬表面处理镀锡板用水性表面处理剂，其特征在于，所述的增强剂为聚乙烯醇，所述的润湿剂为聚乙二醇。
  11. 根据权利要求9所述的无铬表面处理镀锡板用水性表面处理剂，其特征在于，所述的有机酸调节剂选自柠檬酸、醋酸或富马酸。
  12. 根据权利要求8所述的无铬表面处理镀锡板用水性表面处理剂，其特征在于，所述锌盐选自硫酸锌、醋酸锌、硝酸锌、葡萄糖酸锌、蛋氨酸锌中的至少一种。
  13. 根据权利要求8所述的无铬表面处理镀锡板用水性表面处理剂，其特征在于，所述锆盐选自硫酸氧锆、硝酸氧锆、碳酸锆铵、锆酸四丁酯、异丙醇锆中的至少一种。
  14. 根据权利要求8所述的无铬表面处理镀锡板用水性表面处理剂，其特征在于，所述钼盐选自钼酸、钼酸铵、钼酸钠、钼酸钾中的至少一种。
  15. 根据权利要求8所述的无铬表面处理镀锡板用水性表面处理剂，其特征在于，所述的有机硅氧烷或聚硅氧烷由环氧基硅烷偶联剂水解而得到。
  16. 一种无铬表面处理镀锡板的生产方法，包括如下步骤：
    1)电镀锡工艺和软熔处理
    电镀锡工艺采用苯酚磺酸镀锡或甲基磺酸镀锡工艺，镀锡完成后对锡层进行软熔处理；
    2)清洗
    对软熔后的镀锡板表面进行清洗，将镀锡板浸渍在水中或将水喷淋至镀锡板表面进行清洗，然后通过挤干辊除去镀锡板表面多余水分；
    3)涂覆
    将权利要求8-15任一项所述水性表面处理剂通过喷淋或辊涂的方式涂覆到镀锡板表面上，用挤干辊挤掉多余的水性表面处理剂，使水性表面处理剂的液膜涂覆均匀；
    4)烘干
    对涂覆有水性表面处理剂的镀锡板表面进行热风烘干，热风温度控制在80～120℃，烘干时间0.2～2秒，水性表面处理剂干燥成膜，获得无铬表面处理镀锡板。
  17. 根据权利要求16所述的无铬表面处理镀锡板的生产方法，其特征在于，在步骤3)涂覆步骤前还包括浸渍步骤，所述的浸渍步骤为：将镀锡板浸渍在权利要求8-15任一项所述水性表面处理剂中，浸渍时间为0.2～5秒。
PCT/CN2016/107673 2015-11-30 2016-11-29 一种无铬表面处理镀锡板、其生产方法及表面处理剂 WO2017092648A1 (zh)

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