• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    An aftertreatment composition of an environmentally friendly galvanized steel sheet containing no chromium is provided. It contains colloidal silica, methoxy silane and polyvinyl alcohol in a weight ratio of 1: 0.01 to 0.3: 0.15 to 0.5 and at least one metal salt selected from molybdate and vanadate and is free of chromium. Not only is it harmful but also shows the same level of corrosion resistance as when treated with a conventional chromium-containing post-treatment composition upon post-treatment on a steel sheet using the same.
    公开号:KR20030052410A
    申请号:KR1020010082359
    申请日:2001-12-21
    公开日:2003-06-27
    发明作者:전재호；박치록
    申请人:포스코신기술연구조합；주식회사 포스코；재단법인 포항산업과학연구원；포항강판 주식회사；
    IPC主号:
    专利说明:

    Chromium-Free Surface Treatment Composition for Galvanized Steel
    [1] The present invention relates to a post-treatment composition for maintaining the corrosion resistance of galvanized steel sheet, and more particularly to a post-treatment composition of an environmentally friendly galvanized steel sheet containing no chromium.
    [2] Conventionally, by applying a solution containing hexavalent Cr ions to a galvanized steel sheet by spraying or using a roll, a chromium film layer is formed on the surface of the steel sheet to impart corrosion resistance to the galvanized steel sheet. However, hexavalent chromium not only destroys the environment, but also is harmful to the human body. In other words, hexavalent chromium is a very toxic substance that causes cancer, and solutions containing hexavalent chromium must be treated with wastewater using special techniques.
    [3] Therefore, recently, non-chromate (Non-chromate) technology for applying a chromium-free solution that does not use hexavalent chromium has been developed, and examples thereof include US Pat.
    [4] Accordingly, an object of the present invention is to provide an environmentally friendly after-treatment composition for galvanized steel sheet containing no chromium.
    [5] Another object of the present invention is to provide a post-treatment composition for a galvanized steel sheet which gives the galvanized steel sheet the same level of corrosion resistance as when chromated and does not contain any chromium.
    [6] According to the invention,
    [7] It consists of at least one metal salt and balance water selected from the group consisting of colloidal silica, methoxy silane, polyvinyl alcohol, molybdate and vanadate,
    [8] The colloidal silica, methoxy silane and polyvinyl alcohol is provided with a galvanized steel sheet after-treatment composition is mixed in a weight ratio of 1: 0.01 to 0.3: 0.15 to 0.5.
    [9] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
    [10] The post-treatment composition for galvanized steel sheet consisting of colloidal silica, methoxy silane and polyvinyl alcohol of the present invention in a specific ratio and further comprising at least one metal salt selected from molybdate and vanadate has no chromium that is harmful to humans and the environment. The post-treatment composition of the galvanized steel sheet, which is not contained, is used to post-treat the galvanized steel sheet to form a film on the galvanized steel sheet to ensure corrosion resistance equivalent to that of a conventional chromate treated product. The aftertreatment composition of the present invention is further harmless to the human body and environmentally friendly.
    [11] In the post-treatment aqueous solution of the present invention, colloidal silica, methoxy silane and polyvinyl alcohol (PVA) are dissolved in water in a weight ratio of 1: 0.01 to 0.3: 0.15 to 0.5, and further divided into groups composed of molybdate and vanadate. At least one metal salt selected from is added.
    [12] Colloidal silica is a stable dispersion of silica particles of very small size (usually 10-100 nm) in water. Colloidal silica is the main basis for forming a coating layer on the steel sheet, and serves to increase the corrosion resistance of the coating layer by forming a continuous -O-Si-O- structure on the surface.
    [13] Mepoxy silane functions to increase the adhesion between the substrate and the polyvinyl alcohol, which is a metal, the hydroxy group is hydrogen-bonded to the substrate such as metal by the hydration reaction and condensation reaction during the drying process, the organic functional group is polyvinyl alcohol To form a dense coating layer.
    [14] Polyvinyl alcohol combines with colloidal silica to harden the coating layer and also act as a filler to increase the coating amount.
    [15] Colloidal silica, methoxy silane and polyvinyl alcohol not only form a firm coating on the surface of the galvanized layer by bonding with each other, but also serve to increase adhesion to metal.
    [16] The colloidal silica, methoxy silane and polyvinyl alcohol are dissolved in water in a weight ratio of 1: 0.01 to 0.3: 0.15 to 0.5 in order for the post-treatment aqueous solution of the present invention to impart the intended corrosion resistance on the steel sheet. If the amount of methoxy silane and polyvinyl alcohol is less than the lower limit, the adhesion is inferior, and if it is more than the upper limit, solution stability is lowered.
    [17] Furthermore, in the case of post-treatment of the steel plate with the post-treatment aqueous solution, at least one metal salt selected from the group consisting of molybdate and vanadate is added to further increase the corrosion resistance. Molybdate may be used any water-soluble molybdate that can be dissolved in an aqueous solution to generate Mo ions, including, but not limited to, K 2 MoO 4 , Na 3 PO 4 · 12MoO 3 , Na 2 MoO 4 is included. Vanadate may also be used any water-soluble vanadate that can be dissolved in an aqueous solution to generate V ions, but is not limited thereto, and examples thereof include NaVO 3 , KVO 3 and the like. These metal salts, together with colloidal silica, serve to increase the corrosion resistance of the coating layer. When too little of these metal salts are added, the corrosion resistance does not exhibit an additional effect of increasing corrosion resistance, and when too much is added, solution stability is lowered.
    [18] When molybdate or vanadate are added alone, the addition of molybdate at 0.1 to 0.8 wt% based on the weight of the composition and the vanadate at 0.02 to 0.5 wt% provide excellent solution stability and corrosion resistance. .
    [19] When molybdate is added at the same time vanadate may be added in a sum of the amounts added alone. That is, for example, in the case of the maximum value, 0.8 wt% molybdate and 0.5 wt% vanadate may be added, so that up to 1.3 wt% metal salt may be added. Metal salts are added based on the amount of water, regardless of the amount of colloidal silica.
    [20] The coating amount pretreated on the steel sheet varies depending on the concentration of the solution, the viscosity of the solution, pretreatment conditions, and the like. The most significant of these is the concentration of solids in the solution. In general, when coating the pre-treatment solution through the roll coating method it is usually applied to a substrate solution of 1~1.5cc / m 2, dried coat weight of in the steel sheet is generally required from about 40~80mg / m 2 randomly present The solid content concentration of the post-treatment aqueous solution of the invention can be arbitrarily adjusted in consideration of the desired coating amount and other coating conditions.
    [21] That is, in order to increase the amount of coating, it is possible to simply increase the concentration of solids by reducing the amount of water in the post-treatment aqueous solution. In this invention, the solid content concentration of the post-treatment aqueous solution at the time of manufacture was 40 to 80 mg / m <2> in the amount of coatings.
    [22] The after-treatment aqueous solution of the present invention is applied to any steel sheet by any common coating method shows excellent corrosion resistance.
    [23] Hereinafter, the present invention will be described in detail through examples.
    [24] <Example>
    [25] To prepare a post-treatment aqueous solution of the composition of Table 1a and 1b, respectively. The solution thus prepared was coated on a galvanized steel sheet using a roll coater. The coated film was dried by setting the surface temperature of the steel sheet to 70 ° C. Solid content concentration of the pretreatment aqueous solution was 4-5 wt%. Each of the above components was added based on the weight of the composition.
    [26] Then, the film amount, adhesiveness, solution stability, and corrosion resistance of the galvanized steel plate post-treated with the composition of each invention example and a comparative example were evaluated as follows.
    [27] The film amount adhered to the surface of the galvanized steel sheet was evaluated as (circle) if it was in the target 50-100 mg / m <2> , and if the film amount was less than 50 mg / m <2> .
    [28] After forming a corrosion-resistant film on the surface of a galvanized steel plate, adhesiveness was evaluated as (x) when a coating layer peeled using an adhesive test tape, and when it was not peeled.
    [29] The solution stability was expressed by o when the prepared solution was exposed to room temperature for one month, after which gelation of the solution occurred, when the solution was separated, or when a precipitate was formed.
    [30] Corrosion resistance test was carried out using a salt spray device according to ASTM B3317-73 method. If 5% white blue did not occur for 72 hours on the surface of the specimen, it is marked with × when 5% white blue occurred within 72 hours.
    [31] Invention Examples 1-3
    [32] The solution used in Inventive Example (1) through Inventive Example (3) was changed from 0.1 wt% to 0.8 wt% of silica sol 3 wt%, polyvinyl alcohol 1 wt%, Na 2 MoO 4 0.3 wt% and methoxy silane in 1 liter of water. A coating solution was prepared.
    [33] (Invention Examples 4-6)
    [34] The solution used in Inventive Example (4) through Inventive Example (6) was changed from 0.5 wt% to 2 wt% of silica sol 3 wt%, methoxy silane silane 0.3 wt%, Na 2 MoO 4 0.3 wt% and polyvinyl alcohol in 1 L of water. Post-treatment solution was prepared by pouring.
    [35] (Comparative Examples 1 to 6)
    [36] Comparative Example (1) to Comparative Example (6) prepared a post-treatment composition while varying the concentrations of silica sol, methoxy silane, polyvinyl alcohol, Na 2 MoO 4 in 1 L of water in the amounts shown in Table 1, respectively. Specifically, Comparative Example (1) is a case where 1 wt% of polyvinyl alcohol and 0.3 wt% of Na 2 MoO 4 are added without adding methoxy silane, and Comparative Example (2) is methoxy silane without addition of a metal salt. 0.3 wt% and 1 wt% of polyvinyl alcohol were added, and Comparative Example (3) was added when 0.3 wt% of methoxy silane and 0.3 wt% of Na 2 MoO 4 were added without adding polyvinyl alcohol. (4) shows the case where 0.3 wt% of methoxy silane, 1 wt% of polyvinyl alcohol, and 0.3 wt% of Na 2 MoO 4 are added without adding a silica sol. On the other hand, Comparative Example (5) is a case where 3wt% silica sol, 0.3wt% methoxy silane, 3wt% polyvinyl alcohol and 0.3wt% Na 2 MoO 4 are added, and Comparative Example (6) is 3wt% silica sol, 1 wt% of oxy silane, 1 wt% of polyvinyl alcohol, and 0.3 wt% of Na 2 MoO 4 were added.
    [37] (Comparative Example 7)
    [38] Comparative example (7) is an example of applying the existing chromate solution. Here, chromium concentration means hexavalent chromium ion and was prepared by adding CrO 3 to 1 L of water.
    [39] (Invention Examples 7-9)
    [40] Inventive Example (7) to Inventive Example (9) are a case in which the amounts of Na 2 MoO 4 added to 1 wt% of silica sol, 0.3 wt% of silane, and 1 wt% of polyvinyl alcohol were changed by 0.1, 0.5, and 0.8 wt%, respectively.
    [41] (Invention Examples 10-13)
    [42] Invention example from 10 Inventive Example 13 is the amount added to the silica sol NaVO 3 3wt% in water 1ℓ, silane 0.3wt%, 1wt% of polyvinyl alcohol, each of 0.02, 0.1, 0.2. It is a case where 0.5 wt% is changed.
    [43] (Invention Examples 14 and 15)
    [44] Inventive examples (14) and (15) are cases where Na 2 MoO 4 and NaVO 3 are added together to 3 wt% of silica sol, 0.3 wt% of methoxy silane, and 1 wt% of polyvinyl alcohol. Inventive Example (14) is the case where 0.1% Na 2 MoO 4 and 0.02% NaVO 3 are added, and Inventive Example (15) is the case where 0.2% Na 2 MoO 4 and 0.1% NaVO 3 are added.
    [45] (Comparative Examples 8-12)
    [46] Comparative Examples (8) to (12) vary the addition amounts of molybdate and vanadate, which are metal salts, to 3 wt% silica sol, 0.3 wt% methoxy silane, and 1 wt% polyvinyl alcohol. and no addition and Comparative example 9 Na 2 MoO 4 0.02wt%, Comparative example 10 is NaVO 3 0.01wt%, Comparative example 11 Na 2 MoO 4 1.0wt%, Comparative example (12 ) Is the case where 0.8 wt% of NaVO 3 is added.
    [47] Solution composition (wt%)Characteristic evaluationSilica solSilanePVAMetal saltCoating amountAdhesionSolution stabilityCorrosion resistance Inventive Example 130.1One0.3○○○○ Inventive Example 230.3One0.3○○○○ Inventive Example 330.8One0.3○○○○ Inventive Example 430.30.50.3○○○○ Inventive Example 530.31.50.3○○○○ Inventive Example 630.320.3○○○○ Comparative Example 130One0.3○×○○ Comparative Example 230.3One0○○○× Comparative Example 330.300.3○×○○ Comparative Example 400.3One0.3×○○× Comparative Example 530.330.3○○×○ Comparative Example 63OneOne0.3○○×○ Comparative Example 7One004 (Cr)×○○×
    [48] Solution composition (wt%)Characteristic evaluationSilica solSilanePVAMoVCoating amountAdhesionSolution stabilityCorrosion resistance Inventive Example 730.3One0.10○○○○ Inventive Example 830.3One0.50○○○○ Inventive Example 930.3One0.80○○○○ Inventive Example 1030.3One00.02○○○○ Inventive Example 1130One00.1○○○○ Inventive Example 1230.3One00.2○○○○ Inventive Example 1330.3200.5○○○○ Inventive Example 1430.3One0.10.02○○○○ Inventive Example 1530.3One0.20.1○○○○ Comparative Example 830.3One00○○○× Comparative Example 930.3One0.020○○○× Comparative Example 1030.3One00.01○○○× Comparative Example 1130.3One1.00○○×○ Comparative Example 1230.3One00.8○○×○
    [49] The post-treatment composition of the galvanized steel sheet according to the present invention does not contain chromium and is not harmful to humans and the environment, and the same level of corrosion resistance as when treated with a conventional chromium-containing post-treatment composition during post-treatment on a steel plate using the same Indicates.
    权利要求:
    Claims (4)
    [1" claim-type="Currently amended] It consists of at least one metal salt and balance water selected from the group consisting of colloidal silica, methoxy silane, polyvinyl alcohol, molybdate and vanadate,
    The colloidal silica, methoxy silane and polyvinyl alcohol is 1: 0.01 to 0.3: 0.15 to 0.5 in a weight ratio of a galvanized steel sheet after-treatment composition.
    [2" claim-type="Currently amended] The composition of claim 1, wherein molybdate is used as the metal salt at 0.1-0.8% by weight based on the weight of the composition.
    [3" claim-type="Currently amended] The composition of claim 1, wherein vanadate is used as the metal salt at 0.02-0.5% by weight based on the weight of the composition.
    [4" claim-type="Currently amended] According to claim 1, wherein the metal salt composition based on the weight of the composition, 0.1 to 0.8% molybdate and 0.02-0.5% by weight vanadate is used together.
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    同族专利:
    公开号 | 公开日
    KR100447599B1|2004-09-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-12-21|Application filed by 포스코신기술연구조합, 주식회사 포스코, 재단법인 포항산업과학연구원, 포항강판 주식회사
    2001-12-21|Priority to KR20010082359A
    2003-06-27|Publication of KR20030052410A
    2004-09-07|Application granted
    2004-09-07|Publication of KR100447599B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR20010082359A|KR100447599B1|2001-12-21|2001-12-21|Chromium-Free Surface Treatment Composition for Galvanized Steel|
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