WO2016163461A1 - Ｚｎ－Ｍｇ合金めっき鋼板 - Google Patents

Ｚｎ－Ｍｇ合金めっき鋼板 Download PDF

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WO2016163461A1
WO2016163461A1 PCT/JP2016/061404 JP2016061404W WO2016163461A1 WO 2016163461 A1 WO2016163461 A1 WO 2016163461A1 JP 2016061404 W JP2016061404 W JP 2016061404W WO 2016163461 A1 WO2016163461 A1 WO 2016163461A1
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acid
alloy
steel sheet
carboxylic acid
salt
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PCT/JP2016/061404
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English (en)
French (fr)
Japanese (ja)
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哲也 鳥羽
山口　伸一
雅充 松本
公平 ▲徳▼田
保明 河村
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新日鐵住金株式会社
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Priority to MYPI2017703234A priority Critical patent/MY186250A/en
Priority to CN201680019274.2A priority patent/CN107429405B/zh
Priority to KR1020177027192A priority patent/KR101986930B1/ko
Priority to JP2016560013A priority patent/JP6070914B1/ja
Publication of WO2016163461A1 publication Critical patent/WO2016163461A1/ja

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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Definitions

  • the present invention relates to a Zn—Mg alloy plated steel sheet.
  • the plating layer formed on the steel surface by plating is a barrier anti-corrosion plating layer type that shields the steel from the outside environment, and a sacrificial anti-corrosion plating layer that protects the steel from corrosion by preferentially corroding the steel. It is roughly divided into two types. Zn has been conventionally used for plating steel, but the plating layer formed by Zn plating is classified as a sacrificial anticorrosion plating layer type.
  • the surface of the plated steel sheet (that is, the surface of the plating layer) is subjected to a coating treatment, a chemical conversion treatment, or a lamination process. Rust prevention is improved by applying the surface treatment.
  • the chemical conversion treatment is mainly intended to improve the primary rust prevention property that rusts the surface of the plated steel sheet until the plated steel sheet is processed and assembled to become the final product.
  • a layer having suitable adhesion to the surface of the plating layer hereinafter referred to as a chemical conversion treatment layer) is formed on the surface of the plating layer.
  • Patent Documents 1 to 4 in recent years, in order to improve the corrosion resistance, a Zn—Mg alloy in which a plating layer containing a Zn—Mg alloy is formed on the surface of the steel plate instead of the Zn plated steel plate. Plated steel sheets have been proposed. A Zn—Mg alloy-plated steel sheet has corrosion resistance superior to that of a Zn-plated steel sheet by stabilizing the corrosion product generated in a corrosive environment with Mg.
  • Japanese Unexamined Patent Publication No. 2005-146340 Japanese Unexamined Patent Publication No. 2007-23309 Japanese Unexamined Patent Publication No. 2010-248541 Japanese Unexamined Patent Publication No. 2011-218823
  • the Zn—Mg alloy-plated steel sheet has excellent corrosion resistance compared to the Zn-plated steel sheet.
  • blackening phenomenon the case where the Zn-Mg alloy-plated steel sheet turns black
  • chemical conversion treatment the case where the Zn-Mg alloy-plated steel sheet turns black
  • swelling occurs in the layer (hereinafter referred to as a swelling formation phenomenon), and a suitable primary rust preventive property may not be obtained.
  • the blackening phenomenon is caused by Mg ions eluted from the plating layer forming non-stoichiometric oxides, and the swelling formation phenomenon is caused by the Mg ions eluted from the plating layer continuously producing unstable corrosion. It is thought that it originates in forming a thing.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a Zn—Mg alloy-plated steel sheet having a chemical conversion treatment layer having excellent primary rust prevention properties.
  • the present inventors examined a method for improving the primary rust prevention property by forming a stable corrosion product with Mg ions eluted from the Zn—Mg alloy.
  • the present inventors have included a substance having a low solubility of Mg salt and a high solubility of alkali metal salt in the chemical conversion treatment layer, so that Mg eluted from the plating layer in a corrosive environment and the chemical conversion treatment layer It was found that the dissolved substances were combined and the corrosion portion of the plating layer was covered with the formed stable corrosion product, thereby suppressing the blackening phenomenon and the swelling formation phenomenon.
  • the present inventors have further studied, and the chemical conversion treatment layer contains an alkali metal salt of a carboxylic acid having 4 to 20 carbon atoms or an alkali metal salt of an alkanesulfonic acid having 4 to 20 carbon atoms.
  • the primary rust prevention property of the Zn—Mg alloy plated steel sheet was remarkably improved, and the present invention was completed.
  • the present invention adopts the following means in order to solve the above problems and achieve the object.
  • a Zn—Mg alloy-plated steel sheet according to one aspect of the present invention is formed on the surface of the steel sheet and the steel sheet, contains 1.0 to 70.0 mass% Mg, and the balance contains Zn and impurities.
  • a Zn-Mg alloy plating layer including the Mg salt of a carboxylic acid having 4 to 20 carbon atoms and an Mg salt of an alkanesulfonic acid having 4 to 20 carbon atoms formed on the surface of the Zn-Mg alloy plating layer.
  • a corrosion product layer containing any one of the above, and an alkali metal salt of the carboxylic acid when formed on the surface of the corrosion product layer and the corrosion product layer contains the Mg salt of the carboxylic acid.
  • a chemical conversion treatment layer containing the alkali metal salt of the alkanesulfonic acid is included in the chemical conversion treatment layer
  • Alkali metal Li metal salts or alkali metal salts of the alkanesulfonic acid is at least one of Li, Na, K, selected from the group consisting of Rb and Cs.
  • the Zn—Mg alloy plating layer contains 0.3 to 25.0 mass% Al and 0 And at least one selected from the group consisting of 0.01 to 5.00% by mass of Si, 1.0 to 5.0% by mass of Ca, and 0.1 to 1.5% by mass or less of Ni. You may employ
  • the content of the alkali metal salt of the carboxylic acid or the alkali metal salt of the alkanesulfonic acid contained in the chemical conversion layer is converted to Na.
  • a configuration of 10 to 1500 mg / m 2 may be employed.
  • the chemical conversion treatment layer may employ a configuration that does not contain fluoride, trivalent chromium, and vanadium. Good.
  • FIG. 1 is a schematic diagram showing a layer configuration of a Zn—Mg alloy-plated steel sheet according to an embodiment.
  • FIG. 1 is a schematic diagram showing a layer structure of a Zn—Mg alloy plated steel sheet 1.
  • the Zn—Mg alloy-plated steel sheet 1 is formed on the surface of the steel sheet 2, the Zn—Mg alloy plating layer 3 formed on the surface of the steel sheet 2 and containing 10 to 70% by mass of Mg, the balance containing Zn and impurities, and Zn— Corrosion product formed on the surface of the Mg alloy plating layer 3 and containing either Mg salt of carboxylic acid having 4 to 20 carbon atoms or Mg salt of alkanesulfonic acid having 4 to 20 carbon atoms
  • the corrosion product layer 4 contains an Mg salt of a carboxylic acid
  • the corrosion product layer 4 contains an alkali metal salt of a carboxylic acid
  • the corrosion product layer 4 contains an alkane sulfone.
  • a chemical conversion treatment layer 5 containing an alkali metal salt of alkanesulfonic acid is provided.
  • the conventional Zn—Mg alloy-plated steel sheet 1 when the chemical conversion treatment layer 5 was formed on the Zn—Mg alloy plating layer 3, the blackening phenomenon and the swelling formation phenomenon were remarkable.
  • the Zn—Mg alloy-plated steel sheet 1 according to the present embodiment suppresses the formation of Mg non-stoichiometric oxides and unstable corrosion products even when the chemical conversion treatment layer 5 is formed. Primary rust resistance is remarkably improved.
  • the above-described primary rust prevention effect can be improved by adding an alkali metal salt of a carboxylic acid or alkanesulfonic acid having 4 to 20 carbon atoms to the chemical conversion treatment layer 5.
  • an alkali metal salt of a carboxylic acid or alkanesulfonic acid having 4 to 20 carbon atoms to the chemical conversion treatment layer 5.
  • Mg ions eluted from the Zn—Mg alloy plating layer 3 and carboxylic acid ions or alkanesulfonic acid ions eluted from the chemical conversion treatment layer 5 are combined to form a stable corrosion product, carboxylic acid.
  • An Mg salt of an acid or an alkane sulfonic acid is formed.
  • the produced Mg salt of carboxylic acid or Mg salt of alkanesulfonic acid is deposited in a layer form on the Zn—Mg alloy plating layer 3 to form a corrosion product layer 4.
  • Carboxylic acid or alkanesulfonic acid having 4 to 20 carbon atoms forms Mg salt by bonding with Mg, and particularly coats the corroded portion. As a result, elution of Mg ions from the Zn—Mg alloy plating layer 3 is suppressed.
  • the Zn—Mg alloy plating layer 3 contains a Zn—Mg alloy, and may contain at least one selected from the group consisting of Al, Si, Ca and Ni as necessary. Further, elements such as Y, La, Ce, Ti, Cr, Fe, Co, V, Nb, Cu, Sn, Mn, Sr, Sb, and Pb may be contained in an amount of about 0 to 5% by mass. Below, content of Mg, Al, Si, Ca, Ni is demonstrated.
  • the balance other than these alloy elements includes Zn and impurities.
  • the impurity is a component mixed due to various factors of the raw material and the manufacturing process, and is a so-called inevitable impurity.
  • the balance other than the above alloy elements is preferably composed of Zn and inevitable impurities.
  • Mg manganesium
  • the Mg content in the Zn—Mg alloy plating layer 3 is 1.0 mass% or more in order to improve sacrificial corrosion resistance.
  • the Mg content is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more.
  • the Mg content exceeds 70.0% by mass, the Mg phase is crystallized in the Zn—Mg alloy plating layer 3 and the corrosion resistance is remarkably lowered.
  • Mg in the Zn—Mg alloy plating layer 3 reacts with the carboxylic acid or alkanesulfonic acid applied on the surface to generate an Mg salt.
  • This Mg salt has a function of further improving the corrosion resistance of the Zn—Mg alloy layer 3 as compared with the case where there is no Mg salt. This is the reason why the corrosion resistance is further improved by the above-mentioned preferable Mg concentration, and there is an effect more than the corrosion resistance obtained by simply increasing the Mg concentration (Tanaka additional note).
  • the Zn—Mg alloy plating layer 3 does not contain Mg, the carboxylic acid or alkanesulfonic acid Mg salt described later is not formed, and therefore the corrosion product layer 4 is not formed. Therefore, since suitable corrosion resistance cannot be obtained, it is not preferable.
  • Al is an element that improves the corrosion resistance of the planar portion of the Zn—Mg alloy plating layer 3.
  • the Zn—Mg alloy plating layer 3 preferably contains 0.30% by mass or more of Al.
  • the upper limit is preferably made 25.0% by mass or less.
  • the content of Al is more preferably 20.0% by mass or less.
  • Si is an element that suppresses growth of the alloy phase formed at the interface between the steel plate 2 and the Zn—Mg alloy plating layer 3 and prevents deterioration of workability. It is preferable to contain 010 mass% or more. If the Si content exceeds 5.0% by mass, bottom dross is likely to be formed in the plating bath and the operability is lowered, so 5.0% by mass or less is preferable.
  • ⁇ Ca 1.0 to 5.0% by mass> Ca is added to the Zn—Mg alloy plating layer 3 as necessary to improve the operability of hot dipping.
  • an Mg-containing alloy is used as a plating bath.
  • Ni is an element that improves wettability during plating.
  • the interface between the steel plate 2 and the Zn—Mg alloy plating layer 3 is greater than when the Zn—Mg alloy plating layer 3 is formed on the steel plate 2.
  • the formation of Al—Fe-based intermetallic compounds in the vicinity is suppressed, and workability is improved.
  • the upper limit of the Ni content of the Zn—Mg alloy plating layer 3 is preferably 1.50%.
  • the content of Ni in the Zn—Mg alloy plating layer 3 is preferably 0.10% by mass or more.
  • Ni may be included in the plating alloy as pre-Ni plating as described above, or may be previously included as a component in the plating alloy.
  • an element constituting the steel plate 2 as a base material may be mixed.
  • the Zn—Mg alloy plating layer 3 is formed by the hot dipping method, or when heat treatment is performed after the formation of the Zn—Mg alloy plating layer 3, the element is formed at the interface between the steel plate 2 and the Zn—Mg alloy plating layer 3. Interdiffuse. In such a case, the adhesiveness between the steel plate 2 and the Zn—Mg alloy plating layer 3 is improved by forming an alloy phase of Fe, Al, Zn or the like.
  • an alloy phase containing Fe, Al, and Zn formed at the interface between the steel plate 2 and the Zn—Mg alloy plating layer 3 is less likely to affect the corrosion resistance of the Zn—Mg alloy plating layer 3.
  • the content of Fe in the Zn—Mg alloy plating layer 3 may be about 2.0 mass%.
  • the Zn—Mg alloy plating layer 3 may contain 2.0 mass% or less of Fe.
  • the Zn—Mg alloy-plated steel sheet 1 contains Mg salt of carboxylic acid having 4 to 20 carbon atoms or Mg salt of alkanesulfonic acid having 4 to 20 carbon atoms on the surface of the Zn—Mg alloy plated layer 3.
  • the corrosion product layer 4 has The Mg salt of carboxylic acid or alkanesulfonic acid having 4 to 20 carbon atoms is a stable corrosion product, and improves the corrosion resistance of the Zn—Mg alloy-plated steel sheet 1.
  • the alkali metal salt of carboxylic acid or the alkali metal salt of alkanesulfonic acid contained in the chemical conversion treatment layer 5 is ionized by eluting into the aqueous solution under the chemical conversion treatment step and the corrosive environment.
  • the ions generated in this manner react with the Mg ions eluted from the Zn—Mg alloy plating layer 3 to generate Mg salt of carboxylic acid or Mg salt of alkanesulfonic acid contained in the corrosion product layer 4. Is done.
  • alkali metal salt of carboxylic acid or alkali metal salt of alkanesulfonic acid contained in chemical conversion treatment layer 5 is added to Zn—Mg alloy plating layer 3. It must be in a position where it touches.
  • the carboxylic acid In order to prevent the alkali metal salt of carboxylic acid or the alkali metal salt of alkanesulfonic acid from eluting in the aqueous solution and the Mg salt of carboxylic acid or Mg salt of alkanesulfonic acid from eluting into the aqueous solution, the carboxylic acid Alternatively, it is necessary that the difference in solubility between the alkali metal salt of alkanesulfonic acid and the Mg salt is large.
  • the solubility of the Mg salt of carboxylic acid or alkanesulfonic acid in water needs to be low. . Therefore, the carbon number of carboxylic acid or alkanesulfonic acid is 4 or more.
  • the solubility of the carboxylic acid or alkanesulfonic acid alkali metal salt in water needs to be high. Therefore, carbon number of carboxylic acid or alkanesulfonic acid shall be 20 or less.
  • the preferred carbon number of the carboxylic acid or alkanesulfonic acid is 5-20, more preferably 8-12.
  • the carboxylic acid is not particularly limited as long as it has 4 to 20 carbon atoms, and saturated fatty acid, hydroxycarboxylic acid, benzenecarboxylic acid, dicarboxylic acid, unsaturated fatty acid and the like can be used. From an economical viewpoint, it is preferable to use a saturated fatty acid as the carboxylic acid.
  • saturated fatty acids include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, etc. be able to.
  • particularly preferred compounds among the saturated fatty acids include caprylic acid, pelargonic acid, capric acid and lauric acid having 8 to 12 carbon atoms.
  • Examples of hydroxycarboxylic acid include malic acid, citric acid, tartaric acid and the like.
  • benzenecarboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, cinnamic acid, and the like.
  • Examples of the dicarboxylic acid include fumaric acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like.
  • unsaturated fatty acids include crotonic acid, sorbic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidonic acid, eicosadienoic acid, eicosapentaenoic acid, etc. Can be mentioned.
  • the alkanesulfonic acid is not particularly limited as long as it has 4 to 20 carbon atoms, butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, tetradecane.
  • Sulfonic acid, hexadecane sulfonic acid, octadecane sulfonic acid, icosane sulfonic acid and the like can be used.
  • Examples of particularly preferable compounds among alkanesulfonic acids include octanesulfonic acid, decanesulfonic acid and dodecanesulfonic acid having 8 to 12 carbon atoms.
  • the Zn—Mg alloy-plated steel sheet 1 has a chemical conversion treatment layer 5 made of an alkali metal salt of carboxylic acid or alkanesulfonic acid and a film forming component on the surface of the corrosion product layer 4.
  • the chemical conversion treatment layer 5 may contain an inhibitor component and polyethylene wax as necessary.
  • the chemical conversion treatment layer 5 is preferably so-called chromate-free.
  • the alkali metal of the alkali metal salt of carboxylic acid or alkanesulfonic acid contained in the chemical conversion treatment layer 5 is at least one selected from the group consisting of Li, Na, K, Rb and Cs. From an economical point of view, the alkali metal is only Na (the alkali metal salt of carboxylic acid or alkanesulfonic acid is only the Na salt of carboxylic acid or alkanesulfonic acid, and does not include alkali metal salts other than Na salt). preferable.
  • the content of alkali metal salt of carboxylic acid or alkanesulfonic acid contained in the chemical conversion treatment layer 5 is preferably 10 to 1500 mg / m 2 in terms of Na amount.
  • the content of the alkali metal salt of carboxylic acid or alkanesulfonic acid is less than 10 mg / m 2 in terms of Na, the amount of Mg salt of carboxylic acid or alkanesulfonic acid contained in the corrosion product layer 4 is small. May not provide good corrosion resistance.
  • the content of the alkali metal salt of carboxylic acid or alkanesulfonic acid exceeds 1500 mg / m 2 in terms of Na amount, the uniformity of the chemical conversion treatment layer 5 may deteriorate.
  • carboxylic acid Alternatively, the carboxylic acid component of the alkali metal salt of alkanesulfonic acid or the substance of alkanesulfonic acid can be identified.
  • qualitative analysis and quantitative analysis by atomic absorption spectrophotometry can be performed to identify an alkali metal component and measure its content.
  • Na can be qualitatively and quantitatively analyzed by the uranyl acetate method.
  • the chemical conversion treatment layer 5 may contain Mg salt of carboxylic acid or alkanesulfonic acid
  • the Mg salt of carboxylic acid or alkanesulfonic acid contained in the chemical conversion treatment layer 5 hardly contributes to the improvement of corrosion resistance.
  • the carboxylic acid or alkanesulfonic acid in the chemical conversion treatment layer 5 exists only in the form of an alkali metal salt or Mg salt, and the carboxylic acid or alkanesulfonic acid does not exist alone in the chemical conversion treatment layer 5.
  • the alkali metal does not exist alone.
  • ⁇ Film forming component> As long as the film-forming component is so-called chromate-free, regardless of the type, it is possible to use one that includes one or both of a resin and a metal compound.
  • the resin include polyurethane resin, epoxy resin, acrylic resin, and polyamide resin.
  • the metal compound may include a basic zirconium compound and a silicon compound.
  • the silicon compound include organic silicon compounds and inorganic silicon compounds.
  • a film-forming component (film-forming component A) containing at least one of a basic zirconium compound, a phosphoric acid compound and a cobalt compound and an organic acid, an organic silicon compound and an aqueous urethane are used.
  • a film-forming component containing a resin (film-forming component B), an ethylene-unsaturated carboxylic acid copolymer resin having one or both of a silanol group and an alkoxysilyl group, a silicon oxide particle and an organic titanium compound ( The film-forming component C) will be described.
  • the film-forming component A contains at least one of a basic zirconium compound, a phosphoric acid compound, and a cobalt compound and an organic acid.
  • a basic zirconium compound include zirconium carbonate compounds having [Zr (CO 3 ) 2 (OH) 2 ] 2 ⁇ or [Zr (CO 3 ) 2 (OH) 2 ] 2 ⁇ as cations, and their cations
  • phosphoric acid compounds include phosphoric acid and its ammonium salts such as orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, phytic acid, phosphonic acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphorus Examples thereof include diammonium oxyhydrogen, sodium phosphate, and potassium phosphate.
  • the cobalt compound include cobalt carbonate, cobalt nitrate, and cobalt acetate.
  • organic acids examples include glycolic acid, malic acid, tartaric acid, succinic acid, citric acid, ascorbic acid, lactic acid, dehydrobenzoic acid, dehydroascorbic acid, gallic acid, tannic acid, phytic acid, and the like.
  • the ammonium salt may be used.
  • the film-forming component B contains an organosilicon compound and a water-based urethane resin.
  • organosilicon compound include compounds obtained by blending a silane coupling agent containing one amino group in the molecule and a silane coupling agent containing one glycidyl group in the molecule.
  • the silane coupling agent containing one amino group in the molecule is not particularly limited, and examples thereof include 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
  • Examples of the silane coupling agent containing one glycidyl group in the molecule include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.
  • the number of functional groups in the organosilicon compound is preferably 2 or more. When the number of functional groups is one, the adhesion to the Zn—Mg alloy plating layer 3, the self-crosslinking property of the organosilicon compound, and the binding property to the polyether polyurethane resin are lowered, and the chemical conversion treatment layer 5 It may not be formed suitably.
  • the number of functional groups of the organosilicon compound can be analyzed by gas chromatography.
  • the water-based urethane resin is preferably a polyether system.
  • the polyester polyurethane resin may be hydrolyzed by acid or alkali, and the polycarbonate polyurethane is likely to form a hard and brittle film, and may be inferior in adhesion during processing and corrosion resistance of the processed part.
  • the film-forming component C includes an ethylene-unsaturated carboxylic acid copolymer resin having one or both of a silanol group and an alkoxysilyl group, silicon oxide particles, and an organic titanium compound.
  • An ethylene-unsaturated carboxylic acid copolymer resin having either or both of a silanol group and an alkoxysilyl group includes, for example, an aqueous solution in which a copolymer resin of ethylene and an unsaturated carboxylic acid is dispersed, a silane compound, Is obtained by reacting.
  • the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic anhydride and the like.
  • the silicon oxide particles colloidal silica, fumed silica, or the like is preferably used.
  • organic titanium compounds include dipropoxybis (triethanolaminato) titanium, dipropoxybis (diethanolaminato) titanium, dibutoxybis (triethanolaminato) titanium, dibutoxybis (diethanolaminato) titanium, dipropoxybis (acetylacetonato).
  • titanium, dibutoxybis (acetylacetonato) titanium dihydroxybis (lactato) titanium monoammonium salt
  • dihydroxybis (lactato) titanium diammonium salt propanedioxytitanium bis (ethylacetoacetate), oxotitanium bis (monoammonium o
  • the film-forming component C may include a polyurethane resin having one or both of a silanol group and an alkoxysilyl group in addition to the above-described components.
  • a polyurethane resin having one or both of a silanol group and an alkoxysilyl group can be obtained by reacting a polyurethane prepolymer with alkoxysilanes and polyamines having an active hydrogen group.
  • the film-forming component C contains an unsaturated carboxylic acid, as described above, the solution obtained by immersing the chemical conversion layer 5 in pure water is dried, and the obtained residue is analyzed. For example, discrimination from an alkali metal salt of carboxylic acid or alkanesulfonic acid is possible.
  • the chemical conversion treatment layer 5 contains at least one selected from the group consisting of fluoride, trivalent chromium and vanadium
  • the Mg salt of carboxylic acid or alkanesulfonic acid does not precipitate properly, and therefore the corrosion product layer 4 is preferably used. Not formed. Therefore, it is preferable that the chemical conversion treatment layer 5 does not contain fluoride, trivalent chromium, and vanadium.
  • the film-forming component does not contain fluoride, trivalent chromium and vanadium.
  • the interface between the Zn—Mg alloy plating layer 3 and the corrosion product layer 4 and the interface between the corrosion product layer 4 and the chemical conversion treatment layer 5 were obtained by photographing a cross section of the Zn—Mg alloy plated steel sheet 1 with an SEM-reflection electron image. And can be identified by the brightness of the reflected electron image.
  • the Zn—Mg alloy plated steel sheet 1 forms a Zn—Mg alloy plating layer 3 on the surface of the steel sheet 2 by a plating process, and forms a corrosion product layer 4 on the surface of the Zn—Mg alloy plating layer 3 by a chemical conversion treatment process. At the same time, the chemical conversion treatment layer 5 is formed on the surface of the corrosion product layer 4.
  • a Zn—Mg alloy plating layer 3 is formed on the surface of the steel plate 2 by a plating process.
  • the method of the plating step is not particularly limited, and a known hot dipping method can be used. A well-known method can be used also about addition of Mg etc. in Zn plating bath.
  • the corrosion product layer 4 is formed on the surface of the Zn—Mg alloy plating layer 3 and the chemical conversion treatment layer 5 is formed on the surface of the corrosion product layer 4.
  • a solution in which an alkali metal salt of carboxylic acid or alkanesulfonic acid and the film forming component are dissolved in water or an organic solvent hereinafter referred to as chemical conversion treatment liquid. Is applied to the surface of the Zn—Mg alloy plating layer 3 and dried.
  • the concentration of the alkali metal salt of carboxylic acid or alkanesulfonic acid in the chemical conversion treatment liquid is not particularly limited, but the alkali metal salt of carboxylic acid or alkali metal salt of alkanesulfonic acid is eluted in the aqueous solution, and Mg salt of carboxylic acid Or from the viewpoint of preventing the Mg salt of alkanesulfonic acid from eluting into the aqueous solution, the content is preferably 0.1 to 10% by mass.
  • the method for applying the chemical conversion liquid is not particularly limited, and for example, a spray method, a dipping method, a roll coating method, a shower ringer method, an air knife method, or the like may be employed.
  • the chemical conversion treatment liquid may contain a surfactant, an antifoaming agent, a lubricant, or a filler.
  • the Zn—Mg alloy-plated steel sheet 1 coated with the chemical conversion solution may be heated to 50 ° C. to 200 ° C. in order to dry it.
  • the formation method of the corrosion product layer and the chemical conversion treatment layer is as follows.
  • the chemical conversion treatment solution containing 1% by mass of an alkali metal salt of carboxylic acid or alkanesulfonic acid, 20% by mass of a film-forming component and water is coated with Zn-Mg. It apply
  • Tables 1 to 5 show the composition of the Zn—Mg alloy plating layer, the alkali metal salt of carboxylic acid or alkanesulfonic acid contained in the chemical conversion treatment layer, and the film-forming components. Using these Zn—Mg alloy plated steel sheets as test pieces, blackening resistance and corrosion resistance were evaluated as primary rust resistance indicators. The evaluation results are shown in Tables 6 to 10.
  • the invention examples described in Tables 1 and 2 include an alkali metal salt of carboxylic acid in the chemical conversion treatment layer
  • the invention examples described in Tables 3 and 4 include an alkali metal salt of alkanesulfonic acid in the chemical conversion treatment layer. It is out.
  • the chemical conversion treatment layer may contain an alkali metal salt of carboxylic acid, may contain an alkali metal salt of alkanesulfonic acid, or may not contain both of them.
  • the above L * represents a brighter color as the value is larger, and represents a darker color (black) as the value is smaller.
  • the blackening resistance is evaluated based on ⁇ L * , which is the difference between the L * values of the test pieces before and after 144 hours of standing, but the lightness close to that before standing is maintained as the value of ⁇ L * is smaller. Represents that Further, the larger the value of ⁇ L *, the lower the brightness after standing (becomes darker) than before standing.
  • Corrosion resistance was evaluated by performing a salt spray test in accordance with JIS Z 2371 for 240 hours on the test piece. Specifically, the corrosion resistance was determined according to the following criteria based on the corrosion area ratio after the salt spray test (the ratio of the corrosion area to the surface area of the test piece). “Very Good”, “Good”, and “Fair” were accepted. Very Good: Corrosion area rate is 0% Good: Corrosion area ratio is more than 0% and less than 5% Fair: Corrosion area ratio is more than 5% and less than 30% Bad: Corrosion area ratio is more than 30%
  • Comparative Examples 1, 2, 5 and 6 shown in Table 10 the Mg content of the alloy plating layer was outside the range of the present invention, and blackening resistance, corrosion resistance and comprehensive evaluation were insufficient.
  • Comparative examples 1 and 5 are comparative examples in which the alloy plating layer has a high Mg content. In Comparative Examples 1 and 5, the corrosion product layer was formed, but blackening resistance, corrosion resistance, and comprehensive evaluation were insufficient. As a cause of this, although the formation of the corrosion product layer itself occurs in Comparative Examples 1 and 5, it is considered that the corrosion of the Mg phase existing in the plating was fast and the corrosion could not be suppressed.
  • Comparative Examples 3, 4, 7 and 8 the carbon number of the carboxylic acid or alkanesulfonic acid was outside the range of the present invention, and the blackening resistance, corrosion resistance and comprehensive evaluation were insufficient. Since Comparative Examples 9 to 12 did not contain an alkali metal salt of carboxylic acid or alkanesulfonic acid, blackening resistance, corrosion resistance, and comprehensive evaluation were insufficient.
  • Comparative Example 13 Since the comparative example 13 did not plate on a steel plate, blackening resistance, corrosion resistance, and comprehensive evaluation were inadequate. In Comparative Example 13, since the steel sheet is not plated, there is no Mg ion supply source. Therefore, since Mg salt of carboxylic acid was not formed and the corrosion product layer was not formed, it is considered that blackening resistance, corrosion resistance and comprehensive evaluation were insufficient. Comparative Examples 14 and 15 contained carboxylic acid or alkanesulfonic acid but did not contain an alkali metal salt of carboxylic acid or alkanesulfonic acid, and thus blackening resistance, corrosion resistance and comprehensive evaluation were insufficient.
  • Comparative Example 16 is a comparative example in which the film-forming component contains trivalent chromium, but the blackening resistance, corrosion resistance, and comprehensive evaluation were insufficient.
  • Comparative Example 17 is a comparative example in which the film forming component contains vanadium, but the blackening resistance, corrosion resistance, and comprehensive evaluation were insufficient.
  • Comparative Example 18 is a comparative example in which the film-forming component contains fluorine, but the blackening resistance, corrosion resistance, and comprehensive evaluation were insufficient.
  • the film-forming component contains trivalent chromium, vanadium or fluorine
  • the Mg salt of carboxylic acid or alkanesulfonic acid is This is probably because the corrosion product layer is not properly formed and the corrosion product layer is not suitably formed.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)
PCT/JP2016/061404 2015-04-07 2016-04-07 Ｚｎ－Ｍｇ合金めっき鋼板 WO2016163461A1 (ja)

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MYPI2017703234A MY186250A (en) 2015-04-07 2016-04-07 Zn-mg alloy coated steel sheet
CN201680019274.2A CN107429405B (zh) 2015-04-07 2016-04-07 Zn-Mg合金镀覆钢板
KR1020177027192A KR101986930B1 (ko) 2015-04-07 2016-04-07 Zn-Mg 합금 도금 강판
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KR102209546B1 (ko) * 2018-12-19 2021-01-29 주식회사 포스코 광택도 및 표면특성이 우수한 도금강판 및 그 제조방법
TWI820931B (zh) * 2022-03-03 2023-11-01 日商日本製鐵股份有限公司 表面處理鋼板

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