WO2016163461A1

WO2016163461A1 - Zn-mg alloy coated steel sheet

Info

Publication number: WO2016163461A1
Application number: PCT/JP2016/061404
Authority: WO
Inventors: 哲也鳥羽; 山口　伸一; 雅充松本; 公平 ▲徳▼田; 保明河村
Original assignee: 新日鐵住金株式会社
Priority date: 2015-04-07
Filing date: 2016-04-07
Publication date: 2016-10-13
Also published as: KR20170120165A; CN107429405B; JP6070914B1; KR101986930B1; CN107429405A; MY186250A; JPWO2016163461A1

Abstract

This Zn-Mg alloy coated steel sheet is provided with: a steel sheet; a Zn-Mg alloy coating layer that is formed on the surface of the steel sheet and contains 10-70% by mass of Mg, with the balance made up of Zn and impurities; a corrosion product layer that is formed on the surface of the Zn-Mg alloy coating layer and contains an Mg salt of a carboxylic acid having 4-20 carbon atoms or an Mg salt of an alkanesulfonic acid having 4-20 carbon atoms; and a chemical conversion coating layer that is formed on the surface of the corrosion product layer and contains an alkali metal salt of the carboxylic acid in cases where the corrosion product layer contains an Mg salt of the carboxylic acid, while containing an alkali metal salt of the alkanesulfonic acid in cases where the corrosion product layer contains an Mg salt of the alkanesulfonic acid. In this connection, the alkali metal of the alkali metal salt of the carboxylic acid or the alkali metal salt of the alkanesulfonic acid contained in the chemical conversion coating layer is at least one element selected from the group consisting of Li, Na, K, Rb and Cs.

Description

Zn-Mg alloy plated steel sheet

The present invention relates to a Zn—Mg alloy plated steel sheet.
This application claims priority based on Japanese Patent Application No. 2015-78585 filed in Japan on April 7, 2015, the contents of which are incorporated herein by reference.

Steel materials used in automobiles, home appliances, building materials, etc. may be plated to improve corrosion resistance. 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.

When using a steel sheet with a plating layer formed on the surface (hereinafter referred to as a plated steel sheet) for a long period of time, 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. In the chemical conversion treatment, 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.

As shown in 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

As described above, the Zn—Mg alloy-plated steel sheet has excellent corrosion resistance compared to the Zn-plated steel sheet. However, when the conversion treatment used for the Zn-plated steel sheet is applied to the Zn-Mg alloy-plated steel sheet, the case where the Zn-Mg alloy-plated steel sheet turns black (hereinafter referred to as blackening phenomenon), or the chemical conversion treatment In some cases, 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. As a result, 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.

Further, 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. As a result, it was found that 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.

(1) 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. And when the corrosion product layer contains the Mg salt of the alkanesulfonic acid, a chemical conversion treatment layer containing the alkali metal salt of the alkanesulfonic acid, and is included in the chemical conversion treatment layer Carboxylic acid 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.

(2) In the Zn—Mg alloy-plated steel sheet described in (1) above, a configuration in which the Zn—Mg alloy plating layer contains 5.0 to 70.0 mass% Mg may be adopted.

(3) In the Zn—Mg alloy-plated steel sheet described in (2) above, a configuration in which the Zn—Mg alloy plating layer contains 10.0 to 70.0% by mass of Mg may be employed.

(4) In the Zn—Mg alloy-plated steel sheet described in (3) above, a configuration in which the Zn—Mg alloy plating layer contains 15.0 to 70.0% by mass of Mg may be adopted.

(5) In the Zn—Mg alloy-plated steel sheet according to any one of the above (1) to (4), 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 | adopt the structure containing.

(6) In the Zn—Mg alloy-plated steel sheet according to any one of the above (1) to (5), a configuration in which the alkali metal is Na may be adopted.

(7) In the Zn—Mg alloy-plated steel sheet according to (6), 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.

(8) In the Zn—Mg alloy-plated steel sheet according to any one of the above (1) to (7), a configuration in which the carboxylic acid or the alkanesulfonic acid has 5 to 20 carbon atoms is employed. Also good.

(9) In the Zn—Mg alloy-plated steel sheet described in (8) above, a configuration in which the carboxylic acid or the alkanesulfonic acid has 8 to 12 carbon atoms may be employed.

(10) In the Zn—Mg alloy-plated steel sheet according to any one of the above (1) to (9), a configuration in which the carboxylic acid is a saturated fatty acid may be adopted.

(11) In the Zn—Mg alloy-plated steel sheet according to any one of the above (1) to (10), the chemical conversion treatment layer may employ a configuration that does not contain fluoride, trivalent chromium, and vanadium. Good.

According to each aspect described above, it is possible to provide a Zn—Mg alloy-plated steel sheet having a chemical conversion treatment layer having excellent primary rust prevention properties.

1 is a schematic diagram showing a layer configuration of a Zn—Mg alloy-plated steel sheet according to an embodiment.

Hereinafter, a Zn—Mg alloy plated steel sheet and a manufacturing method according to an embodiment will be described with reference to the drawings.
(Zn-Mg alloy plated steel sheet 1)
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 When 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, and the corrosion product layer 4 contains an alkane sulfone. In the case of containing an Mg salt of an acid, a chemical conversion treatment layer 5 containing an alkali metal salt of alkanesulfonic acid is provided.
In 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. However, 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.

Although details will be described later, 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. In the chemical conversion treatment process and in a corrosive environment, 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.

<Zn-Mg alloy plating layer 3>
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. Here, 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: 1.0 to 70.0% by mass>
Mg (magnesium) is a main element constituting the Zn—Mg alloy plating layer 3 together with Zn. 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. On the other hand, if 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.
As will be described later, 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).
When 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: 0.30 to 25.0 mass%>
Al is an element that improves the corrosion resistance of the planar portion of the Zn—Mg alloy plating layer 3. In order to obtain this effect, the Zn—Mg alloy plating layer 3 preferably contains 0.30% by mass or more of Al. On the other hand, if the Al content exceeds 25.0% by mass, red rust is likely to occur and the corrosion resistance may be lowered, so the upper limit is preferably made 25.0% by mass or less. Considering the adhesion of the chemical conversion treatment layer 5 to the Zn—Mg alloy plating layer 3, the content of Al is more preferably 20.0% by mass or less.

<Si: 0.010 to 5.0% by mass>
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. When manufacturing the Zn—Mg alloy-plated steel sheet 1 according to this embodiment, an Mg-containing alloy is used as a plating bath. In order for the molten Mg-containing alloy to form a suitable oxide film on the surface, it is preferable to add 1.0 mass% or more of Ca, which is an element effective in preventing Mg oxidation. Since Ca may deteriorate the corrosion resistance when the content is large, the upper limit of the Ca content in the Zn—Mg alloy plating layer 3 is preferably 5.0 mass%.

<Ni: 0.10 to 1.50 mass%>
Ni is an element that improves wettability during plating. When the Zn—Mg alloy plating layer 3 is formed on the steel plate 2 plated with Ni in advance, 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. On the other hand, if the Ni content is large, the corrosion resistance may deteriorate, so 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.

In the Zn—Mg alloy plating layer 3, an element constituting the steel plate 2 as a base material may be mixed. In particular, when 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. Note that 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.
For the above reason, even if the plating bath does not contain Fe, the content of Fe in the Zn—Mg alloy plating layer 3 may be about 2.0 mass%. Has little effect on the corrosion resistance of layer 3. Therefore, the Zn—Mg alloy plating layer 3 may contain 2.0 mass% or less of Fe.

<Corrosion product layer 4>
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. In order to produce Mg salt of carboxylic acid or Mg salt of alkanesulfonic acid, 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.
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.

In order to precipitate the Mg salt of carboxylic acid or alkanesulfonic acid between the chemical conversion treatment layer 5 and the Zn—Mg alloy plating layer 3, 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.
In order to elute carboxylic acid or alkanesulfonic acid as an ion in an aqueous solution in a corrosive environment, 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.
Examples of 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.
Examples of 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. Examples of 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.
Examples of 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.

<Chemical conversion treatment layer 5>
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.

<Alkali metal>
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. When 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. On the other hand, when 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.

If the solution obtained by immersing the chemical conversion treatment layer 5 in pure water is dried, and the resulting residue is used for qualitative analysis and quantitative analysis by infrared spectroscopic analysis or pyrolysis gas chromatography, carboxylic acid Alternatively, the carboxylic acid component of the alkali metal salt of alkanesulfonic acid or the substance of alkanesulfonic acid can be identified. Using the residue obtained in the same manner as described above, qualitative analysis and quantitative analysis by atomic absorption spectrophotometry can be performed to identify an alkali metal component and measure its content. Of the alkali metal components, Na can be qualitatively and quantitatively analyzed by the uranyl acetate method.

Although 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.
In addition, 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. Similarly, 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.
Examples of 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. Examples of the silicon compound include organic silicon compounds and inorganic silicon compounds.

In the following, as examples of preferable film-forming components, 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.

<Film forming component A>
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.
Examples of basic zirconium compounds 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 Ammonium salt, potassium salt, sodium salt and the like containing
Examples of 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.
Examples of the cobalt compound include cobalt carbonate, cobalt nitrate, and cobalt acetate.

Examples of organic acids 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.

<Film forming component B>
The film-forming component B contains an organosilicon compound and a water-based urethane resin.
Examples of the 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.

Structure of the water-based urethane ^resin, 3330cm -1 (N-H stretch) in the infrared ^{spectroscopy,} 1730cm -1 (C = O ^{stretch), 1530cm -1 (C-N} ), 1250cm -1 of (C-O) It can be analyzed by characteristic absorption.

<Film forming component C>
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. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic anhydride and the like.
As the silicon oxide particles, colloidal silica, fumed silica, or the like is preferably used.

Examples of 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 oxalate), etc. Can be mentioned.

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.

Even when 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.

When 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.
Moreover, since the chemical conversion treatment layer 5 does not contain fluoride, trivalent chromium and vanadium, it is preferable that 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.

(Method for producing Zn-Mg alloy-plated steel sheet 1)
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.

<Plating process>
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.

<Chemical conversion treatment process>
By the chemical conversion treatment step, 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.
In the chemical conversion treatment step, regardless of the type of film forming component of the chemical conversion treatment layer 5, 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.
After applying the chemical conversion solution, 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.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited thereto.

Zn—Mg alloy plating with an adhesion amount per side of 180 g / m ² (attachment amount per side 90 g / m ² ) on a steel plate having a thickness of 0.8 mm using a known hot dipping method A layer was formed. Further, a corrosion product layer and a chemical conversion treatment layer having a total film thickness of 1.2 μm were formed on the Zn—Mg alloy plating layer.
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 | coated on the alloy plating layer.
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.

In addition, the invention examples described in Tables 1 and 2 include an alkali metal salt of carboxylic acid in the chemical conversion treatment layer, and 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. In the comparative example described in Table 5, 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.

[Blackening resistance]
Using a constant temperature and humidity tester, the test piece was allowed to stand for 144 hours under an atmosphere of 80 ° C. and 85% relative humidity (RH). The color tone of the test piece before and after standing for 144 hours was measured with a spectrocolorimeter to evaluate blackening resistance. Specifically, an L ^* value representing the brightness of the CIE color system (L ^* a ^* b ^* color system) is measured with a spectrocolorimeter, and the L ^* value before standing for 144 hours and the static value for 144 hours are measured. After incubation of the ^{L *} value and the difference (i.e., (the value of ^{L *} of 144 hours electrostatic置前) - (value of ^{L *} of 144 hours after standing)) was determined △ ^{L *} a.
Based on the value of ΔL ^* , the blackening resistance was evaluated as follows. “Very Good”, “Good”, and “Fair” were accepted.
Very Good: ΔL ^* is 5 or less Good: ΔL ^* is more than 5 to 10 or less Fair: ΔL ^* is more than 10 to 15 or less Bad: ΔL ^* is more than 15

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 ΔL ^* , 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 ΔL ^* is smaller. Represents that Further, the larger the value of ΔL ^*, the lower the brightness after standing (becomes darker) than before standing.

[Corrosion resistance]
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%

In Tables 6 to 10, the overall evaluation that combines the above two evaluations is also shown. In the comprehensive evaluation, “Very Good”, “Good”, and “Fair” were accepted.

As shown in Tables 6 to 9, all of the inventive examples were excellent in blackening resistance and corrosion resistance, and the overall evaluation was acceptable.

On the other hand, in 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.
In 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.

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 reason why it is not preferable that the film-forming component contains trivalent chromium, vanadium or fluorine is that when 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.

According to the one embodiment, it is possible to provide a Zn—Mg alloy-plated steel sheet having a chemical conversion treatment layer having excellent primary rust prevention properties.

DESCRIPTION OF SYMBOLS 1 Zn-Mg alloy plating steel plate 2 Steel plate 3 Zn-Mg alloy plating layer 4 Corrosion product layer 5 Chemical conversion treatment layer

Claims

With steel plate;
A Zn—Mg alloy plating layer formed on the surface of the steel sheet, containing 1.0 to 70.0% by mass of Mg and the balance containing Zn and impurities;
Corrosion formed on the surface of the Zn—Mg alloy plating layer 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 A product layer;
When formed on the surface of the corrosion product layer, and the corrosion product layer contains the Mg salt of the carboxylic acid, the alkali metal salt of the carboxylic acid is contained, and the corrosion product layer is the alkanesulfonic acid. A chemical conversion treatment layer containing an alkali metal salt of the alkanesulfonic acid when containing the Mg salt of
With
The alkali metal salt of the carboxylic acid or the alkali metal salt of the alkanesulfonic acid contained in the chemical conversion layer is at least one selected from the group consisting of Li, Na, K, Rb and Cs.
A Zn—Mg alloy-plated steel sheet.
The Zn-Mg alloy-plated steel sheet according to claim 1, wherein the Zn-Mg alloy plated layer contains 5.0 to 70.0 mass% Mg.
The Zn-Mg alloy-plated steel sheet according to claim 2, wherein the Zn-Mg alloy plating layer contains 10.0 to 70.0 mass% Mg.
The Zn-Mg alloy-plated steel sheet according to claim 3, wherein the Zn-Mg alloy plating layer contains 15.0 to 70.0 mass% Mg.
The Zn-Mg alloy plating layer is
0.3-25.0 mass% Al;
0.01 to 5.00% by mass of Si;
1.0 to 5.0 mass% Ca;
0.1 to 1.5 mass% or less of Ni;
The Zn-Mg alloy-plated steel sheet according to any one of claims 1 to 4, further comprising at least one selected from the group consisting of:
The Zn-Mg alloy-plated steel sheet according to any one of claims 1 to 5, wherein the alkali metal is Na.
7. 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 10 to 1500 mg / m 2 in terms of Na. Zn-Mg alloy-plated steel sheet as described in 1.
The Zn-Mg alloy-plated steel sheet according to any one of claims 1 to 7, wherein the carboxylic acid or the alkanesulfonic acid has 5 to 20 carbon atoms.
The Zn-Mg alloy-plated steel sheet according to claim 8, wherein the carboxylic acid or the alkanesulfonic acid has 8 to 12 carbon atoms.
The Zn-Mg alloy-plated steel sheet according to any one of claims 1 to 9, wherein the carboxylic acid is a saturated fatty acid.
The Zn-Mg alloy-plated steel sheet according to any one of claims 1 to 10, wherein the chemical conversion treatment layer does not contain fluoride, trivalent chromium and vanadium.