JPH09209174A - Galvanized steel and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a film having hardness and m.p. higher than those of a galvanizing or galvannealing layer, excellent in peeling strength after adhesion and furthermore excellent in chemical convertibility on a galvanized steel sheet. SOLUTION: An insular or mosaic Fe-Ni-0 film in which the coating weight of metal in the film is regulated to 10 to 1500mg/m<2> and the surface coating rate is regulated to 30 to 90% is formed. In this film, Fe/Fe+Ni is regulated to 0.004 to 0.9, and the content of 0 is regulated to 0.5 to 10wt.%. A mist-shaped soln. of pH1 to 3.5 contg. Fe and Ni ions is sprayed on a plating layer, which is held for >=1sec at 20 to 70 deg.C and is thereafter subjected to heating treatment to form the film. In the mist-shaped soln., Fe/Fe+Ni is regulated to 0.004 to 0.9. The heating temp. is regulated to 80 to 500 deg.C. A galvanized steel sheet is previously subjected to skinpass rolling, is subjected to acid or alkali treatment and is thereafter subjected to film forming treatment. As the treating process, electrolyzing, dipping or spraying is adapted, and the treating is executed so as to regulate the soln. compsn., pH and treating time to optimum ones.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a zinc-based plated steel sheet, and more particularly to a zinc-based plated steel sheet excellent in press formability, spot weldability, adhesiveness and chemical conversion treatment property, and a method for producing the same.

[0002]

2. Description of the Related Art Zinc-based plated steel sheets are widely used as various anticorrosion steel sheets because they have various excellent characteristics. In order to use this zinc-based plated steel sheet as an anticorrosive steel sheet for automobiles, in addition to corrosion resistance, paint compatibility, etc., the performance required in the vehicle body manufacturing process includes press formability, spot weldability, adhesiveness and chemical conversion. It is important to have good processability.

However, zinc-based plated steel sheets generally have a drawback that they are inferior in press formability to cold-rolled steel sheets.
This is because the sliding resistance between the zinc-based plated steel plate and the press die is
This is because it is higher than in the case of cold-rolled steel sheet, and if this sliding resistance is large, it becomes difficult for the steel sheet to flow into the press die at the part where the bead slides heavily, and the steel sheet easily breaks. Because it will be.

As a method of improving the press formability of a zinc-based plated steel sheet, a method of applying a high-viscosity lubricating oil is generally widely used. However, in this method, since the lubricating oil has a high viscosity, there are problems that a coating defect occurs due to poor degreasing in the next coating step, and that the press performance becomes unstable due to oil shortage. Therefore, there is a high demand for improvement in press formability of galvanized steel sheets.

On the other hand, in the zinc-based plated steel sheet, the copper which is the electrode during spot welding easily reacts with the molten zinc to form a brittle alloy layer, so that the wear of the copper electrode is severe and its life is short. There is a problem that continuous hot spotting properties are inferior to cold rolled steel sheets.

Further, in the manufacturing process of automobile bodies,
Various adhesives are used for the purpose of rust prevention, vibration control, etc., but recently it has become clear that zinc-based plated steel sheets have inferior adhesiveness to cold-rolled steel sheets.

[0007] As a method for solving the above problem, Japanese Patent Laid-Open No. Hei 2
JP-A-190483 discloses that an electrolytic film, a dipping process, a coating oxidation process, or a heating process is performed on the surface of a zinc-based plated steel sheet to generate an oxide film mainly composed of ZnO, thereby improving weldability or workability. JP-A-3-17282 discloses a technique (hereinafter, referred to as Prior Art 1) for allowing the surface of a zinc-based plated steel sheet to be coated with one or more metals selected from Fe, Ni and Co. Disclosed is a method of substitution precipitation (hereinafter referred to as Prior Art 2),
Japanese Unexamined Patent Publication No. 3-191093 discloses a technique of forming Ni oxide to improve press formability and chemical conversion treatability (hereinafter referred to as prior art 3), and
Japanese Unexamined Patent Publication No. 60-63394 discloses a method of applying an aqueous solution of an inert film component (hereinafter referred to as Prior Art 4).

[0008]

The above-mentioned prior art 1 has the following problems. That is, Prior Art 1
Then, since it is a method of producing an oxide mainly composed of ZnO on the plating surface by various treatments, the effect of reducing the sliding resistance between the press die and the plated steel sheet is small, and the effect of improving press formability is small. small. Further, an oxide mainly composed of ZnO deteriorates the adhesiveness.

Prior art 2 has the following problems. With the method of depositing a metal such as Ni or Fe, sufficient adhesion cannot be obtained because the wettability of the metal with respect to the adhesive is small. In addition, there is a problem that the effect of improving press formability and spot weldability is small due to the strong metallic properties of the coating. Further, the pH of the aqueous solution is low and the substitution precipitation efficiency is low, so that a sufficient deposition amount cannot be secured, and the temperature of the aqueous solution needs to be raised to secure the deposition amount, which causes an increase in energy consumption rate. In addition, there is a problem that the manufacturing cost increases, such as installation of heating equipment for the aqueous solution.

In the prior art 3, since it is a Ni oxide single-phase coating, the press formability is improved, but the adhesiveness is deteriorated.

The prior art 4 is a method of forming an inactive film and is therefore effective in improving press moldability, but has a problem of deteriorating chemical conversion processability and adhesiveness.

Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a zinc-based plated steel sheet excellent in press formability, spot weldability, adhesiveness and chemical conversion treatment property, and a method for producing the same. .

[0013]

As a result of intensive studies to solve the above problems, the present inventors have obtained the following results. It has been found that press-formability, spot weldability and adhesiveness can be improved by forming an Fe-Ni-O-based film in the form of islands or mosaics on the surface of the plated layer of a zinc-based plated steel sheet.

The conventional galvanized steel sheet is inferior in press formability to the cold rolled steel sheet. The reason for this is that under high surface pressure, the low melting point zinc and the die cause a cohesion phenomenon, which increases the sliding resistance. In order to prevent this, it is effective to form a film that is harder and has a higher melting point than the zinc or zinc alloy plating layer on the surface of the plating layer of the zinc-based plated steel sheet. Fe- in this invention
Since the Ni-O-based coating is hard and has a high melting point, Fe-N is formed in an island shape or a mosaic shape on the surface of the zinc-based plated steel sheet.
By forming the i-O-based film, the sliding resistance between the surface of the plating layer and the press die during press molding is reduced, the zinc-based plated steel sheet easily slips into the press die, and the press formability is improved. .

The conventional galvanized steel sheet is inferior to the cold-rolled steel sheet in continuous spotting property in spot welding. The cause is that the zinc melted at the time of welding and the copper of the electrode come into contact with each other and melt to form a brittle alloy layer, which causes severe deterioration of the electrode. Therefore, in the present invention, since the Fe-Ni-O-based coating is formed in an island shape or a mosaic shape, the fact that the contact area between the copper electrode and zinc during spot welding is reduced means that the spot weldability is improved. It contributes to the improvement. Further, as a method for improving the continuous spotting property of a zinc-based plated steel sheet, it is considered effective to form a high melting point film on the plated surface. The present inventors have studied various coatings in order to improve the spot weldability of zinc-based plated steel sheets, and have found that Ni or Ni oxide coatings are particularly effective. Although the details of this reason are not clear, Ni reacts with Zn and high melting point Zn
It is considered that the reason for forming an Ni alloy, that Ni and Ni oxide have a very high melting point, and that since Ni oxide has a semiconductive property, electric conductivity is high among various coatings.

It has been known that the adhesiveness of the conventional zinc-based plated steel sheet is inferior to that of the cold rolled steel sheet, but the cause has not been clarified. Then, as a result of investigating the cause, the present inventors have revealed that the adhesiveness is controlled by the composition of the oxide film on the surface of the steel sheet. That is, in the case of a cold-rolled steel sheet, the oxide film on the surface of the steel sheet is mainly Fe oxide, whereas in the case of a zinc-based plated steel sheet, Zn oxide is mainly. The adhesiveness differs depending on the composition of this oxide film.
The adhesiveness was inferior to that of the oxide. Therefore, it is possible to improve the adhesiveness by forming a film containing Fe oxide on the surface of the zinc-based plated steel sheet as in the present invention.

The chemical conversion treatability of the conventional zinc-based plated steel sheet is
What is inferior to cold-rolled steel sheets is that the phosphate film crystals formed are coarse and non-uniform due to the high Zn concentration on the steel sheet surface, and the crystal structure and composition of the phosphate film Due to the difference. When the Zn concentration on the surface of the steel sheet is high, the phosphate crystals mainly consist of hopite, and the secondary adhesion of hot water after coating is poor. This is because the Fe film in the phosphate film has a low concentration, and when exposed to a wet environment after coating, the chemical conversion film condenses and loses its adhesion to the steel sheet.

In order to suppress the condensate of the chemical conversion coating,
It is effective to include metals such as Fe and Ni in the phosphate crystals. By forming the Fe-Ni-O-based coating of the present invention, Ni and Fe in the coating are taken into the phosphate crystals during the chemical conversion treatment, and the chemical conversion coating has good adhesion. Further, since the Fe-Ni-O-based coating is formed by being distributed in an island shape or a mosaic shape, it does not cover the entire zinc-based plating layer. Therefore,
Since the direct reaction between the chemical conversion treatment film and the zinc-based plating layer also occurs at the same time, the adhesion with the zinc-based plating layer itself is secured.

As described above, a mixed film of Ni and Fe composed of a metal and an oxide, that is, an Fe-Ni-O-based film is formed on the surface of a zinc-based plated steel sheet in an island or mosaic pattern. Therefore, it was found that excellent press moldability, spot weldability, adhesiveness and chemical conversion treatability can be obtained.

The present invention has been made on the basis of the above-mentioned findings, and the zinc-based plated steel sheet of the present invention is a zinc-based steel sheet having a Fe-Ni-O-based coating film on the surface of at least one plating layer. Fe-Ni-O plated steel sheet
The system film is distributed in the form of islands or mosaics, and Fe-Ni-
The amount of the O-based coating adhered is in the range of 10 to 1500 mg / m ^{2 in} terms of the total amount of metal elements in the Fe-Ni-O-based coating, and the surface coverage of the Fe-Ni-O-based coating is 30. ~
Characterized by being in the range of 90% (hereinafter,
"First invention").

The preferable zinc-based plated steel sheet of the present invention is
In the steel sheet of the first invention, Fe of the Fe-Ni-O-based film
The ratio of the Fe content (wt.%) To the sum of the content (wt.%) And the Ni content (wt.%) Is 0.004 to
It is in the range of 0.9 and the oxygen content in the Fe-Ni-O-based coating is 0.5 to 10 wt. Characterized by being in the range of% (hereinafter referred to as "second invention")
It is.

The method for producing a zinc-plated steel sheet according to the present invention contains Fe ions and Ni ions and has a pH of 1 to 1.
A mist-like solution within the range of 3.5 is sprayed onto the surface of the plating layer on at least one surface of the zinc-based plated steel sheet,
Next, the zinc-based plated steel sheet is kept for 20 seconds to 70 seconds or more.
The zinc-plated steel sheet thus obtained is subjected to a heat treatment after being kept in a temperature range of ℃, and the adhesion amount is in the range of 10 to 1500 mg / m ² in the total conversion amount of metal elements. , The coverage is in the range of 30 to 90%,
And Fe-N whose distribution form is island-like or mosaic-like
It is characterized by forming an i-O based film on the surface of the plating layer (hereinafter referred to as "third invention").

A desirable method for producing a zinc-plated steel sheet according to the present invention is the method of the third aspect, wherein the sum of the Fe content (g / l) and the Ni content (g / l) in the mist-like solution is calculated. The Fe content (g / l) ratio is 0.004 to
Characterized by being in the range of 0.9 (hereinafter,
It is referred to as the "fourth invention".

Another preferable method for producing the zinc-plated steel sheet according to the present invention is the method of the third or fourth invention, wherein F
In forming the e-Ni-O-based coating, the zinc-plated steel sheet is heat-treated at a temperature of 80 to 500 ° C (hereinafter referred to as the fifth invention).

Another method for producing the zinc-plated steel sheet of the present invention will be described. An important feature of the present invention is that an Fe-Ni-O-based film having an island-shaped or mosaic-shaped form is formed on the surface of a predetermined zinc-based plated steel sheet, and a method for forming the same. In order to properly form the above-mentioned island-shaped or mosaic-shaped Fe-Ni-O-based coating, the zinc-based plated steel sheet is subjected to the following pretreatment to obtain Fe.
A minute portion where a Ni—O based film is easily formed and a minute portion where it is difficult to form are formed on the surface of the plating layer. Then
The Fe-Ni-O-based coating is formed on a zinc-based plated steel sheet having such minute portions formed on the surface. The method of forming this film is characterized in that the amount of adhesion is within the range of 10 to 1500 mg / m ^{2 in} terms of the total conversion amount of metal elements, and the coverage is within the range of 30 to 90%. I have.

The pretreatment method for zinc-plated steel sheet is as follows. Fine unevenness is formed on the surface of the plating layer by temper rolling a zinc-based plated steel sheet (hereinafter, referred to as “sixth invention”).
That). A zinc-plated steel sheet is temper-rolled to form a new surface on the surface of the plating layer (hereinafter referred to as "seventh invention"). By immersing the zinc-plated steel sheet in an acid solution or by anodic electrolysis in an acid solution, a part of the air oxide film existing on the surface of the plating layer is dissolved and the active part and the inactive part are formed on the surface of the plating layer. Part and form (hereinafter,
"Eighth invention"). The zinc-based plated steel sheet is immersed in an alkaline solution or is subjected to anodic electrolysis in an alkaline solution to dissolve a part of the air-oxidized film present on the surface of the plating layer, thereby forming a part that is not active on the surface of the plating layer. And an active portion (hereinafter referred to as the ninth invention).

A preferable method for producing the zinc-plated steel sheet according to the present invention is any one of the sixth to ninth inventions,
As a method for forming the Fe-Ni-O-based coating, a cathodic electrolysis method is used, and the electrolytic solution contains nickel sulfate, ferrous sulfate and ferric sulfate in a total amount of 0.3 to 2.0 mo.
It is contained within the range of 1 / l and satisfies the pH within the range of 1 to 2 (hereinafter referred to as "the tenth invention").

A preferable method for producing a zinc-plated steel sheet according to the present invention is that the electrolytic solution used in the method according to the tenth invention is
The ratio of the Fe content (g / l) to the sum of the Fe content (g / l) and the Ni content (g / l) is 0.004.
Within the range of 0.9 and ferrous sulfate (mol /
l) and ferric sulfate (mol / l) to the sum of the ferric sulfate (mol / l) molar ratio is within the range of 0.5 to less than 1.0 (hereinafter, "Eleventh Invention"
That is).

A desirable method for producing a zinc-plated steel sheet according to the present invention is the method according to any one of the sixth to ninth inventions.
A method of using an aqueous solution for forming a Fe-Ni-O-based film, the aqueous solution containing FeCl ₂ and NiCl ₂
Is contained, the pH is within a range of 2.0 to 3.5, and the temperature is within a range of 20 to 70 ° C. (hereinafter, referred to as “twelfth invention”).

A preferable method for producing the zinc-plated steel sheet according to the present invention is the method of the twelfth invention, wherein Fe--Ni--O is used.
The aqueous solution used for forming the system coating contains Fe (g /
The ratio of the Fe content (g / l) to the sum of 1) and the Ni content (g / l) is in the range of 0.004 to 0.9 (hereinafter, referred to as “13th Invention ”).

[0031]

1 is a schematic view showing a vertical cross section of one embodiment of a zinc-based plated steel sheet according to the present invention. As shown in the figure, the zinc-based plated steel sheet of the present invention is steel sheet 1
And a zinc-based plating layer 2 formed on at least one surface of the steel sheet 1, and an Fe-Ni-O-based coating 3 formed on the surface of the zinc-based plating layer 2 and distributed in an island shape or a mosaic shape.
It consists of

Fe-Ni of the zinc-based plated steel sheet of the present invention
The reason why the -O-based film is limited as described above will be described.
The deposition amount of Fe-Ni-O based film, the reason should be 10~1500mg / m ² in total in terms of the metal element, in this coating weight is less than 10 mg / m ^2, press formability, spot weldability and The effect of improving the adhesiveness cannot be obtained. on the other hand,
This is because when the amount of adhesion exceeds 1500 mg / m ² , not only the above effects are saturated, but also the formation of phosphate crystals is suppressed by the presence of the oxide film, and the chemical conversion treatability deteriorates.

The coverage of the Fe-Ni-O coating 3 distributed in the form of an island or a mosaic covering the surface of the zinc-based plating layer 2 should be limited to the range of 30 to 90% per one side of the steel sheet. Is the street. If the coverage of the Fe-Ni-O-based coating 3 is less than 30% per one side of the steel sheet, the effect of improving press formability and spot weldability cannot be obtained. On the other hand, when the coverage of the Fe-Ni-O-based coating 3 exceeds 90% per one side of the steel sheet, the area in which the phosphate crystals directly react with the zinc-based plated steel sheet decreases, and the zinc-based plating layer 3
This is because the adhesiveness with

Here, it is essential that the form of the Fe-Ni-O-based film is island-like or mosaic-like. The reason for this is that if this coating covers the entire zinc-based plating layer, a direct reaction with the zinc-based plating layer does not occur when the chemical conversion coating is formed. This is because the adhesive strength with the layer itself is not secured and the adhesive strength between the chemical conversion coating and the zinc-based plating layer itself is poor.

As the Fe-Ni-O type coating 3, the Fe ratio (Fe / (Fe + Ni)) in the coating is 0.004 to.
It is desirable to set it within the range of 0.9. The reason is that if Fe / (Fe + Ni) is less than 0.004, the effect of improving the adhesiveness is small, while if it exceeds 0.9, the effect of improving the spot weldability is small.

The oxygen content in the Fe-Ni-O type coating is
0.5-10 wt. It is desirable to set it within the range of%. The reason is that the oxygen content is 0.5 wt. Below%,
Since the metallic properties of the coating become stronger, the effect of improving press formability becomes smaller, while 10 wt. This is because, when the content exceeds%, the formation of phosphate crystals is suppressed by the presence of the oxide film, and the chemical conversion treatability tends to decrease.

Next, the zinc-based plated steel sheet used in the present invention is a steel sheet in which a plated layer is formed on the surface of a base steel sheet by a method such as hot dipping, electroplating or vapor phase plating. And the composition of the zinc-based plating layer is
In addition to pure zinc, Fe, Ni, Co, Mn, Cr, Al, M
It is composed of a metal or oxide such as o, Ti, Si, W, Sn, Pb, Nb and Ta, or a single-layer or multi-layer plating layer containing one or more kinds of organic substances. In addition, SiO ₂ and Al ₂ O are added to the plated layer.
_It may contain fine particles such as ₃ . Further, as the zinc-based plated steel sheet, a multi-layer plated steel sheet and a functionally graded plated steel sheet in which the composition of the plating layer is changed can be used.

Next, the first embodiment of the method for producing a zinc-based plated steel sheet according to the present invention will be described. In the first embodiment, at least one surface of a zinc-based plated steel sheet has a pH of 1 to 1 containing Fe and Ni ions on the surface of the plating layer.
Spray a mist-like solution of 3.5 for 1 second or longer, 20
After being held at ˜70 ° C., by heating this steel sheet, the adhesion amount on the surface of the plating layer is 1 in terms of the total conversion amount of metal elements.
This is to form an Fe-Ni-O-based film having a distribution of 0 to 1500 mg / m ² and a coverage of 30 to 90% in an island shape or a mosaic shape.

The reason for limiting the pH of the mist-like solution to the range of 1 to 3.5 is that when the pH is outside this range, the substitution precipitation reaction does not occur when the solution adheres to the surface of the galvanized steel sheet, Metallic Ni and metallic F in the Fe-Ni-O-based coating
This is because e cannot be formed. After spraying the mist-like solution, the reason why the temperature is kept at 20 to 70 ° C. for 1 second or longer is to secure the time for the substitution reaction to occur, and
This is because Ni and Fe are incorporated into the —Ni—O based film. The mist-like solution is preferably a chloride bath having a high substitution precipitation efficiency, and other solutions such as a sulfuric acid bath and a nitric acid bath may be used as long as the substitution reaction is secured. Further, an additive such as an oxidant or a surfactant may be added in order to improve the efficiency of substitution and precipitation or to facilitate the decomposition of the salt during heating.

The amount of the Fe-Ni-O-based coating adhered is 10 to 1500 mg / m ² in terms of the total conversion of metal elements, and the coverage is 3.
In order to set the content within the range of 0 to 90%, the size and amount of the droplets of the sprayed mist or the concentration of the solution may be adjusted.

The heat treatment temperature of the zinc-based plated steel sheet sprayed with the mist-like solution is limited within the range of 80 to 500 ° C. When the temperature is lower than 80 ° C., salts are not decomposed so that proper Fe content is obtained. This is because it is not desirable because the characteristics of the steel sheet and the plating layer change when the temperature is made into a -Ni-O-based coating, while the temperature exceeds 500 ° C.

The second embodiment of the method for producing a zinc-based plated steel sheet according to the present invention will be described. This second embodiment is
A zinc-based plated steel sheet is temper-rolled to form fine irregularities on the surface of the plated layer, and then a Fe-Ni-O-based film forming treatment is applied to at least one surface of the plated layer, so that the amount of the deposited metal element is 10 to 1500 mg / m ² in total converted amount of
This is to form an Fe-Ni-O-based film having a coverage of 30 to 90% and distributed in an island shape or a mosaic shape.

The zinc-based plated steel sheet is temper-rolled for the purpose of straightening the shape and smoothing the surface. In the present invention, the rolling is performed using a rolling roll having fine irregularities formed on the surface. FIG. 2 is a schematic diagram of a steel plate cross section when a zinc-based plated steel plate is temper-rolled using a rolling roll having fine irregularities formed on the surface. As shown in the figure, fine protrusions 2 a and recesses 2 b are formed on the surface of the zinc-based plating layer 2 of the steel plate 1. Then, the surface of the zinc-based plated steel sheet on which fine irregularities are formed is subjected to a treatment for forming an Fe-Ni-O-based coating, so that an Fe-Ni-O-based coating is formed only on the convex portions 2a, and thus, , Island-like or mosaic Fe-N
An i-O based film is formed. This is because the formation reactivity of the Fe-Ni-O-based coating is higher in the convex portion than in the concave portion. When the Fe-Ni-O-based film is formed by the electrolytic method, the electrolytic current concentrates on the convex portions. When it is formed by the aqueous solution immersion method, the diffusion behavior of the reacting ions in the solution is Due to the difference.

A third embodiment of the method for producing a zinc-based plated steel sheet according to the present invention will be described. This third embodiment is
A zinc-based plated steel sheet is temper-rolled to form a new surface on the plating layer surface, and then at least one surface of the plating layer is subjected to Fe-Ni-O-based film forming treatment, so that the deposition amount is the total of metallic elements. 10 to 1500 mg / m ^{2 in} terms of converted amount, F having a coverage of 30 to 90% distributed in an island shape or a mosaic shape
It is to form an e-Ni-O-based film. The zinc-plated steel sheet is temper-rolled for the purpose of straightening the shape and smoothing the surface. In the present invention, rolling is particularly performed with a rolling roll having a relatively smooth surface. FIG. 3 is a schematic diagram of a steel plate cross section when a zinc-based plated steel plate is temper-rolled by a rolling roll having a relatively smooth surface. As shown in the figure, among the fine irregularities originally present on the surface of the zinc-based plating layer 2 of the steel sheet 1, the convex portion comes into contact with the roll, so that the convex portion 2a where the new surface appears and the new surface are not exposed. The recess 2b is formed. Then, Fe-Ni-O was formed on the surface of the zinc-plated steel sheet in which the new surface appeared on the above-mentioned convex portion.
The Fe-Ni-O-based coating is formed only on the new surface of the convex portion 2a by performing the formation treatment of the coating-based coating, thus forming the island-shaped or mosaic Fe-Ni-O-based coating. This is because the formation reactivity of the Fe-Ni-O-based coating is higher in the convex portion than in the concave portion. Also in this case, as in the case of the second embodiment, when the Fe-Ni-O-based film forming treatment is performed by the electrolytic method, the electrolytic current concentrates on the convex portion, and thus the electrolytic solution immersion method is performed. Is due to the difference in the diffusion behavior of the reacting ions in the solution.

A fourth embodiment of the method for producing a zinc-plated steel sheet according to the present invention will be described. This fourth embodiment is
By immersing a zinc-plated steel sheet in an acid solution or by anodic electrolysis in an acid solution, a part of the air oxide film existing on the surface of the plating layer is dissolved to form an active part and an inactive part. Then, the Fe-Ni-O-based film is subjected to a forming treatment so that the adhesion amount is 10 to 1500 mg / m < ² > in the total conversion amount of the metal elements, and the coverage is 30 to 9.
Fe-Ni-O distributed in 0% islands or mosaic
This is to form a system film.

FIG. 4 shows that the zinc-based plated steel sheet is immersed in an acidic solution or is subjected to anodic electrolysis in an acidic solution to dissolve a part of the air oxide film on the surface of the plated layer, FIG. 6 is a schematic cross-sectional view in the case where an active portion and an inactive portion are formed in the. As shown in the figure,
On the surface of the zinc-based plating layer 2, an inactive part 4 where the air oxide film remains and an active part 5 where the air oxide film remains in a thin state are generated. Then, on the zinc-based plated steel sheet having the above-mentioned active portion and inactive portion, Fe-Ni
The Fe-Ni-O-based coating 3 is formed only on the active portion 5 by performing the formation treatment of the -O-based coating, thus forming an island-shaped or mosaic Fe-Ni-O-based coating. This is because the Fe—Ni—O-based coating has higher generation reactivity in the active portion. When the Fe-Ni-O-based film is formed by the electrolytic method, the electrolytic current is concentrated in the active portion, and when it is formed by the aqueous solution immersion method, the active portion is highly reactive. .

A fifth embodiment of the method for producing a zinc-based plated steel sheet according to the present invention will be described. This fifth embodiment is
In the manufacturing method of the fourth embodiment, an alkaline solution is used instead of the acidic solution, and the effect is exactly the same. That is, by immersing the zinc-based plated steel sheet in an alkaline solution, or by anodic electrolysis in an alkaline solution, a part of the air oxide film existing on the surface of the plating layer is dissolved to form an active part and an inactive part. Is formed, and then the Fe-Ni-O-based film is formed to obtain an adhesion amount of 10 to 1500 m in terms of the total conversion amount of metal elements.
This is to form an Fe-Ni-O-based film having g / m ² and a coverage of 30 to 90% distributed in an island shape or a mosaic shape.

The zinc-plated steel sheet is immersed in an alkaline solution or subjected to anodic electrolysis in an alkaline solution to dissolve a part of the air-oxidized film present on the surface of the plated layer, thereby making it active and inactive. Even when the portions are formed, the cross-sectional state is similar to the state shown in FIG. Then, the Fe-Ni-O-based coating is formed to form the Fe-Ni-O-based coating only on the active portion,
Thus, an island-shaped or mosaic Fe-Ni-O-based film is formed. This is because the Fe—Ni—O-based coating has higher generation reactivity in the active portion. Also in this case
As in the case of the embodiment, when the Fe-Ni-O-based film forming treatment is performed by the electrolytic method, the electrolytic current concentrates on the active portion. It is due to its high quality.

Here, in the formation treatment of the Fe-Ni-O-based coating, the total pH of nickel sulfate, ferrous sulfate and ferric sulfate is 0.3 to 2.0 mol / l
Fe-N by performing cathodic electrolysis using the electrolytic solution of No. 2
An i-O based film can be formed. Further, the Fe content (g / l) and the Ni content (g / l) in the electrolytic solution
The ratio of the Fe content (g / l) to the sum of
Adjusted within the range of 04 to 0.9, and ferrous sulfate (m
ol / l) and ferric sulfate (mol / l) to the sum of the ferrous sulfate (mol / l) molar ratio is 0.5-
It is desirable to adjust within the range of less than 1.0. The reason why such a condition is desirable is that the Fe ratio (Fe
/ (Fe + Ni)) is less than 0.004, Fe-Ni
The Fe content in the -O-based coating becomes low, and the effect of improving the adhesiveness becomes small, while when it exceeds 0.9, Fe-Ni-O.
This is because the Fe content in the system coating increases and the effect of improving spot weldability decreases. The molar ratio of ferric sulfate (ferric sulfate / ferrous sulfate + ferric sulfate) is 0.5.
When it is less than 1, the oxygen concentration in the Fe-Ni-O-based coating becomes low, and on the other hand, the higher the molar ratio, the more easily iron oxide is taken into the Fe-Ni-O-based coating, and the oxygen concentration rises. Is. However, ferric sulfate alone is not desirable because it causes plating burns.

Further, in forming the Fe-Ni-O-based coating, p containing FeCl ₂ and NiCl ₂ is added.
It is desirable to form the Fe-Ni-O-based coating by treating with an aqueous solution of H 2.0 to 3.5 and a temperature of 20 to 70 ° C. Furthermore, the Fe content (g /
It is desirable to adjust the ratio of the Fe content (g / l) to the sum of 1) and the Ni content (g / l) to 0.004 to 0.9.

[0051]

Next, the present invention will be described in more detail with reference to Examples. Examples carried out within the scope of the present invention and comparative examples carried out outside the scope of the present invention were carried out as follows. The zinc-based plated steel sheets used in Examples and Comparative Examples were appropriately selected from the following seven types of plating types represented by the symbols A to G according to the plating method, composition, and amount of deposition. A: Alloyed hot-dip galvanized steel sheet (10 wt.% Fe, balance Zn), and the adhesion amount was 60 g / m ² on both sides. B: hot-dip galvanized steel sheet, the amount of which is 90 on both sides
It is g / m ² . C: Electrogalvanized steel sheet with a deposition amount of 40g on both sides
/ M ² . D: Electric Zn-Fe alloy plated steel sheet (15 wt.% F
e), and the adhesion amount is 40 g / m ² on both sides. E: Electric Zn-Ni alloy plated steel plate (12 wt.% N
i), and the adhesion amount is 30 g / m ² on both sides. F: Electric Zn-Cr alloy plated steel plate (4 wt.% Cr)
And the adhesion amount is 20 g / m ² on both sides. G: Molten Zn-Al alloy plated steel plate (5 wt.% Al)
And the amount of adhesion is 60 g / m ² on both sides.

Regarding the embodiments of the present invention, the following I) to
According to the method V), Fe-distributed in the form of islands or mosaics on the surface of the plating layer of the zinc-based plated steel sheet of the above plating type.
A Ni-O based film was formed.

I) According to the first embodiment of the present invention, F
A zinc-based plated steel sheet in which the e-Ni-O-based coating was distributed in an island shape and a mosaic shape was manufactured. A mist-like solution containing Fe and Ni ions was sprayed onto a zinc-based plated steel sheet, and then this steel sheet was heat-treated to form the above-mentioned film. Other main conditions are as follows. Solution components: nickel chloride and iron chloride Content of metal ions in the solution: 1 to 10 g / l Solution spraying amount: adjusted to obtain a predetermined amount of adhesion Holding time after spraying the solution: 1 to 30 seconds Heating Treatment temperature: 200-350 ° C Heat treatment time: 1 minute

II) Based on the second embodiment of the present invention,
A zinc-based plated steel sheet having an Fe-Ni-O-based coating distributed in an island shape and a mosaic shape was manufactured. Fine unevenness (unevenness pitch: 50 to 300 μm) is formed on the surface of the zinc-based plated layer by temper rolling the zinc-based plated steel sheet, and then 1. Cathodic electrolysis method or 2. The Fe-Ni-O-based film was formed by an aqueous solution dipping method. 1. Cathodic electrolysis method Electrolyte: Nickel sulfate, ferrous sulfate and ferric sulfate containing solution Electrolyte concentration: 0.3-2.0 mol / l (however, total concentration of components) pH: 1-2 Fe in electrolyte Ratio (Fe / (Fe + Ni)): 0.004 to 0.9 Ferric sulfate molar ratio in the electrolyte (ferric sulfate / ferrous sulfate + ferric sulfate): 0.5 to 1.0 2. Aqueous solution immersion method Aqueous solution and component concentration: Nickel chloride = 120 g / l Ferrous chloride = varied to various concentrations. pH: 2.5 to 3.5 Fe ratio in aqueous solution (Fe / (Fe + Ni)): 0.004 to 0.9 Immersion time: 1 to 30 seconds

III) Based on the third embodiment of the present invention, a zinc-based plated steel sheet having an Fe-Ni-O-based coating distributed in an island shape and a mosaic shape was manufactured. A zinc-plated steel sheet is temper-rolled to form a new surface on the surface of the zinc-plated layer (pitch of the new surface: 10 to 50 μm), and then a Fe-Ni-O-based coating is formed. . The film formation is shown in II) 2. It was performed by an aqueous solution immersion method.

IV) Based on the fourth embodiment of the present invention,
A zinc-based plated steel sheet having an Fe-Ni-O-based coating distributed in an island shape and a mosaic shape was manufactured. Zinc plated steel sheet
Dip in a sulfuric acid acid solution of H: 3 for 2 to 5 seconds to dissolve a part of the air oxide film existing on the surface of the zinc-based plating layer, and to make active and inactive parts on the surface of the plating layer. After being formed, an Fe-Ni-O-based film was formed. The formation of the film is as shown in II) 1. Cathodic electrolysis method and 2. It was performed by an aqueous solution immersion method.

V) According to the fifth embodiment of the present invention, F
A zinc-based plated steel sheet in which the e-Ni-O-based coating was distributed in an island shape and a mosaic shape was manufactured. Zinc plated steel sheet
Dip in an alkaline aqueous solution of H: 12 for 2 to 5 seconds to dissolve a part of the air oxide film existing on the surface of the zinc-based plating layer, and to make the active and inactive parts on the surface of the plating layer. Was formed, and then the Fe-Ni-O-based film was formed. The formation of the film is as shown in II) 1. Cathodic electrolysis method and 2. It was performed by an aqueous solution immersion method.

On the other hand, in the comparative example, a zinc-based plated steel sheet on which an Fe-Ni-O-based coating is formed under the conditions outside the scope of the present invention described above, or which is not subjected to the formation treatment of the coating, Was prepared.

Tables 1 to 5 show the plating species (symbols) of the zinc-based plating layer and their adhesion amount, the method for forming the Fe-Ni-O-based coating (symbols), and the metal elements for Examples and Comparative Examples. For the examples and comparative examples shown in Tables 4 and 5, the amount of adhesion and the coverage by the total converted amount of Fe are (Fe / (Fe + N
i)) and its oxygen content.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

The amount of Fe-Ni-O-based film deposited, the coverage,
The measurement of the Fe ratio in the film and the oxygen content in the film is as follows.

[Amount of deposited film and Fe / Fe in film]
(Measurement of (Fe + Ni)] The plating species are hot-dip galvanizing of the symbol B, electrogalvanizing of the symbol C, and electric Zn− of the symbol F.
For the specimens of the Cr alloy plating and the molten Zn-Al alloy plating of the symbol G, a Fe-Ni-O-based coating was used.
The surface layer of the lower plating film (Zn-based plating, the same applies below) is dissolved and peeled off with dilute hydrochloric acid, and F by the ICP method.
By performing a quantitative analysis of e, Ni and metals,
The amount and composition of the Fe-Ni-O-based coating were measured.
Then, Fe / (Fe + Ni) in the film was calculated.

With respect to the specimens of the galvanized alloy galvanized plating having the symbol A, the electric Zn-Fe alloy plating having the symbol D, and the electric Zn-Ni alloy plating having the symbol E, Fe was contained in the lower plating film. It is difficult to completely separate the upper Fe-Ni-O-based coating composition element and the lower-layer plating coating composition element by the ICP method because they contain the constituent elements in the -Ni-O-based coating. Therefore, by the ICP method, Fe
Among the elements in the —Ni—O-based coating, only the elements not included in the lower plated coating were quantitatively analyzed. Furthermore, after Ar ion sputtering, measurement of each component element in the Fe—Ni—O-based coating was repeated from surface to surface by XPS method to measure the composition distribution of each component element with respect to the depth of the plating layer. In this measuring method, the half of the depth at which the element of the Fe-Ni-O-based film not contained in the lower plated film is the maximum concentration and the depth at which the element is no longer detected, and the surface The spacing is Fe-Ni-O
The thickness of the system film. And the result of ICP method and XPS
From the result of the method, the amount of Fe-Ni-O-based coating and the composition were calculated. Then, Fe / (Fe + Ni) in the film was calculated.

[Measurement of Coverage] The coverage of the Fe—Ni—O-based film formed in an island shape or a mosaic shape was measured as follows. By AES analysis method (Auger electron spectroscopy) or EPMA analysis method, mapping analysis of the plating surface on which the Fe-Ni-O-based film is formed is performed.
The distribution state of Ni, Fe and O on the surface was measured, and Fe-
The amount of Ni-O-based coating adhered is 10 in terms of the total conversion of metal elements.
The coverage was calculated by regarding the point at which a strength of mg / m ² or more was obtained as the covered point and determining the ratio of the covered point to the total number of measured points. Figure 5 shows EP
The distribution state of Ni in the Fe-Ni-O-based film is analyzed by MA, and an example of a micrograph obtained by image processing is shown. This is measured by EPMA in a range of 600 × 600 μm on the surface to be inspected at a pitch of 3 μm and under an acceleration voltage of 5 keV.
White part is 10 mg / m in Fe-Ni-O system film
^This is a portion where Ni strength of ² or more is obtained. White parts are distributed in an island shape or a mosaic shape, and Fe-Ni-O
It shows that the system film is formed in an island shape or a mosaic shape.

[Measurement of Oxygen Content of Coating] The oxygen content of the coating was determined from the results of AES depth direction analysis.

Specimens of the above Examples and Comparative Examples (No.
1 to 72), the press moldability, spot weldability and chemical conversion treatability were evaluated, and the test piece No. 1
For Nos. 48 to 48, the adhesion between the chemical conversion coating and the zinc-based plating layer itself was evaluated, and for Nos. 49 to 72, the adhesion was evaluated.

[Measurement of Friction Coefficient] In order to evaluate press formability, the friction coefficient of each sample was measured by the following device. FIG. 6 is a schematic front view showing the friction coefficient measuring device. As shown in the figure, a friction coefficient measurement sample 6 collected from a sample is fixed to a sample table 7, and the sample table 7 is fixed to an upper surface of a horizontally movable slide table 8.
On the lower surface of the slide table 8, there is a roller 9 in contact with it.
A slide table support base 10 having an up-and-down movement is provided, and by pushing up the slide table support base 10, a first load cell 12 for measuring a pressing load N on a friction coefficient measuring sample 6 by a bead 11 is provided. Are attached to the slide table support 10. A second portion for measuring a sliding resistance force F for moving the slide table 8 in the horizontal direction is provided at one end portion of the slide table 8 in the horizontal movement direction while the pressing force is applied. A load cell 13 is attached to one end of the slide table 8. In addition,
As a lubricating oil, press cleaning oil Preton R352L manufactured by Sugimura Chemical Co., Ltd. was used and applied to the surface of the sample 6 for measuring the friction coefficient, and the test was conducted.

The friction coefficient μ between the specimen and the bead is
Formula: Calculated by μ = F / N. However, pressing load N: 400
kgf, sample withdrawing speed (horizontal moving speed of slide table 3): 100 cm / min.

FIG. 7 is a schematic perspective view showing the shape and dimensions of the beads used. The lower surface of the bead 11 slides while being pressed against the surface of the sample 6. Its bottom surface has a flat surface with a width of 10 mm and a length in the sliding direction of 3 mm, and the front and rear surfaces have a width of 10 mm, and the 1/4 cylinder surface of the cylinder surface having 4.5 mmR on each line is as shown in the figure. Touching.

[Continuous Dotting Property Test] In order to evaluate the spot weldability, a continuous Dotting property test was performed on each test piece. Resistance welding (spot welding), in which two specimens of the same No. were stacked, sandwiched by a pair of electrode tips from both sides, and current was concentrated by applying pressure, was continuously performed under the following welding conditions. .・ Electrode tip: dome type with a tip diameter of 6 mm ・ Pressure force: 250 kgf ・ Welding time: 0.2 seconds ・ Welding current: 11.0 KA ・ Welding speed: 1 point / sec. As the evaluation of continuous spotting property, during spot welding, the diameter of the melted and solidified metal part (shape: go-stone, hereafter referred to as nugget) generated at the joint of two welded base materials (specimen) was 4 The number of spots continuously welded until it became less than × t ^1/2 (t: plate thickness of one sheet) was used. The above number of dots is called the electrode life.

[Chemical Treatment Coating Adhesion Test] The specimen was treated with an immersion type zinc phosphate treatment agent for automobile coating base, and further 2
ED coating with a coating thickness of 0 μm was performed. As shown in FIG. 8, between the test pieces 15 of 100 × 25 mm size, 0.1
A test body was prepared such that the thickness of the adhesive 17 was 0.15 mm and the adhesion area was 25 × 10 mm via the spacer 16 of 5 mm, and baking was performed at 170 ° C. for 30 minutes. As the adhesive, an epoxy-based structural adhesive was used. Note that the specimens are various steel sheets with a thickness of 0.8 mm, but depending on the material, the strength is low and the base metal may break during the tensile test. Was used as a reinforcing plate 19 and was used as a test body. This test body was pulled at a speed of 200 mm / min using a tensile tester to measure the average peel strength during peeling, and the peeled surface was observed with a scanning electron microscope (SEM). Peeling occurs at the weakest point. When GA (symbol A) is used, peeling occurs at the interface between the GA plating film and the steel sheet, and the peel strength is the interface adhesion strength between the GA plating film and the steel sheet. GI (symbol B), EG (symbol C), Zn
-Fe (symbol D), Zn-Ni (symbol E), Zn-Cr
(Symbol F) and Zn-Al (symbol G) are used,
Cohesive failure occurs inside the adhesive, and the peel strength is the strength of the adhesive itself. When the coating film of the present invention covers the entire zinc-based plating layer, the adhesion between the chemical conversion treatment film and the zinc-based plating layer itself is not secured, and the peel strength decreases. The peel strength equivalent to that of the untreated material was represented by ◯, and the peel strength lower than that of the untreated material was represented by x.

[Adhesiveness Test] The following adhesiveness test specimens were prepared from the respective specimens. FIG. 9 is a schematic perspective view illustrating the assembly process. As shown in the figure, width 25m
Specimen 13 in which two test pieces 10 having a length of m and a length of 200 mm are laminated and bonded so that the thickness of the adhesive 12 is 0.15 mm with a spacer 11 having a diameter of 0.15 mm interposed therebetween.
And baking at 150 ° C. × 10 min. The test body prepared in this manner was bent into a T-shape as shown in FIG.
A tensile test was performed at a speed of m / min to measure the average peel strength (n = 3 times) when the test body peeled. Peel strength is
The average load was determined from the load chart of the tensile load curve at the time of peeling and expressed in units: kgf / 25 mm. In FIG.
P indicates a tensile load. The adhesive used was a vinyl chloride-based hemming adhesive.

[Chemical conversion treatability test] In order to evaluate the chemical conversion treatability, the following tests were conducted. Each test piece was treated with an immersion type zinc phosphate treatment solution (PBL3080 manufactured by Nippon Parkerizing Co., Ltd.) for an automobile coating base under ordinary conditions to form a zinc phosphate film on the surface thereof. The crystalline state of the zinc phosphate film formed in this way is examined by a scanning electron microscope (SE
M). As a result, the case where the zinc phosphate film was normally formed was represented by ◯, and the case where the zinc phosphate film was not formed or the crystal had a scale was represented by x.

The test results of each test piece measured by the above-mentioned test method are also shown in Tables 1-5. From these tables it is clear that:

In the examples within the scope of the present invention, the coefficient of friction was small and the press formability was good. In particular, in the present invention, since the Fe-Ni-O-based coating is distributed in an island shape or a mosaic shape, when the adhesion amount is the same and other conditions can be regarded as the same, plating by this coating is performed. As the coverage of the layer surface increases, the friction coefficient decreases, which further contributes to the improvement of press formability.

Further, the results of the continuous spotting property test in the spot weldability were all 5000 points or more in all the examples, which were very good.

The chemical conversion treatability is also good in the examples since the crystals of the zinc phosphate coating are formed normally.

Regarding the adhesion between the chemical conversion treatment film and the zinc-based plating layer itself, when the Fe-Ni-O-based coating covers the entire zinc-based plating layer, the chemical conversion treatment film and the zinc-based plating layer itself Since the adhesion is not secured and the peel strength is lowered, the adhesion is not secured in the comparative example of No. 17 in which the coverage with the Fe—Ni—O-based coating is 100%. On the other hand, it is ensured in all the embodiments.

The peel strength was 1 in most of the examples.
2 kgf / 25 mm or more is good.

In Comparative Examples outside the scope of the present invention, any of the friction coefficient, continuous spotting property, adhesiveness and chemical conversion treatability was inferior.

[0085]

Since the present invention is constructed as described above,
Fe- formed on the surface of the plating layer of the zinc-based plated steel sheet
The Ni-O-based coating has improved performance, is harder and has a higher melting point than the zinc or zinc alloy plated layer, and since this coating is distributed in an island shape or a mosaic shape, it can be used during press molding. The sliding resistance between the surface of the plating layer and the press die is remarkably reduced, the zinc-based plated steel sheet easily slips into the press die, and the press formability is improved. Further, the presence of the high melting point Fe-Ni-O-based coating improves the continuous spotting property in spot welding. Furthermore, Fe-Ni
The presence of Fe oxide in the —O-based coating increases the peel strength of the adhesive plate and improves the adhesiveness. Further, the fact that the film is distributed in an island shape or a mosaic shape is added, and the chemical conversion treatability is further improved. Thus, according to the present invention, it is possible to provide a zinc-based plated steel sheet having excellent press formability, spot weldability, adhesiveness, and chemical conversion treatability, which brings about an extremely useful effect industrially.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a vertical cross section of an embodiment of a zinc-based plated steel sheet of the present invention.

2] Fe-Ni- after temper-rolling a zinc-based plated steel sheet using a rolling roll having fine irregularities formed on the surface.
It is a schematic diagram which shows the longitudinal cross section of the Example of the zinc type plated steel plate of this invention at the time of performing the formation process of O type film.

FIG. 3 is an example of a zinc-based plated steel sheet according to the present invention when the zinc-based plated steel sheet is temper-rolled by a rolling roll having a relatively smooth surface and then subjected to a treatment for forming a Fe—Ni—O-based coating. It is a schematic diagram which shows the vertical cross section.

FIG. 4 is a method of immersing a zinc-based plated steel sheet in an acidic solution,
Alternatively, according to the present invention, a part of the air oxide film on the surface of the plating layer is dissolved by anodic electrolysis in an acidic solution to form an active portion and an inactive portion on the plating layer surface. FIG. 3 is a schematic view showing a vertical cross section of an example of the zinc-based plated steel sheet.

FIG. 5: Ni in Fe-Ni-O based coating by EPMA
3 is an example of a micrograph showing a distribution state of.

FIG. 6 is a schematic front view showing a friction coefficient measuring device.

7 is a schematic perspective view showing the shape and dimensions of the beads in FIG.

FIG. 8 is a schematic perspective view showing a method for evaluating the adhesion between the chemical conversion treatment film and the zinc-based plated layer itself, which is one of the characteristics of the zinc-based plated steel sheet of the present invention.

FIG. 9 is a schematic perspective view illustrating a load of a tensile load when measuring peel strength in an adhesiveness test.

FIG. 10 is a schematic perspective view illustrating a load of a tensile load when measuring peel strength in an adhesion test.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 steel plate, 2 zinc-based plating layer, 2a convex part, 2b concave part, 3 Fe-Ni-O type film, 4 inactive part, 5 active part, 6 friction coefficient measurement sample, 7 sample stand, 8 slide table, 9 roller, 10 slide table support, 11 bead, 12 first load cell, 13 second load cell, 14 rail, 15 sample, 16 spacer, 17 adhesive, 18 Test specimen for adhesion test, 19 Reinforcing plate P Tensile load, F Sliding resistance force, N Pressing load.

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[Procedure amendment]

[Submission date] May 15, 1996

[Procedure Amendment 1]

[Document name to be amended] Drawing

[Name of item to be corrected] Figure 5

[Correction method] Change

[Correction contents]

[Figure 5]

Front Page Continuation (72) Inventor Junichi Inagaki Marunouchi 1-2-2 Marunouchi, Chiyoda-ku, Tokyo Japan Steel Tube Co., Ltd. (72) Masaaki Yamashita Marunouchi 1-2-2 Marunouchi, Chiyoda-ku, Tokyo Stock In the company

Claims (13)

[Claims] 1. An F coating on at least one surface of the plating layer.
A zinc-based plated steel sheet having an e-Ni-O-based coating, wherein the Fe-Ni-O-based coating is distributed in an island shape or a mosaic shape, and the adhesion amount of the Fe-Ni-O-based coating is the F-type.
10 to 10 in total converted amount of metal elements in the e-Ni-O-based coating
It is in the range of 1500 mg / m ² , and the Fe-
A zinc-based plated steel sheet, wherein the surface coverage of the Ni-O-based coating is in the range of 30 to 90%. 2. The ratio of the Fe content (wt.%) To the sum of the Fe content (wt.%) And the Ni content (wt.%) Of the Fe—Ni—O-based coating is 0. 004 ~
It is in the range of 0.9 and the oxygen content in the Fe-Ni-O-based coating is 0.5-10 wt. The zinc-based plated steel sheet according to claim 1, which is in the range of%. 3. A p-containing Fe ion and a Ni ion
A mist-like solution having H in the range of 1 to 3.5 is sprayed onto the surface of the plating layer on at least one side of the zinc-based plated steel sheet, and then the zinc-based plated steel sheet is applied for 1 second or longer, 2
After being kept in the temperature range of 0 to 70 ° C., the zinc-based plated steel sheet thus obtained is subjected to a heat treatment, so that the adhesion amount is 10 to 1500 in terms of the total conversion amount of metal elements.
in the range of mg / m ^2, is in the range coverage of 30% to 90%, and the Fe-Ni-O based film is a distribution form islands or mosaic, formed on the plating layer surface A method for producing a zinc-based plated steel sheet, comprising: 4. The Fe content (g in the mist-like solution)
/ L) and the Ni content (g / l)
The method for producing a zinc-plated steel sheet according to claim 3, wherein the content (g / l) ratio is in the range of 0.004 to 0.9. 5. The temperature of the zinc-based plated steel sheet in the heat treatment is 80 to 500 ° C. 3.
A method for producing the zinc-based plated steel sheet described above. 6. The zinc-based plating having the surface of the plating layer on which fine unevenness is formed by temper-rolling a zinc-based plated steel sheet and then forming the fine unevenness on the surface of the plated layer. Fe-Ni-O for steel sheet
An Fe-Ni-O-based coating distributed in an island shape or a mosaic shape is formed on at least one surface of the zinc-based plated steel sheet by performing the formation treatment of the coating-based coating, and the amount of the adhesion is further increased. Is 10 in the total conversion amount of metal elements
It is within the range of 1500 mg / m ² and the coverage is 3
A method for producing a zinc-based plated steel sheet, which comprises forming an Fe-Ni-O-based coating within a range of 0 to 90%. 7. A zinc-plated steel sheet is temper-rolled to form a new surface on the plating layer surface, and then the zinc-based plating steel sheet having the plating layer surface on which the new surface is formed is applied. An Fe-Ni-O-based coating distributed in an island shape or a mosaic shape is formed on at least one surface of the zinc-based plated steel sheet by performing a formation treatment of the Fe-Ni-O-based coating. Moreover, the adhered amount is 10 to 1500 in the total conversion amount of metal elements.
It is in the range of mg / m ² and the coverage is 30 to 90.
% Of Fe-Ni-O type coating film is formed, and the manufacturing method of the zinc-based plated steel sheet characterized by the above-mentioned. 8. A zinc-based plated steel sheet is immersed in an acidic solution or is subjected to anodic electrolysis in an acidic solution to dissolve a part of the air-oxidized film present on the surface of the plated layer and activate it on the surface of the plated layer. Fe-Ni-O is formed on the zinc-based plated steel sheet having the plating layer surface on which the active portion and the inactive portion are formed. Fe-distributed in the form of islands or mosaics by forming the system film
At least one of the zinc-based plated steel sheets is coated with a Ni-O-based coating.
It is formed on the surface of the plating layer on the other side, and the amount of adhesion is in the range of 10 to 1500 mg / m ^{2 in} terms of the total amount of metal elements, and the coverage is in the range of 30 to 90%. A method for producing a zinc-based plated steel sheet, which comprises forming an Fe-Ni-O-based coating. 9. A zinc-based plated steel sheet is immersed in an alkaline solution or is subjected to anodic electrolysis in an alkaline solution to dissolve a part of the air-oxidized film present on the surface of the plated layer so that the surface of the plated layer is dissolved. Fe-Ni- is applied to the zinc-based plated steel sheet having an active portion and an inactive portion, and then having the plating layer surface on which the active portion and the inactive portion are formed. An Fe-Ni-O-based coating distributed in an island shape or a mosaic shape is formed on at least one surface of the zinc-based plated steel sheet by performing an O-based coating forming treatment,
Moreover, the adhesion amount is 10 to 150 in terms of the total conversion amount of metal elements.
Within the range of 0 mg / m ² , and the coverage is 30 to 9
A method for manufacturing a zinc-based plated steel sheet, which comprises forming an Fe-Ni-O-based coating within a range of 0%. 10. The formation treatment of the Fe—Ni—O-based coating is performed by cathodic electrolysis, and the electrolytic solution of the cathodic electrolysis is nickel sulfate, ferrous sulfate and ferric sulfate in total. It is contained in the range of 0.3 to 2.0 mol / l,
Moreover, the manufacturing method of the zinc-based plated steel sheet according to any one of claims 6 to 9, which satisfies the condition that the pH is in the range of 1 to 2. 11. The electrolytic solution contains Fe contained in the electrolytic solution.
The ratio of the Fe content (g / l) to the sum of the content (g / l) and the Ni content (g / l) is 0.004 to
Within the range of 0.9 and ferrous sulfate (mol /
The molar ratio of the ferrous sulfate (mol / l) to the sum of 1) and ferric sulfate (mol / l) is in the range of 0.5 to less than 1.0. Claim 10
A method for producing the zinc-based plated steel sheet described above. 12. The treatment for forming the Fe—Ni—O-based coating uses an aqueous solution as a treatment liquid, wherein the aqueous solution contains FeCl ₂ and NiCl ₂ , and p
H is in the range of 2.0 to 3.5, and the temperature is 20.
The method for producing a zinc-based plated steel sheet according to any one of claims 6 to 9, which satisfies the condition of being in the range of to 70 ° C. 13. The treatment for forming the Fe—Ni—O-based coating uses an aqueous solution as a treatment liquid, wherein the aqueous solution contains FeCl ₂ and NiCl ₂ , and
The ratio of the Fe content (g / l) to the sum of the e content (g / l) and the Ni content (g / l) is 0.004 to
It is within the range of 0.9, the pH is within the range of 2.0 to 3.5, and the temperature is within the range of 20 to 70 ° C. The method for manufacturing a zinc-plated steel sheet according to any one of claims.