JPH10204600A - Galvannealed steel sheet excellent in adhesion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a galvannealed steel sheet capable of producing excellent adhesion even in the case where baking finish is applied at low temp. after respective overlapping parts of mutual steel sheets are joined with an adhesive and also capable of manufacture at a low cost. SOLUTION: This steel sheet is a galvannealed steel sheet where a galvannealing layer of 7-20wt.% Fe content is formed at least on one side of the steel sheet. In the surface of the plating layer, a part where the ratio between Al2 O3 concentration and ZnO concentration, [Al2 O3 /ZnO], exceeds 0.85 and a part where the above ratio, [Al2 O3 /ZnO], is below 0.85 are present as a mixture, and the average concentration of Al2 O3 and the average concentration of ZnO are regulated to 5-50mol%, and 15-95mol%, respectively. Moreover, it is desirable that the ratio between the average concentration of Al2 O3 and the average concentration of ZnO, [Al2 O3 /ZnO], is regulated to 0.05-1.5. It is more desirable that the area ratio of a part, where Al2 O3 concentration is 5-35mol% and ZnO concentration is 20-95mol%, comprising in the surface of the plating layer is regulated to 25-80%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a galvannealed steel sheet having excellent adhesiveness.

[0002]

2. Description of the Related Art Galvannealed steel sheets are widely used as surface-treated steel sheets for automobile bodies because of their excellent corrosion resistance. In the assembly work of an automobile body using such an alloyed hot-dip galvanized steel sheet, conventionally, spot welding has been used to join two superposed alloyed hot-dip galvanized steel sheets. For the purpose of reducing the number of points and improving corrosion resistance, vibration damping properties, etc., joining with an adhesive has come to be performed instead of spot welding. As an adhesive for such bonding, a thermosetting adhesive that is cured in a subsequent step of baking an electrodeposition paint is generally used. On the other hand, with respect to paints applied to automobile bodies, etc., low-temperature baking type electrodeposition coatings have been developed in order to reduce costs and reduce CO ₂ emissions from the viewpoint of global environmental measures. , The baking temperature of the paint is lower than before. However, when the baking temperature is lowered as described above, there arises a problem that the adhesiveness of the alloyed hot-dip galvanized steel sheet when the adhesive is used is inferior to that of the cold-rolled steel sheet.

[0003] As a method of solving such a problem and improving the adhesiveness of an alloyed hot-dip galvanized steel sheet, for example, Japanese Patent Laid-Open No. 4-131386 discloses a method in which a hot-dip galvanized steel sheet is formed on a steel sheet surface. By forming an Al or Al alloy plating layer and then performing an alloying treatment thereon, a Zn—Fe—Al alloy having a Fe content of 7 to 20% by weight is formed on the steel sheet surface.
A technique for forming a system-based alloy plating layer (hereinafter referred to as prior art 1) is disclosed in Japanese Patent Application Laid-Open No. 3-215885.
A technique of forming a coating layer of a metal or alloy such as Cu or Ni after forming an e or Fe-based alloy layer (hereinafter referred to as Conventional Technique 2) is disclosed. Also, Japanese Patent Laid-Open No. 6-10
The 156 publication consists of phosphate, Al ₂ O ₃ and ZnO containing silicates such as that generated in the order of 5~20nm the surface of the galvanized layer formed on the steel plate surface thickness A technique is disclosed in which after removing impurities or initial oxides, an oxide layer made of Al ₂ O ₃ or ZnO having a thickness of 1 nm or more is reformed (hereinafter referred to as Conventional Technique 3).

[0004]

However, the above prior art has the following problems. First, in prior art 1, an Al or Al alloy plating layer is formed on a hot-dip galvanized layer on a steel sheet surface, and then an alloying process is performed. Therefore, the outermost plating layer is an Al-based oxide film. For this reason, sufficient adhesiveness cannot be obtained, and since the Al-based oxide film has a high melting point and low electric conductivity, there is a drawback that the continuous spotting property in spot welding is poor. Also,
Since the plating layer has a two-layer structure, the production cost is high and is not practical.

[0005] The prior art 2 also has a high manufacturing cost because the plating layer has a three-layer structure, which is not practical.
Furthermore, the prior art 3 requires a process for removing impurities and initial oxides present on the surface of the hot-dip galvanized layer, so that the production cost is high and this is not practical. Therefore, the object of the present invention is to solve the problems of the prior art as described above, excellent adhesion is obtained even when painting and baking at a low temperature after joining the overlap portion of the steel plates with an adhesive,
Moreover, it is to provide an alloyed hot-dip galvanized steel sheet that can be manufactured at low cost.

[0006]

In the case of joining an alloyed hot-dip galvanized steel sheet with an adhesive, there is a problem not only in the adhesive strength but also in the form of peeling of the joined portion. There are three possible forms of peeling of the bonded portion: peeling inside the adhesive (cohesive failure), peeling at the interface between the adhesive and the plated steel sheet (interfacial peeling), and breaking on the plated steel sheet side. When the peeling form of the joint portion is cohesive failure inside the adhesive, the steel sheet surface is covered with the adhesive and the corrosion resistance is good.

[0007] When the peel strength at the interface between the adhesive and the plated steel sheet is lower than the cohesive failure strength inside the adhesive, interfacial peeling occurs. When such interfacial peeling occurs, there arises a problem that sufficient adhesive strength cannot be obtained, and that the peeled surface is exposed to the metal and the corrosion resistance is deteriorated. This interfacial delamination is more likely to occur in the alloyed hot-dip galvanized steel sheet than in the cold-rolled steel sheet, and thus the adhesiveness is poor. Since the cohesive failure strength of the adhesive depends on the properties of the adhesive itself, it can be improved by selecting the adhesive, but interfacial fracture is affected by the properties of the surface of the coated steel sheet. Need to be improved. On the other hand, when an adhesive having a high adhesive strength level is used, the peel strength at the interface between the adhesive and the coated steel sheet and the cohesive fracture strength of the adhesive are higher than the fracture strength at the plated layer / ground iron interface of the galvannealed steel sheet. As a result, the steel plate is broken. However, such a fracture on the steel sheet side is a problem inside the alloyed hot-dip galvanized steel sheet (base iron or a coating layer / base metal interface) or a problem in selecting an adhesive, and a problem in the properties of the surface of the plated steel sheet. Therefore, the problem is out of the scope of the present invention.

The present inventors have studied the relationship between the morphology (composition and properties) of the surface of the coating layer of the galvannealed steel sheet and the adhesiveness (the adhesiveness related to the interfacial delamination). The following knowledge was obtained. A general alloyed hot-dip galvanized steel sheet is manufactured by being immersed in a zinc bath containing molten Al, subjected to heat treatment for alloying, and then temper-rolled. The alloyed hot-dip galvanized steel sheet manufactured in this manner has a clean plating containing Al oxide (Al ₂ O ₃ ) and Zn oxide (ZnO) and metal Zn and Fe, except for C adhered by contamination. It has a surface. In this plating surface, a portion where the abundance ratio of Al ₂ O ₃ and ZnO (Al ₂ O ₃ / ZnO) exceeds 0.85 and the thickness of the oxide is as thick as about 2 to 40 nm is present in a part thereof. In addition, a portion where the thickness of the oxide is as thin as less than 2 nm and metal Zn and Fe are present in a relatively large amount is present at a rate of about 25 to 80% with respect to the entire area.

As described above, the reason why the thickness of the oxide on the plating surface is non-uniform is that, in the alloying process of iron and zinc by the alloying process, the alloying speed differs depending on the steel sheet portion, and the plating thickness is different. When the temper rolling is applied to this, a portion where the plating layer is thick and convex (hereinafter, for convenience of explanation, this portion is referred to as a “convex portion”)
In this case, the thickness of the oxide layer is reduced because the oxide is elongated. On the other hand, in the portion where the thickness of the plating layer is thin and concave (hereinafter, this portion is referred to as “concave portion” for convenience of explanation), This is because thick oxides remain because they are not extended much. The concave portion has a larger surface roughness than the convex portion, and usually has a Ra of 0.5 to 2.5 μm.
It has a surface roughness of about m.

[0010] As a result of further research based on such facts, the following facts became clear. (1) adhesion of the galvannealed steel sheet, composition and concentration of the oxide of the plating layer surface are particularly governed largely on the concentration of Al ₂ O ₃ and ZnO concentration and Al ₂ O ₃ in the plating layer surface If the amount is large, the adhesiveness is deteriorated, while if the amount of ZnO is large, the adhesiveness is improved. Therefore, basically, if the concentration of Al ₂ O _{3 on the} surface of the plating layer is reduced and the concentration of ZnO is increased, the adhesiveness of the galvannealed steel sheet is improved. (2) As described above, on the surface of the plating layer of a general alloyed hot-dip galvanized steel sheet, a convex portion having a small oxide thickness and A
There are a l ₂ O ₃ concentration is higher oxides produced thick concave portion, but for these originally oxide thin concentration of Al ₂ O ₃ is low convex portion controlling the composition and concentration of the oxide It is possible, and since this portion occupies about 25 to 80% in area ratio with respect to the surface of the plating layer, the oxide composition and concentration of this convex portion are controlled to reduce the Al ₂ O ₃ concentration and the ZnO concentration. , The adhesiveness can be effectively improved.

(3) On the other hand, although the composition and concentration of the oxide can hardly be controlled in the concave portion where the oxide is originally thick, the concave portion has a larger surface roughness than the convex portion. An improvement in adhesiveness utilizing this surface roughness can be expected. In other words, when the surface roughness of the plating layer is large, the adhesive flows around the rough surface of the plating surface to increase the effective bonding area, which contributes to the improvement of the adhesiveness.
The present invention has been made based on the above findings, and the features of the features are as follows.

(1) An alloyed hot-dip galvanized steel sheet in which an alloyed hot-dip galvanized steel sheet having an Fe content of 7 to 20% by weight is formed on at least one side of the steel sheet. The surface has a portion where the ratio of Al ₂ O ₃ concentration and ZnO concentration [Al ₂ O ₃ / ZnO] exceeds 0.85 and 0.8%.
5 or less, the average concentration of Al ₂ O ₃ is 5 to 50 mol%, and the average concentration of ZnO is 15 to 95.
A galvannealed steel sheet with excellent adhesion, characterized in that it is mol%. (2) In the galvannealed steel sheet of (1) above, the average concentration of Al ₂ O _{3 on} the surface of the galvannealed layer and Zn
The ratio of the average concentration of O [Al ₂ O ₃ / ZnO] is 0.05 to
An alloyed hot-dip galvanized steel sheet having an excellent adhesiveness, which is 1.5.

(3) In the galvannealed steel sheet according to the above (1) or (2), the Al ₂ O ₃ concentration is 5 to 35 mol% and the ZnO concentration is 20 to 95 mol% on the surface of the galvannealed layer. An alloyed hot-dip galvanized steel sheet having excellent adhesiveness, wherein an area ratio of a portion of the plating layer to the surface of the plating layer is 25 to 80%. (4) In the galvannealed steel sheet according to (1) or (2), the concentration of Al ₂ O ₃ in the galvannealed layer surface and ZnO concentration 5~35mol% 20~95m
ol%, the ratio of Al ₂ O ₃ concentration to ZnO concentration [Al
₂ O ₃ / ZnO] is excellent galvannealed steel sheet adhesive, wherein the area ratio in the plating layer surface portion is 0.05 to 0.85 is 25 to 80%.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention and the reasons for limitation will be described below. In the present invention, the alloyed hot-dip galvanized steel sheet is a steel sheet having a hot-dip galvanized material steel sheet and then subjected to an alloying treatment to form an alloyed hot-dip galvanized layer on at least one side of the steel sheet. . In addition,
The alloyed hot-dip galvanized layer contains B, C, P, Mg, Mn, Ti, Si, S for the purpose of improving corrosion resistance and other performances.
One or more elements such as b, Bi, Pb, and W may be contained. The surface of the galvannealed layer is made of Al
The ratio [Al ₂ O ₃ / ZnO] between the ₂ O ₃ concentration and the ZnO concentration is 0.
85, that is, a portion where the Al ₂ O ₃ concentration is extremely high, and a ratio of the Al ₂ O ₃ concentration to the ZnO concentration [Al ₂ O ₃ / Zn
O] of 0.85 or less are mixed. Of these, the portion where the ratio of Al ₂ O ₃ concentration to ZnO concentration [Al ₂ O ₃ / ZnO] exceeds 0.85 corresponds to the above-mentioned concave portion. The other portions (portions having a ratio [Al ₂ O ₃ / ZnO] of 0.85 or less) correspond to the above-mentioned convex portions. Usually, this convex portion occupies about 25 to 80% in area ratio on the plating layer surface.

In the present invention, the ZnO in the convex portion is
For increasing the concentration causes and reduce the concentration of Al ₂ O _3, 50Mo the upper limit of the average concentration of Al ₂ O ₃ in the plating layer surface
1%, and the lower limit of the average concentration of ZnO is 15 mol%. The average concentration of Al ₂ O ₃ on the plating layer surface is 50 mol%
Is exceeded, the Al ₂ O ₃ concentration in the convex portion is too high, so that the effect of improving the adhesive force at the interface between the adhesive and the plating layer by reducing the Al ₂ O ₃ concentration cannot be sufficiently obtained. Is inferior. Similarly, the average concentration of ZnO on the plating layer surface is 1
If it is less than 5 mol%, the ZnO concentration in the above-mentioned convex portion is insufficient, so that the effect of improving the adhesive force between the adhesive and the plating layer interface by ZnO cannot be sufficiently obtained, and in this case also, the adhesiveness is poor. Thus, the Al on the plating layer surface
The presence of ₂ O ₃ reduces the adhesion, while ZnO
Although the reason why the adhesiveness is improved by the presence of is not necessarily clear, it is considered that a chemical bonding force such as a hydrogen bonding force and an intermolecular force at the interface between the adhesive and the plating layer influences.

[0016] On the other hand, in the galvannealed, because Al, which is added to the plating layer in order to control the Fe content in the coating layer is enriched as oxides on the surface, Al ₂ O plating layer surface ₃ Reduce the concentration to less than 5 mol% and the ZnO concentration to 9
Control over the range of more than 5 mol% is practically impossible.
For the above reasons, in the present invention, the average concentration of Al ₂ O _{3 on} the surface of the galvannealed layer is limited to 5 to 50 mol%, and the average concentration of ZnO is limited to 15 to 95 mol%.

The concentration of Al ₂ O ₃ is very high concave portion in galvannealed layer surface as described above (concentration of Al ₂ O ₃ and ZnO concentration ratio of [Al ₂ O ₃ / ZnO] and 0.85 Portion), and since thick oxides are inevitably present at this portion and the Al ₂ O ₃ concentration is high, it is hardly possible to control the composition and concentration of the oxide such as the above-mentioned concave portion. . However, the concave portion has a larger surface roughness than the convex portion, and an effect of improving the adhesiveness by the surface roughness can be obtained. In other words, when the surface roughness of the plating layer is large, the adhesive flows around the rough surface of the plating surface to increase the effective bonding area, which contributes to the improvement of the adhesiveness. Therefore, in the alloyed hot-dip galvanized steel sheet of the present invention, even if such a concave portion having an extremely high Al ₂ O ₃ concentration exists on the surface of the plating layer, high adhesiveness can be secured as a whole.

In the present invention, the average concentration of Al ₂ O ₃ and Z
The ratio of the average concentration of nO [Al ₂ O ₃ / ZnO] is 0.05 to
By setting the ratio to 1.5, the adhesiveness can be further improved. Average concentration of Al ₂ O ₃ and ZnO
When the average concentration ratio [Al ₂ O ₃ / ZnO] exceeds 1.5,
From the viewpoint of further improving the adhesiveness, the proportion of ZnO having an effect of improving the adhesiveness with respect to Al ₂ O ₃ that inhibits the adhesiveness becomes relatively insufficient, and more excellent adhesiveness is obtained. I can't get it. On the other hand, since Al ₂ O ₃ is inevitably present on the plating layer surface including the concave portion,
The ratio of the average concentration of Al ₂ O _{3 to} the average concentration of ZnO [Al ₂ O ₃
/ ZnO] cannot be less than 0.05.

In order to obtain more excellent adhesion, the Al ₂ O ₃ concentration and ZnO concentration on the surface of the plating layer are controlled to the following form, and more preferably to the following form, in addition to the above conditions. Is preferred. Al ₂ O ₃ concentration is 5 to 35 mol% and ZnO concentration is 20 to 95 mol on the surface of the galvannealed layer
The area ratio of the 1% portion to the plating layer surface is 25 to
80% The Al ₂ O ₃ concentration is 5 to 35 mol% and the ZnO concentration is 20 to 95 mol on the surface of the galvannealed layer.
1% and the ratio of the Al ₂ O ₃ concentration to the ZnO concentration [Al ₂ O ₃
[O ₃ / ZnO] has an area ratio of 25 to 80% in a portion of the plating layer surface of 0.05 to 0.85.

These define a more preferable form of the above-mentioned convex portion. Not only the average concentration of Al ₂ O _{3 and} the average concentration of ZnO but also the alloyed molten zinc on the entire steel sheet surface described above. 25 to 80 in area ratio of plating layer surface
%, The reduction of the Al ₂ O ₃ concentration and the securing of the ZnO concentration are specified. the above,
In There regulatory area ratio less than 25%, the area ratio of convex portions is higher ZnO concentration and at a low concentration of Al ₂ O ₃ is too small, the low concentration of Al ₂ O ₃ the convex portion, a high concentration of ZnO Thus, the effect of improving the adhesive force by the conversion becomes insufficient, and more excellent adhesiveness cannot be obtained. On the other hand, since the upper limit of the area ratio occupied on the plating layer surface of the convex portion capable of controlling the composition and concentration of the oxide is 80%, the upper limit of the area ratio defined above is necessarily 80%. .

The Al ₂ O ₃ concentration of the convex portion is 35 mo.
It exceeds l%, the adhesive due to the reduction of the concentration of Al ₂ O ₃ /
The effect of improving the adhesion at the plating layer interface cannot be obtained sufficiently,
Poor adhesion. Similarly, the ZnO concentration of the convex portion is 20 m
If the amount is less than ol%, the effect of improving the adhesive force between the adhesive and the plating layer interface by ZnO cannot be sufficiently obtained, and also in this case, the adhesiveness is poor. On the other hand, regarding the lower limit of the Al ₂ O ₃ concentration and the upper limit of the ZnO concentration, as described above, in the alloyed hot-dip galvanizing, the Al ₂ O ₃ concentration on the surface is less than 5 mol%,
The concentration cannot be controlled in the range above 95 mol%.

Further, as described above, the Al ₂ O ₃ concentration and the Z
nO concentration ratio [Al ₂ O ₃ / ZnO] of 0.05 to 0.8
By setting the condition to be 5, the effect of improving the adhesiveness can be expected. When the ratio of the Al ₂ O ₃ concentration to the ZnO concentration [Al ₂ O ₃ / ZnO] exceeds 0.85, from the viewpoint of further improving the adhesion, the ratio of Al ₂ O ₃ which inhibits the adhesion to Al ₂ O ₃ is reduced. The proportion of ZnO having the effect of improving the adhesiveness becomes relatively insufficient, so that more excellent adhesiveness cannot be obtained. On the other hand, Al ₂
Since O ₃ is inevitably present, the Al ₂ O ₃ concentration and ZnO
It is practically impossible to make the concentration ratio [Al ₂ O ₃ / ZnO] less than 0.05.

The Fe content of the coating layer of the galvannealed steel sheet of the present invention is 7 to 20% by weight. If the iron content in the plating layer is less than 7% by weight, the pure zinc layer (η phase) remains on the surface of the plating layer, causing flaking of the plating layer at the time of press forming, and increasing the friction coefficient. Deteriorates. On the other hand, when the Fe content in the plating layer is 20
If the content is more than 10% by weight, a brittle Γ phase is generated at the steel sheet / plating layer interface, so that the plating layer is easily peeled off during press forming, and the powdering resistance is deteriorated. It is desirable that the adhesion amount of the alloyed hot-dip galvanized layer be in the range of 20 to 120 g / m ² . If the adhesion amount is less than 20 g / m ² , sufficient corrosion resistance cannot be obtained, while if the adhesion amount exceeds 120 g / m ² , workability, weldability, etc., deteriorate.

Various methods for obtaining the composition (Al ₂ O ₃ concentration and ZnO concentration) of the surface of the alloyed hot-dip galvanized layer specified by the present invention can be considered, but a typical method is as follows. Immersion treatment in an oxidizing solution, cathodic electrolysis or anodic electrolysis treatment of an alloyed hot-dip galvanized steel sheet, and a method of heating an alloyed hot-dip galvanized steel sheet under specific conditions. In the method of immersing the galvannealed steel sheet in an oxidizing solution, the galvannealed steel sheet is immersed in an oxidizing agent such as hydrogen peroxide, chloric acid, bromic acid, potassium permanganate, or nitrite ion. 0.1 to 50 g / l in total of one or more selected from
It is immersed in a treatment solution (aqueous solution) to which a certain amount has been added to form an oxide on the surface of the plating layer. At this time, the amount of the oxide formed on the surface of the plating layer is substantially determined by the concentration of the oxidizing agent, the immersion time in the processing solution, and the like, and these are controlled according to the amount of the oxide to be formed.

In the method of heating a galvannealed steel sheet, the galvannealed steel sheet is heated in an air atmosphere or in a gas containing at least 20 vol% of oxygen or ozone to deposit a desired oxide on the surface of the plating layer. Let it form. As the heating conditions in this case, a temperature range in which the alloying reaction between the plating layer and the plated steel sheet base does not excessively proceed and the oxidation of the plating layer surface is promoted is desirable. Heating temperatures in the range of ° C are recommended. Further, since the amount of oxide formed on the plating layer surface is substantially determined by the heating temperature, heating time, oxygen (or ozone) concentration in the heating atmosphere, etc., these are controlled according to the amount of oxide to be formed.

The desired composition of the surface of the galvannealed layer can also be obtained by using the above two methods in combination. The aluminum content in the galvanizing bath when hot-dip galvanizing a steel sheet is 0.05 to 0.3% by weight.
It is preferable that The Al content in the plating bath is 0.
If the content is less than 05% by weight or more than 0.3% by weight, alloying cannot be performed uniformly, and the corrosion resistance, press formability, etc. are deteriorated.

The method for measuring the Al ₂ O ₃ concentration or ZnO concentration on the surface of the galvannealed layer specified by the present invention is not particularly limited. Photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), secondary ion mass spectrometry (SIMS)
And the like. For example, in the case of measuring by AES, the spectrum of each element to be measured is measured after removing a contaminant layer attached to the surface by Ar ion sputtering. The peak of the measured Al spectrum is separated into an Al component present as an oxide and an Al component present as a metal, and similarly, the measured Zn spectrum is converted into a Zn component and a metal present as an oxide. The peak is separated from the existing Zn component. The relative sensitivity factor is corrected for the intensity of these spectra, and the concentrations of Al ₂ O ₃ and ZnO present on the plating layer surface are obtained. Also,
The ratio (area ratio) of the region where Al ₂ O ₃ and ZnO are present at a specific concentration is determined by performing a surface analysis by AES and measuring the distribution of each oxide.

[0028]

[Example] In a hot-dip galvanizing line, a sheet thickness of 0.8
A low-carbon aluminum-killed steel sheet having a thickness of 2 mm was subjected to hot-dip galvanizing and alloying treatment under the following conditions to produce an alloyed hot-dip galvanized steel sheet. Plating bath composition: Al: 0.1-0.2% by weight, balance: Z
n Plating bath temperature: 460 ° C Alloying conditions: Heating was performed in a temperature range of 450 to 600 ° C, and the heating time was adjusted so that the Fe content of the plating layer became a predetermined value. A part of these alloyed hot-dip galvanized steel sheets was subjected to temper rolling at an elongation ratio of 5% or less using a laboratory rolling mill. In addition, No. 12, No. 17, No. 19, N
o. 42-No. For No. 47, temper rolling was not performed. Next, a heat treatment at 350 to 400 ° C. or an immersion treatment in an oxidizing agent solution was performed in the air to adjust the Al ₂ O ₃ concentration and the ZnO concentration on the plating layer surface. In addition, in Comparative Example No. 31 and No. 31. For sample No. 32, after temper rolling, it was immersed in an alkaline solution to remove oxides on the plating surface, and then heated at 300 ° C. in an atmosphere containing oxygen.

With respect to each of the test materials thus obtained, the concentrations of Al ₂ O ₃ and ZnO on the surface of the plating layer were measured, and the adhesion strength was measured and the adhesion was evaluated based on the measured values. . The results are shown in Tables 1 to 5 together with the plating amount of each test material, the Fe content of the plating layer, and the composition and concentration of the plating layer surface. The measurement of the Al ₂ O ₃ concentration and the ZnO concentration on the plating layer surface, the measurement of the adhesive strength, and the evaluation of the adhesiveness were performed as follows.

(1) Al ₂ O ₃ concentration and Z on the plating layer surface
Measurement of nO concentration After the contaminant layer adhered to the surface was removed by AES by sputtering for 0.5 minutes using AES, the spectrum of each element to be measured was measured. The peak of the measured Al spectrum is separated into an Al component present as an oxide and an Al component present as a metal, and similarly, the measured Zn spectrum is converted into a Zn component and a metal present as an oxide. The peak was separated from the existing Zn component. After a relative sensitivity factor correction for the intensities of these spectra, C and Ar due to slight contamination were observed.
With the exception of the above, the concentrations of Al ₂ O ₃ and ZnO on the plating layer surface were determined. The standard sample for the sputtering rate is SiO 2
_{2 Using a} thin film, the sputtering rate is 4.5 nm / min.
Met. The area ratio of the region where Al ₂ O ₃ and ZnO are present at a specific concentration is determined by scanning the plating surface with an electron beam whose beam diameter is reduced to 0.5 mm in AES, and determining the distribution of each oxide. Was measured.

(2) Measurement of Adhesive Strength As shown in FIG. 1, two test pieces (size: 200 mm ×
25 mm) was bonded to each other by interposing a 0.15 mm spacer between the test materials so that the adhesive thickness became 0.15 mm.
The printing was performed at 10 ° C. × 10 minutes. With respect to the test specimen after baking, both test specimens constituting the test specimen were pulled at a speed of 200 mm / min using a tensile tester, and the average peel strength when both test specimens peeled off was measured. The adhesive used was a vinyl chloride resin-based adhesive for hemming. Based on the average peel strength thus measured, the adhesiveness was evaluated as follows. ◎: Average peel strength at the time of peeling is 7.0 kgf / 25 mm
Above: Average peel strength at peeling is 5.0 kgf / 25 mm
Above, less than 7.0 kgf / 25 mm ○-: Average peel strength at the time of peeling is 4.5 kgf / 25 mm.
Above, less than 5.0 kgf / 25 mm △: Average peel strength at the time of peeling is 3.0 kgf / 25 mm.
Above, less than 4.5 kgf / 25 mm ×: The average peel strength at the time of peeling is 3.0 kgf / 25 mm.
Less than

According to Tables 1 to 5, N, which is an example of the present invention,
o. 1 to No. 13, No. 23-No. No. 41 has excellent adhesiveness. Among these examples of the present invention, the ratio [Al ₂ O ₃ / ZnO] of the average concentration of Al ₂ O _{3 to} the average concentration of ZnO on the surface of the plating layer is 0.05 to 1.5. Al ₂ O ₃ concentration on the layer surface is 5
35 mol% and the ZnO concentration is 20 to 95 mol%, and the ratio of the Al ₂ O ₃ concentration to the ZnO concentration [Al ₂ O ₃ / Z
nO] is 0.05 to 0.85 with an area ratio of 25
No. ~ 80%. 1 to No. 10, No. 23-N
o. No. 38 has particularly excellent adhesiveness. On the other hand, each of the comparative examples in which the Al ₂ O ₃ concentration and the ZnO concentration on the surface of the plating layer did not satisfy the conditions of the present invention had poor adhesion.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

As described above, the galvannealed steel sheet of the present invention exhibits excellent adhesion even when the superposed parts of the steel sheets are joined by an adhesive and then baked at a low temperature, and Since there is no need to provide two or more plating layers or remove oxides as in the prior art, it can be manufactured at low cost, and therefore, is a material steel plate which is industrially extremely useful especially in automotive applications and the like. Can be

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a specimen used for measuring an adhesive strength in an example.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Junichi Inagaki 1-2-1, Marunouchi, Chiyoda-ku, Tokyo, Japan Inside the Nippon Kokan Co., Ltd. (72) Inventor Masaaki Yamashita 1-2-1, Marunouchi, Chiyoda-ku, Tokyo, Japan (72) Inventor Hiroshi Kawaguchi 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation

Claims (4)

[Claims] 1. An alloyed hot-dip galvanized steel sheet having an alloyed hot-dip galvanized steel sheet having an Fe content of 7 to 20% by weight on at least one side of the steel sheet, wherein the surface of the galvannealed steel sheet is Means that the ratio of the Al ₂ O ₃ concentration to the ZnO concentration [Al ₂ O ₃ / ZnO] exceeds 0.85 and 0.8
5 or less, the average concentration of Al ₂ O ₃ is 5 to 50 mol%, and the average concentration of ZnO is 15 to 95.
A galvannealed steel sheet with excellent adhesion, characterized in that it is mol%. 2. Al ₂ O _{3 on the} surface of the galvannealed layer
Ratio of the average concentration of ZnO to the average concentration of ZnO [Al ₂ O ₃ / Zn
O] is 0.05-1.5, The alloyed hot-dip galvanized steel sheet excellent in adhesiveness of Claim 1 characterized by the above-mentioned. 3. The method of claim 1, wherein A is applied on the surface of the galvannealed layer.
l ₂ O ₃ concentration is 5 to 35 mol% and ZnO concentration is 20
The alloyed hot-dip galvanized steel sheet having excellent adhesiveness according to claim 1 or 2, wherein an area ratio of a portion of about 95 mol% to a plating layer surface is 25 to 80%. 4. The method according to claim 1, wherein A is applied on the surface of the galvannealed layer.
l ₂ O ₃ concentration is 5 to 35 mol% and ZnO concentration is 20
About 95 mol%, and the area ratio of the portion where the ratio of Al ₂ O ₃ concentration to ZnO concentration [Al ₂ O ₃ / ZnO] is 0.05 to 0.85 to the plating layer surface is 25 to 80%. The galvannealed steel sheet having excellent adhesion according to claim 1 or 2, characterized in that: