JP3354142B2 - Electro-galvanized steel sheet with bright color and excellent conductivity - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrogalvanized steel sheet having a bright color and excellent conductivity, and more particularly to a color tone which can be suitably used without a top coat in the fields of home appliances, building materials, automobiles and the like. To a galvanized steel sheet which is bright and has excellent conductivity.

[0002]

2. Description of the Related Art Electrogalvanized steel sheets are widely used in the fields of home appliances, building materials, automobiles, etc. because of their excellent corrosion resistance. In recent years, in response to demands from customers to omit the coating process, various chemical conversion treatments such as chromate treatment, and thin film type organic and inorganic clear film treatments have been performed on the electro-zinc plating layer, Steel plates having not only improved corrosion resistance but also fingerprint resistance, lubricity and the like have been developed, and their use by consumers has been rapidly increasing. Furthermore, recently, from the viewpoint of environmental improvement, the demand for a so-called non-chromium film containing no Cr has been increasing, and various kinds of films such as an organic system, an inorganic system, and an organic / inorganic composite system have been developed. Since these galvanized steel sheets with an upper layer treatment are often used without a top coat,
Consumers have become extremely demanding for color and appearance, which did not cause any problems when a conventional topcoat was applied. In particular, as for the color tone, since a bright color tone is preferred, the demand for increasing the lightness (L value) is further increased.

Recently, electrogalvanized steel sheets subjected to the above-mentioned upper layer treatment are used in OA equipment such as copying machines,
It is increasingly used as an outer panel material for personal computers, their peripheral devices, AV devices, and the like. In these applications, it is necessary to secure a good grounding property in order to shield the leakage of electromagnetic waves from the inside of the device. Therefore, the demand for increasing the conductivity, that is, reducing the surface resistance is further increased. ing.

[0004] In response to these requirements, electrogalvanized steel sheets having a bright color tone are disclosed in (1) Japanese Patent Publication No. 5-36514, (2) Japanese Patent Publication No. 7-11071, and (3) Japanese Patent Application Laid-Open No. 10-18078. Gazette, (4) JP-A-10-1807
No. 9 has been proposed. These are all aimed at obtaining an electrogalvanized steel sheet having a bright color tone by controlling the orientation of the electrogalvanized plating layer within a predetermined range.

More specifically, the method described in the above (1)
(00 · 2), (1 · 0), (10 · 1), (10 ·
2), X of 6 types of crystal planes of (10.3) and (11.0)
X-ray diffraction peak intensity values were measured, and the (00
・ 1) Attempt to control the brightness by defining the orientation index, which indicates how many times the plane orientation is preferentially oriented compared to the standard zinc powder in a random state, using a specific formula. It is a thing. The method described in the above (2) also specifies the orientation of the (10.3) plane, the (10.1) plane, the (11.0) plane, and the (00/2) plane using exactly the same equation. It was done. Further, the method described in the above (4) also uses exactly the same equation to obtain the (00 · 2) plane, the (10 · 1) plane,
This defines the orientation index of the (10 · 3) plane and the ratio of these orientation indexes. In addition, the method described in the above (3) includes (00 · 2), (00 · 4), (1 · 0), (1)
0.1), (10.2), (10.3), (11.0)
The X-ray diffraction peak intensity values of the seven types of crystal planes were measured, and the angle formed with the zinc base was small (00 · 2).
Sum of orientation indices of (00 · 4) plane and (10 · 3) plane,
(10.0) plane with a large angle with the zinc base, (1
An attempt was made to control the brightness by defining the sum of the orientation indices of the (0.1), (10.2) and (11.0) planes.

[0006]

However, the present inventors have studied in more detail, and found that the brightness of the electrogalvanized steel sheet is determined by the zinc specificity calculated by the method described in the above (1) to (4). Although affected by the orientation index of the crystal plane to some extent, the correlation is unclear.Therefore, even when producing an electro-galvanized steel sheet whose orientation is controlled by these methods, a bright-colored electro-galvanized steel sheet cannot be obtained. It was found that it was not a stable method and was an extremely uncertain method. And the reason was examined in detail.

As a result, the electrogalvanized plating layer is
(11.2), (20.
In some cases, each of the crystal planes (1), (10.4) and (20.3) is also strongly oriented. In order to accurately grasp the relationship between the orientation and the brightness of the electro-zinc plating layer, these crystal planes are required. It has been found that the orientation to the crystal plane should also be considered.

Further, in the method described in the above (3), although the orientation index of the (004) plane is also taken into consideration,
In the line diffraction measurement, since the (00 · 2) plane and the (00 · 4) plane are equivalent planes, this corresponds to counting the intensity from the same zinc crystal twice. The present inventors have overestimated the orientation of the (00 · 2) plane in this method, and have found that the correlation between the orientation index and the brightness is further worsened. .

Further, the orientation index of the method described in the above (1) to (4) is a value obtained by directly using the ratio of the orientation of the specific crystal plane as compared with the case of the standard zinc powder. Originally, the brightness of an electro-zinc plating layer corresponds to the proportion of zinc crystals oriented in various directions existing in the plating layer. Should be given as a ratio. The present inventors also concluded that this is one of the reasons that the correlation between the orientation and the brightness of the electro-zinc plating layer was insufficient in the methods described in the above (1) to (4). I learned.

On the other hand, the above-mentioned various upper layer treatments, that is, various chemical conversion treatments such as chromate treatment; clear coating treatments such as organic and inorganic coatings;
It is known that when various non-chromium treatments such as an inorganic type and an organic / inorganic composite type are performed, corrosion resistance is generally improved, but conductivity is deteriorated. As for the means for improving the conductivity, no effective means has been found so far, and a method for improving the conductivity by reducing the amount of adhesion in the upper layer treatment has been generally used. As a matter of course, the corrosion resistance is deteriorated by reducing the amount of the upper layer treatment, so that in the conventional technology, one of the corrosion resistance and the conductivity had to be selected according to the purpose of use. .

As described above, even if the orientation of the electro-zinc plating layer is controlled by a conventionally proposed method,
An electrogalvanized steel sheet having a bright color tone could not be stably obtained. Conventionally, when various upper layer treatments are performed, deterioration of conductivity is inevitable. To prevent this, there has been no other method than sacrificing corrosion resistance and reducing the amount of adhesion of the upper layer treatment. Under such circumstances, an electrogalvanized steel sheet having a bright color tone and excellent conductivity has long been desired.

Accordingly, an object of the present invention is to provide an electrogalvanized steel sheet having a bright color tone and excellent conductivity, which has solved the above-mentioned problems.

[0013]

Means for Solving the Problems As an electrogalvanized steel sheet capable of solving the above-mentioned problems, the present invention relates to an electrogalvanized steel sheet having an electrogalvanized plating layer formed on one or both sides of a steel sheet, and having a bright color tone and a conductive property. A galvanized steel sheet having excellent resistance , defined by the following formula (1):
When the orientation ratio R of the crystal plane to be formed is (00 · 2) plane,
0.1 or more and a result defined by the following equation (1).
(10.4 ) plane, ( 10.3 ) plane of orientation ratio R of crystal plane,
Provided is an electrogalvanized steel sheet having a sum of (10 · 2) planes of 0.7 or less. Here, the orientation ratio R (hk · l) of each crystal plane of the electrogalvanized steel sheet is calculated from the following formula (1) based on the diffraction peak intensity obtained by X-ray diffraction measurement.
Defined by R (hk · l) = [I (hk · l) / I _s (hk · l)
l)] / Σ [I (hk · l) / I _s (hk · l)]
(1) In the formula (1), I (hk · l) represents each crystal plane (hk · l) of the electrogalvanized plating layer obtained by X-ray diffraction measurement.
Is the diffraction peak intensity value (cps) of I _s (hk ·
l) is the diffraction peak intensity value (cps) of each crystal plane (hk · l) of the standard zinc powder. Further, Σ represents ten kinds of crystal planes required for evaluation, that is, (00 · 2), (10 ·
0), (10.1), (10.2), (10.3),
(11.0), (11.2), (20.1), (10.
4) means summing the values for each crystal plane of (20.3).

The electrogalvanized steel sheet has a bright color and excellent conductivity, and can be suitably used as it is. However, in order to further improve corrosion resistance, fingerprint resistance, lubricity, etc., the electrogalvanized steel sheet is used. Various chemical conversion treatments such as chromate treatment on the plating layer; clear film treatments such as thin film type organic, inorganic and organic / inorganic composites; organic, inorganic and organic / inorganic composites containing no Cr Even if a non-chrome treatment or the like is performed, it can be suitably used.

In particular, according to the present invention, an electrogalvanized plating layer is formed on one or both sides of a steel sheet, and 120 mg / m ^{2 in} terms of Cr is formed on at least one of the electrogalvanized plating layers.
The color tone formed by the following chromate film
An electrogalvanized steel sheet having excellent electrical properties, wherein the crystal plane defined by the following formula (1) of the electrogalvanized plating layer is
The orientation ratio R is 0.1 to 0.8 for the (00 · 2) plane , and the orientation ratio R of the crystal plane defined by the following formula (1).
Of (10.4) plane, (10.3) plane, the (10 · 2) plane
The present invention provides an electrogalvanized steel sheet having a sum of 0.1 to 0.7. Here, the orientation ratio R (hk · l) of each crystal plane of the electrogalvanized steel sheet is defined by the above equation (1).

In a preferred embodiment of the present invention, in the electrogalvanized steel sheet of this aspect, a clear film having a dry mass of 2 g / m ² or less is formed on at least one of the chromate films. It is.

Further, the present invention provides a steel sheet having an electrogalvanized plating layer formed on one or both surfaces thereof, and having a dry mass of 2 g / dry mass substantially free of Cr on at least one of the electrogalvanized plating layers. An electrogalvanized steel sheet having a bright color tone and excellent conductivity formed by forming a non-chromium film of m ² or less, wherein the electrogalvanized plating layer has the following formula:
The orientation ratio R of the crystal plane defined by (1) is (00 · 2)
0.1 to 0.8 for the surface , and the following formula (1)
( 10.4 ) plane of the orientation ratio R of the crystal plane defined by
The sum of the ( 0.3) and (10.2) planes is 0.1 to
An electrogalvanized steel sheet having a ratio of 0.7 is provided. Here, the orientation ratio R (hk) of each crystal plane of the galvanized steel sheet.
L) is defined by the above equation (1).

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present inventors have used a sulfuric acid-based electrogalvanizing bath using an insoluble electrode, which is widely used as a general industrial manufacturing method for electrogalvanized steel sheets, and has a bath composition, an impurity concentration, a bath temperature, and a bath temperature. The plating treatment conditions such as pH, solution flow rate, and current density were variously changed, and the relationship between the color tone and conductivity of the obtained electrogalvanized steel sheet and the crystal plane orientation of the plating layer was investigated in detail. At this time, the color tone of the electrogalvanized steel sheet is JIS Z8730 (S45.3.1, S453.1,
The evaluation was made based on the brightness (L value) specified in the revised H7.3.1). The conductivity was evaluated by measuring the surface resistance using a resistivity meter (Loresta-AP, manufactured by Mitsubishi Chemical Corporation) connected to a four-probe probe (ESP probe).

Further, the crystal plane orientation of the plating layer can be determined by analyzing the diffraction peak intensity obtained by X-ray diffraction measurement in detail, and determining the existence ratio of each crystal plane, which is one of the gist of the present invention, ie, the orientation. The rate was converted to an evaluation.

As described in the JCPDS card, the crystal plane of zinc is the (00 · 2) plane from the side having a large lattice constant, that is, from the low angle side when performing X-ray diffraction measurement.
(10.0) plane, (10.1) plane, (10.2) plane,
(10.3) plane, (11.0) plane, (00/4) plane,
(11.2) plane, (20.0) plane, (20.1) plane,
(10.4) plane, (20.2) plane, (20.3) plane,
(10.5) plane, (11.4) plane, (21.0) plane,
(21.1) plane, (20.4) plane, (00/6) plane,
It is measured in the order of the (21.2) plane. The present inventors performed X-ray diffraction measurement of an electrogalvanized steel sheet manufactured by changing plating conditions in various ways, and the obtained peak was (00 ·
It is found that the peak on the low angle side from the 2) plane to the (20.3) plane is almost concentrated, and the peak on the high angle side from the (10.5) plane to the (21.2) plane is hardly measured. did. Then, in order to accurately evaluate the orientation of the electrogalvanized steel sheet, it is necessary to measure all peaks from the (00 · 2) plane to the (20.3) plane.
It was revealed that the peaks from the (0.5) plane to the (21.2) plane can be ignored.

Next, among the peaks from the (00 · 2) plane to the (20.3) plane, the present inventors have found that the equivalent plane in the X-ray diffraction measurement, that is, the (00 · 2) plane and the (00 · 2) plane.・
4) plane, (10.0) plane, (20.0) plane, (10
Regarding the 1) plane and the (20.2) plane, it was examined whether or not both should be considered. As a result, when both equivalent planes are considered, the correlation between the brightness and the conductivity and the crystal plane orientation becomes poor, and only one of them, that is, (00 · 2)
It has been found that the correlation is better when only the (10.0) plane and the (10.1) plane are handled. This is considered to be because, when both equivalent planes are handled, the intensity from the same zinc crystal is counted twice, and the orientation to the crystal plane is overestimated.

From the above examination results, in order to accurately evaluate the orientation of the electrogalvanized steel sheet, (00 · 2)
(10.0), (10-1), (10-2), (10
3), (11.0), (11.2), (20.1),
The present inventors have revealed that it is necessary to evaluate ten types of crystal planes (10 · 4) and (20 · 3). That is, when the ten types of crystal planes are evaluated, the correlation between the brightness and the crystal plane orientation is as described in the above (1) to (1).
It is significantly improved as compared with the method described in (4).

Further, the present inventors have considered that the brightness of the electro-zinc plating layer corresponds to the abundance ratio of zinc crystals oriented in various directions existing in the plating layer. The method of calculating the abundance ratio of the specific crystal plane in the entire electro-zinc plating layer was studied in detail. When the standard zinc powder in a random state is subjected to X-ray diffraction measurement, the peak intensities of the respective crystal planes are not always equal, but generally have an intensity ratio described on a JCPDS card. On the other hand, the peak strength of each crystal plane when measuring an electro-galvanized steel sheet is preferentially oriented to a specific crystal plane under the influence of the plating process conditions, so the strength ratio in the standard zinc powder is It will be different. Therefore, the present inventors calculated the ratio of the peak strength of the electrogalvanized steel sheet to the peak strength of the standard zinc powder for each crystal plane, and assumed this value as the abundance of each crystal plane. Also, the total value of the abundances of the ten crystal planes required for the evaluation was assumed to be the abundance of the entire electrogalvanized plating layer. Based on these, the abundance ratio of the abundance of each crystal plane to the abundance of the entire electrogalvanized plating layer was calculated, and this was defined as the orientation ratio of each crystal plane.

That is, the present inventors defined the orientation ratio R (hk · l) of each crystal plane of an electrogalvanized steel sheet by the following equation (1) from the diffraction peak intensity obtained by X-ray diffraction measurement. R (hk · l) = [I (hk · l) / I _s (hk · l)] / Σ [I (hk · l) / I _s (hk · l)] (1) where expression (1) In the formula, I (hk · l) is each crystal plane (hk · l) of the electrogalvanized plating layer obtained by X-ray diffraction measurement.
Is the diffraction peak intensity value (cps) of I _s (hk ·
l) is the diffraction peak intensity value (cps) of each crystal plane (hk · l) of the standard zinc powder. Further, Σ represents ten kinds of crystal planes required for evaluation, that is, (00 · 2), (10 ·
0), (10.1), (10.2), (10.3),
(11.0), (11.2), (20.1), (10.
4) means summing the values for each crystal plane of (20.3).

The present inventors have studied the correlation between the orientation ratio of each crystal plane defined by the above formula (1) and the lightness (L value) for various electrogalvanized steel sheets. (2) As the orientation ratio of the plane increases, the brightness increases, and the (10.4) plane, the (10.3) plane, and the (1) plane
It has been found that the brightness decreases as the sum of the orientation ratios of the (0.2) plane increases, and that an extremely good correlation can be obtained. Therefore, it has been clarified that the above-described method for calculating the orientation ratio of each crystal plane is extremely effective as a method for accurately evaluating the orientation of an electrogalvanized steel sheet. Therefore, in the present invention, the “orientation ratio” of each crystal plane of the electrogalvanized steel sheet refers to the one defined by the above formula (1). The present inventors have completed the present invention based on the above findings.

In the first embodiment of the present invention, the color tone obtained by forming an electrogalvanized plating layer on one or both surfaces of a steel sheet is bright.
A galvanized steel sheet having excellent conductivity and a crystal face defined by the following formula (1) of the electrogalvanized plating layer:
Is not less than 0.1 for the (00 · 2) plane.
And the orientation ratio of the crystal plane defined by the following formula (1)
(10.4) plane, (10.3) plane, (10.2) plane of R
Is an electrogalvanized steel sheet having a sum of 0.7 or less. In the first aspect of the present invention, when the electro-zinc plating layers are formed on both surfaces of the steel sheet, at least one of the electro-zinc plating layers only has to satisfy the orientation ratio, It is preferable to satisfy. Hereinafter, the reason for limiting the orientation ratio will be described.

FIG. 1 is a graph showing the relationship between the orientation ratio and the lightness (L value) and conductivity (surface resistance) when the electrogalvanized steel sheet is used, that is, when no upper layer treatment is performed. FIG. 1 is prepared from Table 1 of the embodiment described later.) FIG. 1 (a) is (00 · 2)
FIG. 1B shows the relationship between the orientation ratio of the plane and the brightness (L value), and FIG. 1B shows the sum of the orientation ratios of the (10.4), (10.3), and (10.2) planes and the brightness (L). Values). As is clear from these figures, the correlation between the orientation ratio defined by the above equation (1) and the brightness is extremely good.

Here, the reference value of the brightness required of the customer cannot be specified unconditionally because it differs depending on the customer and the product or part to be used. It is preferably at least 75, more preferably at least 75, even more preferably at least 80. Therefore, from FIG. 1A, (00 · 2)
The orientation ratio of the plane is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.37 or more. From FIG. surface,
The sum of the orientation ratios of the (10 · 3) plane and the (10 · 2) plane is 0.3.
It is preferably at most 7, more preferably at most 0.6, even more preferably at most 0.47.

FIG. 1C shows the relationship between the orientation ratio of the (002) plane and the conductivity (surface resistance), and FIG.
The relationship between the sum of the orientation ratios of the (0.4) plane, (10-3) plane, and (10-2) plane and the conductivity (surface resistance) is shown. In the case of electro-galvanized steel sheet that has not been subjected to any upper layer treatment, since the metallic zinc having conductivity is exposed on the surface, the surface resistance does not depend on the orientation rate of the electro-zinc plating layer It shows a low value and the conductivity is good.

According to a second aspect of the present invention, an electrogalvanized plating layer is formed on one or both surfaces of a steel sheet, and 120 mg in terms of Cr is formed on at least one of the electrogalvanized plating layers.
Bright color tone due to the formation of a chromate film of / m ² or less
An electrogalvanized steel sheet having excellent electrical conductivity, wherein the electrogalvanized layer has a crystal defined by the following formula (1):
The orientation ratio R of the plane is 0.1 to 0.
8 and a crystal plane arrangement defined by the following formula (1).
(10.4) plane of Mukoritsu R, (10-3) surface, (10-
2) An electrogalvanized steel sheet having a sum of 0.1 to 0.7 on the surface. In a second aspect of the present invention,
When chromate films are formed on both surfaces of the steel sheet, at least one of the electro-zinc plating layers only has to satisfy the above-mentioned orientation ratio, but it is preferable that both of them are satisfied. Hereinafter, the reason for limiting the orientation ratio will be described.

FIG. 2 shows the orientation ratio, lightness (L value) and conductivity (surface resistance) of an electrogalvanized steel sheet coated with a reactive chromate film at 50 mg / m ² as the upper layer treatment.
(Note that FIG. 2 is created from Table 2 in Examples described later.) FIG.
2A shows the relationship between the orientation ratio of the (00 · 2) plane and the brightness (L value), and FIG. 2B shows the relation between the (10.4) plane, the (10.3) plane,
The relationship between the sum of the orientation ratio of the (10 · 2) plane and the lightness (L value) is shown. As is clear from these figures, FIG.
As in the cases (a) and (b), the correlation between the orientation ratio defined by the above equation (1) and the brightness is extremely good.

Here, by applying a chromate film on the electrogalvanized plating layer, the brightness (L value) is lower than in the case where the electrogalvanized steel sheet is used as it is. The reference value of the brightness required by the customer cannot be specified unconditionally because it differs depending on the customer and the product or part to be used. However, when a chromate film is formed, the L value should be 65 or more. More preferably, it is 70 or more, and 7
Even more preferably, it is 5 or more. Therefore, FIG.
From (a), the orientation ratio of the (00 · 2) plane is preferably 0.1 or more, more preferably 0.2 or more,
It is even more preferable that the ratio is 0.37 or more.
From (10.4) plane, (10.3) plane, (10.2) plane
The sum of the orientation ratios of the surfaces is preferably 0.7 or less,
It is more preferably 0.6 or less, and even more preferably 0.47 or less.

FIG. 2C shows the relationship between the orientation ratio of the (00 · 2) plane and the conductivity (surface resistance), and FIG.
The relationship between the sum of the orientation ratios of the (0.4) plane, (10-3) plane, and (10-2) plane and the conductivity (surface resistance) is shown. As can be seen from FIGS. 2C and 2D, when a chromate treatment is applied to the upper layer of the electrogalvanized plating layer, the orientation ratio of the (00 · 2) plane and the (10
The present inventors have newly found that they show an extremely good correlation with the sum of the orientation ratios of the (4) plane, the (10-3) plane, and the (10-2) plane. Here, the standard value of the surface resistance required by the customer cannot be unconditionally specified because it differs depending on the customer and the product or part to be used, but the surface resistance of the electro-galvanized steel sheet coated with the chromate film is not , 10mΩ
Or less, more preferably 1 mΩ or less, even more preferably 0.3 mΩ or less.
Therefore, from FIG. 2C, the orientation ratio of the (00 · 2) plane is preferably 0.8 or less, more preferably 0.6 or less, and even more preferably 0.47 or less. preferable. From FIG. 2D, the (10.4) plane and the (10.3) plane
The sum of the orientation ratios of the plane and the (10 · 2) plane is preferably 0.1 or more, more preferably 0.2 or more,
Even more preferably, it is 0.28 or more.

According to a third aspect of the present invention, there is provided the electro-zinc plating according to the second aspect of the present invention, wherein a clear film having a dry mass of 2 g / m ² or less is formed on at least one of the chromate films. It is a steel plate. In the third aspect of the present invention, when a clear film is formed on both surfaces of the steel sheet, at least one of the electro-zinc plating layers only has to satisfy the orientation ratio, but both of them are satisfied. Is preferred. Hereinafter, the reason for limiting the orientation ratio will be described.

FIG. 3 shows the orientation ratio and lightness (L) of an electrogalvanized steel sheet coated with a reactive chromate film of 20 mg / m ² as an upper layer treatment and then with an organic clear film of 1.0 g / m ^2. Value) and conductivity (surface resistance)
(Note that FIG. 3 is created from Table 3 in Examples described later.) FIG.
3A shows the relationship between the orientation ratio of the (00 · 2) plane and the lightness (L value), and FIG. 3B shows the relation between the (10.4) plane, the (10.3) plane,
The relationship between the sum of the orientation ratio of the (10 · 2) plane and the lightness (L value) is shown. As is clear from these figures, FIG.
As in the cases (a) and (b), the correlation between the orientation ratio defined by the above equation (1) and the brightness is extremely good.

Here, by providing a clear film on the chromate film, the brightness (L value) is lower than when only the chromate film is used. The reference value of the brightness required by the customer cannot be specified unconditionally because it differs depending on the customer and the product or part to be used. However, when the clear film is formed on the chromate film, the L value is 60. It is preferably at least 65, more preferably at least 65, and even more preferably at least 70. Therefore, according to FIG. 3A, the orientation ratio of the (002) plane is 0.1%.
It is preferably at least 0.2, more preferably at least 0.2, and even more preferably at least 0.38. From FIG. 3B, the (10.4) plane and the (10.3) plane , (1
The sum of the orientation ratios of the (0.2) plane is preferably 0.7 or less, more preferably 0.6 or less, and even more preferably less than 0.35.

FIG. 3C shows the relationship between the orientation ratio of the (00 · 2) plane and the conductivity (surface resistance), and FIG.
The relationship between the sum of the orientation ratios of the (0.4) plane, (10-3) plane, and (10-2) plane and the conductivity (surface resistance) is shown. Here, by providing a clear film on the chromate film, the surface resistance is increased as compared with the case of using only the chromate film. The standard value of the brightness required by the consumer cannot be unconditionally specified because it differs depending on the consumer and the product or part to be used, but if a clear film is formed on the chromate film, the surface resistance is It is preferably 100 mΩ or less, more preferably 10 mΩ or less, and even more preferably 5 mΩ or less. Therefore, from FIG. 3C, the orientation ratio of the (002) plane is 0.8.
3 or less, more preferably 0.6 or less, and even more preferably 0.47 or less. From FIG. 3D, the (10.4) plane and the (10.3) plane , (1
The sum of the orientation ratios of the (0.2) plane is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.25 or more. These values are the same as in the case of the second embodiment of the present invention.

The fourth aspect of the present invention is directed to a steel sheet having an electrogalvanized plating layer formed on one or both surfaces of a steel sheet, and having a dry mass substantially free of Cr on at least one of the electrogalvanized plating layers. Is a galvanized steel sheet having a bright color tone and excellent conductivity formed by forming a non-chromium film of ² g / m ² or less in the following formula.
The orientation ratio R of the crystal plane defined by (1) is (00 · 2)
0.1 to 0.8 for the surface , and the following formula (1)
( 10.4 ) plane of the orientation ratio R of the crystal plane defined by
The sum of the ( 0.3) and (10.2) planes is 0.1 to
It is an electrogalvanized steel sheet of 0.7. In the fourth aspect of the present invention, when a non-chromium film is formed on both surfaces of the steel sheet, at least one of the electro-zinc plating layers only needs to satisfy the above orientation ratio, but both of them are satisfied. Is preferred. Hereinafter, the reason for limiting the orientation ratio will be described.

FIG. 4 shows the relationship between the orientation ratio, lightness (L value), and conductivity (surface resistance) of an electro-galvanized steel sheet coated with an organic / inorganic composite non-chromium coating at 1.0 g / m ² as an upper layer treatment. 4 is a graph showing the relationship (FIG. 4)
Are created from Table 4 in the examples described later. ). FIG. 4A shows the relationship between the orientation ratio of the (00 · 2) plane and the brightness (L value), and FIG.
The relationship between the sum of the orientation ratios of the (10 · 3) plane and the (10 · 2) plane and the lightness (L value) is shown. As is clear from these figures, similarly to the cases of FIGS. 1A and 1B, the correlation between the orientation ratio defined by the above equation (1) and the brightness is extremely good.

Here, by applying a non-chromium film on the electro-zinc-based plated layer, the brightness (L value) is lower than that when the electro-zinc-plated steel sheet is used as it is. The reference value of the brightness required by the customer cannot be specified unconditionally because it differs depending on the customer and the product or part to be used. However, when a non-chromium film is formed, the L value should be 60 or more. More preferably, it is 65 or more, and 7
Even more preferably, it is 0 or more. Therefore, FIG.
From (a), the orientation ratio of the (00 · 2) plane is preferably 0.1 or more, more preferably 0.2 or more,
More preferably, it is 0.48 or more.
From (10.4) plane, (10.3) plane, (10.2) plane
The sum of the orientation ratios of the surfaces is preferably 0.7 or less,
It is more preferably 0.6 or less, and even more preferably less than 0.35.

FIG. 4C shows the relationship between the orientation ratio of the (00 · 2) plane and the conductivity (surface resistance), and FIG.
The relationship between the sum of the orientation ratios of the (0.4) plane, (10-3) plane, and (10-2) plane and the conductivity (surface resistance) is shown. As can be seen from FIGS. 4 (c) and 4 (d), when the non-chromium treatment is applied to the upper layer of the electrogalvanized plating layer, the orientation ratio of the (00 · 2) plane and the (10
The present inventors have newly found that they show an extremely good correlation with the sum of the orientation ratios of the (4) plane, the (10-3) plane, and the (10-2) plane. Here, the standard value of the surface resistance required by the customer cannot be unconditionally specified because it differs depending on the customer and the product or part to be used, but the surface resistance of the electro-galvanized steel sheet coated with the chromate film is not , 100m
Ω or less, more preferably 10 mΩ or less, and even more preferably 5 mΩ or less.
Therefore, from FIG. 4C, the orientation ratio of the (00 · 2) plane is preferably 0.8 or less, more preferably 0.6 or less, and even more preferably 0.5 or less. Preferably, from FIG. 4D, the (10.4) plane and the (10.3) plane
The sum of the orientation ratios of the plane and the (10 · 2) plane is preferably 0.1 or more, more preferably 0.2 or more,
Even more preferably, it is 0.25 or more.

As is clear from these results,
Electro-galvanized steel sheet, electro-galvanized steel sheet with a chromate film on the upper layer, electro-galvanized steel sheet with a chromate film and clear film on the upper layer, electro-zinc plating with a non-chromium film on the upper layer Regarding any of the steel sheets, the lightness and conductivity were determined by the orientation ratio of the (00 · 2) plane, and the (10.4) plane, the (10.3) plane, and the (1) plane.
It is almost uniquely determined by the sum of the orientation ratios of the (0.2) plane.

The lightness and conductivity of the electrogalvanized steel sheet are determined by the orientation ratio of the (00 · 2) plane and the (10 · 2) plane.
The reason that the orientation is almost uniquely determined by the sum of the orientation ratios of the 4) plane, the (10-3) plane, and the (10-2) plane is presumed as follows. In the present invention, ten kinds of crystal planes used for calculating the orientation ratio, that is, (00 · 2), (1)
(0.0), (10-1), (10-2), (10
3), (11.0), (11.2), (20.1),
By rearranging the crystal planes (10 · 4) and (20 · 3) in ascending angle with the substrate, (00 · 2) = 0
{, (10.4) = 31.7}, (10.3) = 39.
5 ゜, (10 · 2) = 51.1 ゜, (20.3) = 5
8.8 ゜, (11.2) = 65.0 ゜, (10 ・) =
68.0 °, (20.1) = 78.6 °, (11.0)
= 90 ° and (1 · 0) = 90 °. The present inventors have conducted a detailed investigation on the shape of each crystal plane. As a result, the (00 · 2) plane parallel to the substrate has a shape in which plate-like crystals are stacked in parallel with the substrate, and the angle formed with the substrate. Is 31.7
{10.5} plane, {10.3}
The plane and the (10 · 2) plane have a shape similar to a pyramid-shaped quadrangular pyramid or triangular pyramid, and the angle formed with the substrate is 58.8.
(20.3) plane, (11.2) plane,
(10.1) plane, (20.1) plane, (11.0) plane,
It became clear that the (10.0) plane had a shape in which plate-like crystals were stacked in a shape nearly perpendicular to the substrate.

Therefore, since the (00 · 2) plane is parallel to the substrate, it hardly absorbs incident light, and as a result, light (L value) increases because diffused reflected light increases. This is the same when various upper layer treatments are performed on the electrogalvanized plating layer. Conversely, when the upper layer treatment was performed, the surface state of the upper layer treatment film was extremely flat, and as a result, there was no protrusion of zinc crystals from the surface of the upper layer treatment film. Could not be secured, (00
2) It is considered that the conductivity deteriorates as the orientation ratio of the plane increases. Conversely, (10.4) plane, (10.3) plane,
The (10 · 2) plane has a pyramid-shaped surface shape with the most irregularities. Therefore, the amount of incident light absorbed is the largest, and the lightness (L value) is reduced by reducing the irregularly reflected light. This is the same when various upper layer treatments are performed on the electrogalvanized plating layer. In addition, since the surface is highly uneven, when the upper layer treatment is performed, the ratio of zinc crystals protruding from the upper layer treatment film is increased, and abundant energization points are secured. , (10
It is considered that the conductivity increases as the sum of the orientation ratios of the (3) plane and the (10-2) plane increases.

The means for achieving the above-mentioned orientation ratio defined in the present invention is not limited at all. In addition, since the orientation ratio of each crystal plane varies depending on various factors, a means for achieving the same cannot be uniquely determined. For example, electro-zinc plating using an acidic bath generally used on an industrial scale. In the method, various plating conditions such as bath composition, type and concentration of impurities, type and concentration of additives in the bath, bath temperature, bath pH, liquid flow rate, and current density affect the orientation ratio of each crystal plane. Therefore, these conditions may be controlled alone or in combination so as to satisfy the above-mentioned orientation ratio according to the situation at the site.

In the galvanized steel sheet of the present invention,
The adhesion amount of the electro-zinc plating layer is not limited at all, and may be appropriately determined according to the desired corrosion resistance.
If it is less than g / m ² , the corrosion resistance may be insufficient, so it is preferably 1 g / m ² or more, more preferably 3 g / m ² or more, and if it exceeds 120 g / m ² , Since the cost is high, it is preferably 120 g / m ² or less, more preferably 90 g / m ² or less.

In the electrogalvanized steel sheet of the present invention, the electrogalvanized layer may be formed on only one side of the steel sheet or on both sides, depending on its use. Further, prior to the formation of the electro-zinc plating layer, Ni,
A base plating layer containing Zn, Fe, or the like may be formed.

The electro-galvanized steel sheet of the present invention can be suitably used as it is because it has a bright color tone and excellent conductivity. However, in order to further improve corrosion resistance, fingerprint resistance, lubricity, etc. Various chemical conversion coatings such as chromate treatment on a zinc-based plating layer; clear coatings such as thin film type organic, inorganic and organic / inorganic composite coatings;
A non-chromium coating such as an organic, inorganic, or organic / inorganic composite containing no r may be used alone or in combination.

The reason for limiting the amount of the attached chromate film in the second embodiment of the present invention will be described below. FIG. 5 (a) shows the relationship between the amount of chromate film adhesion and lightness (L value).
(B) is a graph showing the relationship between the amount of chromate film adhered and the conductivity (surface resistance) (FIG. 5 is prepared from Table 5 in Examples described later). As the amount of chromate film attached increases, both lightness and conductivity tend to deteriorate. In consideration of the demands of the customers described above, the amount of the chromate film attached is preferably 120 mg / m ² or less in terms of Cr, and more preferably 100 mg / m ² or less in terms of Cr, particularly from the viewpoint of brightness. , And even more preferably 50 mg / m ² or less in terms of Cr. The amount of the chromate film adhered is generally 1 mg / m ² or more in terms of Cr.

In the second embodiment of the present invention, the method for forming the chromate film is not limited at all, and a known method such as a reaction type chromate treatment, a coating type chromate treatment, or an electrolytic chromate treatment may be used. Both are applicable. Further, in order to improve the corrosion resistance and processability of the chromate film, for example, an inorganic oxide such as silica; an organic compound such as an organic resin, wax particles, and an organic silane compound; and a reaction promotion of phosphoric acid, nitric acid, fluoride, and the like. It is also possible to use a chromate treatment liquid containing an agent and the like.

The reason for limiting the amount of the clear film adhered in the third embodiment of the present invention will be described below. FIG. 6A shows C
FIG. 6 (b) shows the relationship between the amount of the clear film deposited and the lightness (L value) when an organic clear film was further applied on the chromate film of 20 mg / m ^{2 in} terms of r. FIG. 6 is a graph showing the relationship between the amount and the conductivity (surface resistance) (FIG. 6 is created from Table 5 in Examples described later). As the amount of the clear film attached increases, both the brightness and the conductivity tend to deteriorate. Considering the demands of the above-mentioned customers, especially from the viewpoint of conductivity, the adhesion amount of the clear film,
Preferably at 2 g / m ² or less by dry weight, more preferably at 1.5 g / m ² or less by dry weight, even more preferably of a dry weight is 1.0 g / m ² or less.

Further, in the third embodiment of the present invention, the coating composition of the clear coating is not limited at all, and a clear coating such as an organic type, an inorganic type, and an organic / inorganic composite type may be used alone or in combination. And then give it. As the organic clear film, for example, ethylene, acrylic,
Urethane-based, epoxy-based, polyester-based, polyvinyl-based, polyamide-based, fluorine-based and other organic resins,
Depending on the required properties such as corrosion resistance and lubricity, a coating further containing an inorganic oxide such as silica, an inorganic pigment such as various phosphates, wax particles, an organic silane compound and the like can be mentioned.
In addition, as the inorganic clear film, for example, sodium silicate, potassium silicate, mainly silicates such as lithium silicate, corrosion resistance, according to required properties such as lubricity,
Further, a coating containing an inorganic oxide such as silica, an inorganic pigment such as various phosphates, wax particles, an organic silane compound, and the like can be given. Further, for the purpose of further improving corrosion resistance, lubricity, and the like, an organic / inorganic composite clear film in which an organic component and an inorganic component are blended is also preferably used.

The reason for limiting the amount of non-chromium film adhered in the fourth embodiment of the present invention will be described below. FIG. 7 (a)
FIG. 7B shows the relationship between the adhesion amount of the organic / inorganic composite non-chromium film and the lightness (L value) when the organic / inorganic composite non-chromium film containing no Cr was applied. FIG. 7 is a graph showing the relationship between the amount of non-chromium film adhered and the conductivity (surface resistance) (FIG. 7 is prepared from Table 5 in Examples described later). Organic /
As the amount of adhesion of the inorganic composite non-chromium film increases, both lightness and conductivity tend to deteriorate. In consideration of the demands of the consumers described above, the amount of the organic / inorganic composite non-chromium coating is preferably ² g / m ² or less in terms of dry mass, particularly from the viewpoint of conductivity, and 1.5 g / m ² in terms of dry mass. m ² or less, more preferably
It is even more preferred that the dry mass be 1.2 g / m ² or less.

In the fourth embodiment of the present invention, the coating composition of the non-chromium coating is not limited as long as the coating does not substantially contain Cr, and is generally 1 mg / m ² or less in terms of Cr. Instead, a non-chromium film such as an organic, inorganic, or organic / inorganic composite may be applied alone or in combination. The organic non-chromium film, for example, ethylene-based, acrylic-based, urethane-based, epoxy-based, polyester-based, polyvinyl-based, polyamide-based, fluorine-based and other organic resins, corrosion resistance,
Depending on the required properties such as lubricity, coatings further containing inorganic oxides such as silica, inorganic pigments such as various phosphates, wax particles, organic silane compounds and the like can be mentioned. Examples of the inorganic non-chromium film include, for example, metal salts such as silicates, phosphates, nitrates, carbonates, acetates, hydroxides, and chlorides of various metal cations, such as corrosion resistance and lubricity. Depending on the required properties, further inorganic oxides such as silica,
A film containing wax particles, an organic silane compound, or the like can be given. For the purpose of further improving corrosion resistance, lubricity, and the like, an organic / inorganic composite non-chromium coating in which an organic component and an inorganic component are blended is also preferably used. Further, a laminated non-chromium film formed by coating two or more non-chromium films of an organic type, an inorganic type, and an organic / inorganic composite type is also preferably used.

The presence, type, and amount of the upper layer film are determined in consideration of the required characteristics such as corrosion resistance and workability according to the type and location of the product used by the customer.

[0056]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. A cold-rolled steel sheet was used as a plating base sheet, and electro-degreased, washed with water, pickled, washed with water, and subjected to electro-zinc plating in this order to produce an electro-zinc-plated steel sheet. The orientation ratio of the electro-zinc plating layer was changed by changing the bath composition, the type of impurities, the impurity concentration, the bath temperature, the bath pH, the liquid flow rate, and the current density among the electro-zinc plating conditions. Samples 1 to 61 were produced. These processing conditions are shown below.

(Electrolytic degreasing conditions) Bath composition: Na orthosilicate, concentration: 30 g / L Bath temperature: 70 ° C. Current density: 10 A / dm ²・ Electrification time: 5 sec

(Pickling conditions) Bath composition: H ₂ SO ₄ , concentration 50 g / L Bath temperature: 50 ° C. Immersion time: 5 sec

[0059] (electrically galvanized Conditions) bath composition: ZnSO ₄ · 7H ₂ O, concentration _{300~350g / L; Na 2 SO 4} , concentration 0 to 80 g / L · impurities: Ni ^2+, concentration 0 to 300 ppm Fe ²⁺ , concentration 0 to 5000 ppm; Pb ²⁺ , concentration 0 to 10 ppm; Sn ²⁺ , concentration 0 to 10 ppm; Cu ²⁺ , concentration 0 to 2 ppm; In ²⁺ , concentration 0 to 100 ppm; Ir ²⁺ , Concentration 0 to 200 ppm Bath temperature: 30 to 60 ° C. Bath pH: 1.0 to 1.8 Liquid flow rate: 0.5 to 1.5 m / sec Current density: 20 to 160 A / dm ² Coating amount: 20 g / m ²

A part of the electrogalvanized steel sheet thus produced was further subjected to an upper layer treatment. As the upper layer treatment, only three types of chromate treatment, chromate treatment, organic clear film treatment, and organic / inorganic composite non-chromium film treatment were performed. These processing conditions are shown below.

(Chromate treatment conditions) Treatment method: reactive type chromate treatment Adhesion amount: 10 to 160 mg / m ^{2 in} terms of Cr

(Organic clear film treatment conditions) Treatment liquid: ethylene acrylic copolymer resin, 85% (in terms of solids); colloidal silica, 10% (in terms of solids); polyethylene wax, 5% (in terms of solids) Drying conditions: 120 ° C. (plate temperature reached after 15 seconds) Adhesion amount: 0.2 to 3.0 g / m ^{2 in} dry mass

(Organic / Inorganic Composite Non-Chromium Film Treatment Conditions) Treatment solution: polyacrylic resin, 50% (solid content); zinc phosphate, 30% (solid content); aluminum nitrate, 10% (solid) Colloidal silica, 10% (solid content conversion) Drying conditions: 120 ° C. (plate temperature reached after 15 sec) Adhesion amount: 0.2 to 3.0 g / m ^{2 in} dry mass.

X-ray diffraction measurements were performed on the various electrogalvanized steel sheets produced in this manner, and the diffraction peak intensities of the respective crystal planes of the plating layer were calculated from the diffraction peak intensities of the respective crystal planes using the above equation (1). The orientation ratio was calculated. The brightness (L value) of various electrogalvanized steel sheets was measured using a color difference meter.
Was measured. Further, in order to evaluate the conductivity, the surface resistance was measured using a resistivity meter (Loresta-AP, manufactured by Mitsubishi Chemical Corporation) to which a four-probe probe (ESP probe) was connected.

The lightness and conductivity measurement results were ranked according to the following criteria. (Brightness) ・ In the case of electrogalvanized as it is (no upper layer treatment) ◎ +: L value ≧ 80 ◎: 80> L value ≧ 75 ○: 75> L value ≧ 70 ×: 70> L value ・ Chromate coating applied Case ◎ +: L value ≧ 75 ◎: 75> L value ≧ 70 ○: 70> L value ≧ 65 ×: 65> L value ・ When chromate film and clear film are applied, and when non-chromium film is applied ◎ +: L value ≧ 70 ◎: 70> L value ≧ 65 ○: 65> L value ≧ 60 ×: 60> L value

(Conductivity) · In the case of electrogalvanized as it is (no upper layer treatment) and in the case of applying a chromate film ＋+: Surface resistance ≦ 0.3 mΩ ：: 0.3 mΩ <Surface resistance ≦ 1 mΩ ○: 1 mΩ <Surface resistance ≦ 10 mΩ ×: 10 mΩ <Surface resistance ・ When a chromate film and a clear film are applied, and when a non-chromium film is applied. ◎ +: Surface resistance ≦ 5 mΩ Resistance ≦ 100 mΩ ×: 100 mΩ <surface resistance

Table 1 shows the case of electrogalvanized as it is (no upper layer treatment), Table 2 shows the case where chromate film is applied, Table 3 shows the case where chromate film and clear film are applied, and Table 4 shows organic / The orientation ratio of the (00 · 2) plane when the inorganic composite non-chromium film is applied, (10.4)
The measurement results of the sum of the orientation ratios of the plane, (10-3) plane, and (10-2) plane, lightness (L value), and surface resistance are shown. Table 5 shows the orientation ratio of the (00 · 2) plane, (10 · 4) plane, (10
The sum of the orientation ratios of the (3) plane and the (10.2) plane satisfies the present invention.
The measurement results of lightness (L value) and surface resistance of samples 62 to 90 in which a chromate film, a clear film, and an organic / inorganic composite-based non-chromium film are appropriately provided and the amount of adhesion is changed are shown. In Tables 1 to 5, samples 1 to 4
Is a comparative example, and samples 5 to 90 are examples of the first embodiment of the present invention.

As is clear from Table 1, the electrogalvanized steel sheet (samples 5 to 60) of the present invention has a bright color tone and excellent conductivity. Among them, Sample 1 in which the orientation ratio of the (00 · 2) plane of the electro-zinc plating layer is 0.2 or more
In the case of 0 to 60, the color tone is particularly bright.

As is evident from Table 2, of the electrogalvanized steel sheets of the present invention,
A chromate film is formed, the orientation ratio of the (00 · 2) plane of the electro-zinc plating layer is 0.8 or less, and (10
Samples 5 to 48 in which the sum of the orientation ratios of the (4) plane, the (10-3) plane, and the (10-2) plane are 0.1 or more have bright colors and excellent conductivity. Among them, Sample 1 in which the orientation ratio of the (00 · 2) plane of the electro-zinc plating layer is 0.2 or more
Nos. 0 to 48 are particularly bright in color tone, and are the (10.4) plane, the (10.3) plane, and the (10.2) plane of the electro-zinc plating layer.
Samples 5 to 36 in which the sum of plane orientation ratios is 0.2 or more
Is particularly excellent in conductivity. Further, as is apparent from Table 5, sample 6 which is the electrogalvanized steel sheet of the present invention was used.
1, when a chromate film is formed (samples 62 to 70), samples 62 to 68 having a chromate film adhesion amount of 120 mg / m ² or less in terms of Cr have bright colors and excellent conductivity. 100m in Cr conversion
Samples 62 to 67 having a g / m ² or less have a particularly bright color tone.

As is clear from Table 3, the electrogalvanized steel sheet of the present invention has an
Chromate film and clear film are formed,
0.8% orientation ratio of electro-zinc plating layer is 0.8
(10 · 4) plane, (10 · 3) plane, (10
・ 2) Samples 5 and 6 in which the sum of the orientation ratios of the surfaces is 0.1 or more
No. 48 has a bright color tone and is excellent in conductivity. Among them, Samples 10 to 48 in which the orientation ratio of the (00 · 2) plane of the electro-zinc plating layer is 0.2 or more have a particularly bright color tone, and have the (10 · 4) plane of the electro-zinc plating layer, (10.
Samples 5 to 36 in which the sum of the orientation ratios of the 3) plane and the (10 · 2) plane are 0.2 or more are particularly excellent in conductivity. Further, as is apparent from Table 5, when the chromate film and the clear film of 20 mg / m ^{2 in} terms of Cr are formed on the sample 61 which is the electrogalvanized steel sheet of the present invention (samples 71 to 80). Samples 71 to 78 having a clear film adhesion amount of 2 g / m ² or less in terms of dry mass have bright colors and excellent conductivity.
Samples 71 to 77 having a weight of 5 g / m ² or less are particularly excellent in conductivity.

As is evident from Table 4, of the electrogalvanized steel sheets of the present invention,
A non-chromium film is formed, the orientation ratio of the (00 · 2) plane of the electro-zinc plating layer is 0.8 or less, and (10
Samples 5 to 48 in which the sum of the orientation ratios of the (4) plane, the (10-3) plane, and the (10-2) plane are 0.1 or more have bright colors and excellent conductivity. Among them, Sample 1 in which the orientation ratio of the (00 · 2) plane of the electro-zinc plating layer is 0.2 or more
Nos. 2 to 48 are particularly bright in color tone, and are (10.4) plane, (10.3) plane, and (10.2) plane of the electro-zinc plating layer.
Samples 5 to 36 in which the sum of plane orientation ratios is 0.2 or more
Is particularly excellent in conductivity. Further, as is apparent from Table 5, sample 6 which is the electrogalvanized steel sheet of the present invention was used.
1, when a non-chromium film is formed (samples 81 to 90), samples 81 to 88 having a non-chromium film adhesion amount of 2 g / m ² or less in terms of dry mass have bright colors and excellent conductivity. 1.5 g / m ² in dry mass
The following samples 81 to 87 are particularly excellent in conductivity.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

[0080]

[Table 9]

[0081]

As described above, the electro-galvanized steel sheet of the present invention has a bright color tone and excellent conductivity, is extremely valuable industrially, and is suitable for a wide range of applications. Used for

[Brief description of the drawings]

FIG. 1 Orientation ratio and lightness (L value) of an electrogalvanized steel sheet as it is, that is, without any upper layer treatment
6 is a graph showing a relationship between the resistance and the conductivity (surface resistance). (A) is a graph showing the relationship between the orientation ratio of the (00 · 2) plane and the lightness (L value), (b) is the (10.4) plane,
It is a graph which shows the relationship between the sum of the orientation rate of a (10-3) plane and a (10-2) plane, and lightness (L value), and (c) is (00)
-2) It is a graph which shows the relationship between the orientation ratio of a plane and conductivity (surface resistance), (d) is a (10.4) plane, a (10.3) plane.
And conductivity (surface resistance) of the sum of the orientation ratios of the (10.2) plane and the (10.2) plane
6 is a graph showing a relationship with the graph.

FIG. 2 shows a reaction type chromate film of 50 as an upper layer treatment.
4 is a graph showing the relationship between the orientation ratio and lightness (L value) and conductivity (surface resistance) in an electrogalvanized steel sheet subjected to mg / m ² . (A) is a graph showing the relationship between the orientation ratio of the (00 · 2) plane and the lightness (L value), and (b) is the (10.4) plane, (10.3) plane, (10 · 2) plane. 4) is a graph showing the relationship between the sum of the orientation ratios of the plane and the brightness (L value);
(C) is the orientation ratio and conductivity (surface resistance) of the (00 · 2) plane.
It is a graph which shows the relationship with (d), (10.4)
It is a graph which shows the relationship between the sum of the orientation rates of the (10-3) plane, the (10-2) plane, and the conductivity (surface resistance).

FIG. 3 shows a reaction type chromate film of 20 as an upper layer treatment.
mg / m ² , and further an organic clear film was applied to 1. mg / m ² .
4 is a graph showing the relationship between the orientation ratio, lightness (L value), and conductivity (surface resistance) in an electrogalvanized steel sheet subjected to 0 g / m ² . (A) is a graph showing the relationship between the orientation ratio of the (00 · 2) plane and the lightness (L value), and (b) is the (10.4) plane, (10.3) plane, (10 · 2) plane. 4) is a graph showing the relationship between the sum of the orientation ratios of the plane and the brightness (L value);
(C) is the orientation ratio and conductivity (surface resistance) of the (00 · 2) plane.
It is a graph which shows the relationship with (d), (10.4)
It is a graph which shows the relationship between the sum of the orientation rates of the (10-3) plane, the (10-2) plane, and the conductivity (surface resistance).

[4] in the electrolytic zinc-plated steel sheet an organic / inorganic composite system non-chromium film was subjected 1.0 g / m ² as an upper layer processing, the orientation ratio and the lightness (L value) and conductive (surface resistance)
6 is a graph showing a relationship with the graph. (A) is a graph showing the relationship between the orientation ratio of the (00 · 2) plane and the lightness (L value),
(B) is the (10 · 4) plane, (10 · 3) plane, (10 ·
2) A graph showing the relationship between the sum of the orientation ratios of the plane and the lightness (L value), and (c) is a graph showing the relationship between the orientation ratio of the (002) plane and the conductivity (surface resistance). (D) is a graph showing the relationship between the sum of the orientation ratios of the (10.4) plane, (10.3) plane, and (10.2) plane and the conductivity (surface resistance).

FIG. 5 (a) shows the amount of chromate film attached and the lightness (L
(B) is a graph showing the relationship between the chromate film adhesion amount and the conductivity (surface resistance).

FIG. 6 (a) is a graph showing the relationship between the amount of clear film deposited and the lightness (L value) when an organic clear film is further applied on the chromate film, and (b) is the clear film at that time. It is a graph which shows the relationship between the amount of adhesion and conductivity (surface resistance).

FIG. 7A is a graph showing the relationship between the adhesion amount of an organic / inorganic composite non-chromium film and the lightness (L value) when an organic / inorganic composite non-chromium film containing no Cr is applied; 3) is a graph showing the relationship between the amount of the organic / inorganic composite non-chromium film deposited and the conductivity (surface resistance) at that time.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-9-67692 (JP, A) JP-A-4-110489 (JP, A) Patent 3212842 (JP, B2) Iron and steel, VOL. 84 (1998), No. 5, pp. 339-344 Iron and Steel, Vol. 85 (1999), No. 11, pages 806-813 Iron and Steel, Vol. 83 (1997), No. 10, pp. 635-640 (58) Fields investigated (Int. Cl. ⁷ , DB name) C25D 5/26 C23C 22/24 C23C 28/00

Claims (4)

(57) [Claims] An electrogalvanized steel sheet having a bright color tone and excellent conductivity obtained by forming an electrogalvanized plating layer on one or both surfaces of a steel sheet, wherein the electrogalvanized plating layer has the following formula (1) ) Defined by
The orientation ratio R of the crystal plane is 0.1 or less for the (002) plane.
And the crystal plane arrangement defined by the following formula (1):
(10.4) plane of Mukoritsu R, (10-3) surface, (10-
2) An electrogalvanized steel sheet having a surface sum of 0.7 or less. R (hk · l) = [I (hk · l) / I _s (hk · l)
l)] / Σ [I (hk · l) / I _s (hk · l)]
(1) However, in equation (1), I (hk · l) is used for X-ray diffraction measurement.
Therefore, each crystal plane (hk · l) of the obtained electro-zinc plating layer
Is the diffraction peak intensity value (cps) of I _s (hk ·
l) is the diffraction peak of each crystal plane (hk · l) of the standard zinc powder.
強度 is (00 · 2), (1)
(0.0), (10-1), (10-2), (10
3), (11.0), (11.2), (20.1),
Total for each crystal plane of (10.4) and (20.3)
It is. 2. A color tone in which an electro-zinc plating layer is formed on one or both surfaces of a steel sheet, and a chromate film of 120 mg / m ² or less in terms of Cr is formed on at least one of the electro-zinc plating layers. Is an electrogalvanized steel sheet which is bright and excellent in conductivity , wherein the electrogalvanized plating layer is formed by the following formula (1).
The orientation ratio R of the crystal plane is 0.1 to
0.8 and a crystal plane defined by the following formula (1)
(10.4) plane of the orientation ratio R of, (10.3) plane, (10
-2) An electro-galvanized steel sheet whose surface sum is 0.1 to 0.7. R (hk · l) = [I (hk · l) / I _s (hk · l)
l)] / Σ [I (hk · l) / I _s (hk · l)]
(1) However, in equation (1), I (hk · l) is used for X-ray diffraction measurement.
Therefore, each crystal plane (hk · l) of the obtained electro-zinc plating layer
Is the diffraction peak intensity value (cps) of I _s (hk ·
l) is the diffraction peak of each crystal plane (hk · l) of the standard zinc powder.
A click intensity value (cp s), Σ is, (00, 2), (1
(0.0), (10-1), (10-2), (10
3), (11.0), (11.2), (20.1),
Total for each crystal plane of (10.4) and (20.3)
It is. 3. The electricity according to claim 2, wherein a clear film having a dry mass of 2 g / m ² or less is formed on at least one of the chromate films. Galvanized steel sheet. 4. An electrogalvanized plating layer is formed on one or both surfaces of a steel sheet, and a Cr-free, dry mass of 2 g / g on at least one electrogalvanized layer.
brightness tones m ² or less of non-chromium coating is formed
A galvanized steel sheet having excellent electrical conductivity, wherein the galvanized steel sheet comprises a zinc-coated steel sheet defined by the following formula (1):
The orientation ratio R of the crystal plane is 0.1 to
0.8 and a crystal plane defined by the following formula (1)
(10.4) plane of the orientation ratio R of, (10.3) plane, (10
-2) An electro-galvanized steel sheet whose surface sum is 0.1 to 0.7. R (hk · l) = [I (hk · l) / I _s (hk · l)
l)] / Σ [I (hk · l) / I _s (hk · l)]
(1) However, in equation (1), I (hk · l) is used for X-ray diffraction measurement.
Therefore, each crystal plane (hk · l) of the obtained electro-zinc plating layer
Is the diffraction peak intensity value (cps) of I _s (hk ·
l) is the diffraction peak of each crystal plane (hk · l) of the standard zinc powder.
強度 is (00 · 2), (1)
(0.0), (10-1), (10-2), (10
3), (11.0), (11.2), (20.1),
Total for each crystal plane of (10.4) and (20.3)
Value.