JPH07292436A - Surface treated steel sheet for deep drawing, excellent in corrosion resistance, and its production - Google Patents

Abstract

PURPOSE:To provide superior corrosion resistance, workability, weldability, and chemical conversion treating property by forming a diffused alloy region on the surface of a steel sheet of specific composition for deep drawing and then forming a zinc type plating layer containing the grains to be dispersed by means of thin coating. CONSTITUTION:The steel sheet for deep drawing has a composition consisting of, by weight, 0.002-0.01% C, <=1% Si, 0.05-1% Mn, 0.02-0.1% P, <=0.01% Si, <=0.1% sol.Al, <=0.004% N, 0.0005-0.002% B, 0.2-0.5% Cu, 0.1-0.5% Ni, 0.002-0.05% Sn, and the balance Fe. In this composition, a relationship represented by inequality is satisfied, and further, specific amounts of either or both of Ti and Nb are incorporated. A diffused alloy region composed essentially of Fe-Ni-P is formed at least in one side of this steel sheet. Then, a galvanizing layer or a zinc type plating layer containing one or >=2 kinds among the metals of Ni, Fe, Co, Cr, Mn, Ti, Mo, Si, and Al and oxides thereof in the form of alloy or grains to be dispersed is formed on the diffused alloy region by thin coating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated steel sheet having excellent corrosion resistance, workability, weldability, chemical conversion treatability, etc., which is most suitable for automobile steel sheets.

[0002]

2. Description of the Related Art For cold-rolled steel sheets and the like currently used for automobiles, it has been considered to reduce the thickness of the automobile from the viewpoint of weight reduction and cost reduction of the automobile itself. However, if the plate pressure is reduced, the residual margin after corrosion is reduced.
The problem of reduced strength after corrosion arises. Generally, the simplest method is to increase the coating weight of galvanizing in order to improve the corrosion resistance of automobile steel sheets, but increasing the amount of coating leads to an increase in cost and also causes the peeling of the coating layer when processing steel sheets. Problems occur, and the base is exposed and easily corroded. In addition, spot welding is used when assembling automobile parts, but the amount of plating adhered greatly affects this welding. That is, it is recognized that the weldability deteriorates with an increase in the adhesion amount. Further, steel sheets used for automobiles are required to have excellent formability such as deep drawability and be inexpensive.

Under such circumstances, as disclosed in Japanese Unexamined Patent Publication No. 4-141554, there is a technique related to a method for producing a steel sheet with improved corrosion resistance of the steel sheet itself.
In addition to Cu, Ni, and Mo and Cr, a considerable amount of elements are added, which increases the manufacturing cost and tends to deteriorate workability. In addition, since the amount of C is as high as 60 ppm or more, improvement in deep drawability of the steel sheet cannot be expected so much, and the amount of Ti added must be increased in order to reduce the solid solution C, which increases the manufacturing cost or the surface. It also leads to deterioration of properties.

[0004]

SUMMARY OF THE INVENTION The inventor has been made in view of the above circumstances, and has a lower cost and corrosion resistance,
The purpose is to develop a surface-treated steel sheet excellent in workability, weldability, and chemical conversion treatment, and a manufacturing method thereof.

In order to achieve this object, the inventors of the present invention have conducted extensive studies, and as a result, based on IF steel (steel without interstitial solid solution element) as a steel sheet, P as an element for improving corrosion resistance, Attention was paid especially to Sn as an element that adds the elements of Cu and Ni and that imparts corrosion resistance. At least one surface of the deep-drawing steel sheet with excellent corrosion resistance, in which Sn is added, has Ni-P
System alloy plating layer or further Ni-P alloy plating layer containing one or more of W, Mo, Cr, Cu is formed and heat-treated in a non-oxidizing atmosphere. After forming a diffusion alloy region containing Fe-Ni-P as the main component at the interface, Zn plating or Zn is used as a matrix and N
By forming a zinc-based plating layer containing one or more metals or oxides of i, Fe, Co, Cr, Mn, Ti, Mo, Si, and Al as alloys or dispersed particles, it is possible to achieve very low weight loss. Succeeded in ensuring high corrosion resistance.

[0006]

The gist of the invention is as follows. 1) C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.
05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less, sol.Al: 0.
1% or less, N: 0.004% or less, B: 0.0005 to 0.002%, Cu: 0.
2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.05%, and 2 ≦ 1000 × Sn × (2 × P + Cu +
Ni) ≤20, Ti: 0.005 to 0.1%, N
b: contains 0.002 to 0.05% of any one kind or two kinds,
At least one surface of the steel sheet with the balance consisting of iron and unavoidable impurity components has a diffusion alloy region containing Fe-Ni-P as the main component, and on top of this, Zn plating or Zn is used as a matrix, and Ni, Fe It has a zinc-based plating layer containing one or two or more metals or oxides of Co, Cr, Mn, Ti, Mo, Si and Al as alloys or dispersed particles. Surface treated steel sheet having. 2) C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.
05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less, sol.Al: 0.
1% or less, N: 0.004% or less, B: 0.0005 to 0.002%, Cu: 0.
2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.05%, and 2 ≦ 1000 × Sn × (2 × P + Cu +
Ni) ≤20, Ti: 0.005 to 0.1%, N
b: contains 0.002 to 0.05% of any one kind or two kinds,
At least one surface of the steel sheet with the balance consisting of iron and inevitable impurities has a diffusion alloy layer region containing Fe-Ni-P as the main component and one or more of W, Mo, Cr, and Cu.
On top of this, zinc containing Zn plating or Zn as a matrix and one or more of Ni, Fe, Co, Cr, Mn, Ti, Mo, Si and Al metals or oxides as an alloy or dispersed particles. A surface-treated steel sheet that has a system coating layer and has a light weight and excellent corrosion resistance and deep drawability. 3) C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.
05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less, sol.Al: 0.
1% or less, N: 0.004% or less, B: 0.0005 to 0.002%, Cu: 0.
2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.05%, and 2 ≦ 1000 × Sn × (2 × P + Cu +
Ni) ≤20, Ti: 0.005 to 0.1%, N
b: contains 0.002 to 0.05% of any one kind or two kinds,
A steel sheet whose balance consists of iron and inevitable impurities is pickled to remove scale and before annealing, or before pickling and cold rolling and before annealing, at least one surface of the steel sheet is electroplated or 8 to 18 P by electroless plating
Ni-P alloy plating containing 100% by weight is applied and diffusion heat treatment is performed at 500 to 880 ℃ in a non-oxidizing atmosphere.
A diffusion alloy region containing e-Ni-P as a main component is formed, and further electroplating or hot dip plating is performed on the diffusion alloy region.
Zn, Zn, Zn as matrix, Ni, Fe, Co, Cr, M
Excellent corrosion resistance and deep drawing with a thin weight, characterized by forming a zinc-based plating layer containing one or more of n, Ti, Mo, Si, Al metals or oxides as alloys or dispersed particles Of a surface-treated steel sheet having heat resistance. 4) C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.
05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less, sol.Al: 0.
1% or less, N: 0.004% or less, B: 0.0005 to 0.002%, Cu: 0.
2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.05%, and 2 ≦ 1000 × Sn × (2 × P + Cu +
Ni) ≤20, Ti: 0.005 to 0.1%, N
b: contains 0.002 to 0.05% of any one kind or two kinds,
A steel sheet whose balance consists of iron and inevitable impurities is pickled to remove scale and before annealing, or before pickling and cold rolling and before annealing, at least one surface of the steel sheet is electroplated or 8 to 18 P by electroless plating
%, W, Mo, Cr, Cu, or one or more of them in an amount of 15% by weight or less, Ni-P alloy plating is applied, and diffusion heat treatment is performed at 500 to 880 ° C in a non-oxidizing atmosphere. A diffusion alloy region containing Fe-Ni-P as a main component and containing one or more of W, Mo, Cr, and Cu is formed on the surface of the steel sheet substrate, and further electroplating or hot dip plating is applied to the diffusion alloy region. Zn plating or Zn as a matrix, Ni, Fe, Co, Cr, Mn, Ti,
Surface with excellent corrosion resistance and deep drawability, which is characterized by forming a zinc-based plating layer containing one or more of Mo, Si, Al metals or oxides as an alloy or dispersed particles Method for manufacturing treated steel sheet. 5) When hot-rolling the slab and preparing the above-mentioned steel sheet, it is hot pressed at Ar3 points or more to obtain the coiling temperature (CT; ° C).
610-2000 × Sn ≤ CT (° C) ≤ 710-2000 × Sn The steps of winding a hot-rolled steel sheet in the range and cold rolling at a reduction rate of 70 to 90% are included in claims 1 and 2. A method for producing a surface-treated steel sheet having excellent corrosion resistance and deep drawability as shown in the table below. 6) When heat treating a steel sheet in a non-oxidizing atmosphere, it is characterized by forming a diffusion alloy region containing Fe-Ni-P as the main component at the interface between the steel sheet substrate and the plating layer by heating in a continuous annealing furnace. A method for producing a surface-treated steel sheet having excellent corrosion resistance and deep drawability with a light weight.

[0007]

The present invention will be described in detail below. The steel sheet applied in the present invention is to secure sufficient corrosion resistance and workability based on IF steel by adding Sn as an element for further improving the corrosion resistance to the steel to which P, Cu and Ni are added. It was successful and is as follows. The reasons for limiting the steel components (all the components are% by weight in the following) as described above are as follows.

C: 0.002 to 0.01% The content of C should be as small as possible in order to maintain excellent mechanical properties. Therefore, as a range that does not impair the effects of the present invention,
The upper limit is limited to 0.01%, preferably 0.006%. Regarding the lower limit, in addition to the extremely low C, the workability does not improve so much.
Since it is necessary to add other elements, which causes a cost increase, it is 0.002%.

Si: 1% or less. Si contributes to the strengthening of the steel sheet as a solid solution strengthening element without deteriorating the press formability. However, if the content exceeds 1%, not only the amount of scale generated during heating in hot rolling becomes remarkable, but if it is added excessively, the deep drawability of the steel sheet deteriorates, and the chemical conversion treatability deteriorates. did.

Mn: 0.05 to 1% Since Mn is an element necessary to fix S contained inevitably and prevent red heat embrittlement, its lower limit was made 0.05%. Also, if the content exceeds 1%, the Rankford value is significantly deteriorated and it is also disadvantageous in terms of cost, so the upper limit was made 1%.

P: 0.02 to 0.1% P is an element that can strengthen steel at the lowest cost and also improves the corrosion resistance of the steel sheet itself. If the content of Fe exceeds 0.1% based on IF steel, the strength will eventually increase and segregation will easily occur at the grain boundaries, and the problem of secondary processing deterioration will become apparent. Therefore, the content was limited to 0.1% or less. ， On the other hand, to impart corrosion resistance,
It was necessary to add 0.02%, which was the lower limit.

S: 0.01% or less. If S content exceeds 0.01%, it deteriorates the ductility of the steel and adversely affects the corrosion resistance, so it was made 0.01% or less. It is preferably 0.007% or less.

Sol.Al: 0.1% or less. Al is deoxidized and
It is necessary to fix N, but if it is added in a large amount, the cost will rise, and since alumina inclusions will increase and the surface quality will deteriorate, it is made 0.1% or less, preferably 0.06% or less.

N: 0.004% or less. N is preferably as small as possible in order to obtain a high Rank Ford value, but its upper limit is 0.004% as a range that does not impair the effects of the present invention.
Below.

Cu: 0.2 to 0.5% Cu is an element that improves the corrosion resistance of the steel sheet itself when it is added together with P, and its effect is obtained at 0.2% or more. If it is added excessively, not only the deep drawability is deteriorated, but also surface defects during hot rolling or coexistence with Sn easily cause hot cracking during hot rolling, so the upper limit is made 0.5%.

Ni: 0.1 to 0.5% Ni is an element effective in reducing surface defects when Cu is added and further improving corrosion resistance. However, excessive addition causes deterioration of deep drawability and cost increase. Therefore, the lower limit is set to 0.1% and the upper limit is set to 0.5%, and B: 0.0005 to 0.002%.

B has the function of segregating to the grain boundaries and strengthening the grain boundaries. In particular, when P is added based on IF steel, the addition is essential to avoid the problem of secondary work embrittlement. If it is less than 0.0005%, its effect is small, and if it exceeds 0.002%, the recrystallization temperature rises and the Rankford value lowers, resulting in the drawbacks.

Ti: 0.005 to 0.1%. Ti has the effect of fixing C in steel and improving the Rankford value.
That is, if it is less than 0.005%, its effect is poor, while if it is added in a large amount, not only the cost increases, but also the cause of surface defects and the chemical conversion processability deteriorate, so the upper limit is made 0.1%.

Nb: 0.002 to 0.05%. Like Ti, Nb has the property of fixing C, and the combined addition with Ti further increases the Rankford value, that is, the effect is poor at less than 0.002%, and the addition of a large amount causes an increase in cost, so the upper limit is set. Is limited to 0.05%.

Sn: 0.002 to 0.05%, and 2 ≤ 1000
The amount of Sn is defined as × Sn × (2 × P + Cu + Ni) ≦ 20. As described above, Sn is an important element in the present invention, and its addition is essential to improve the corrosion resistance of the steel sheet. If the content exceeds 0.05%, not only the hot ductility decreases but also the ductility and deep drawability of the steel sheet decrease. Therefore, the upper limit was 0.05%, and in order to obtain the corrosion resistance improving effect of Sn, 0.00%
The lower limit was 2%. On the other hand, the Sn content is 2 ≦ 1000 × Sn × (2 × P
+ Cu + Ni) ≤20 and is limited by the relational expression.

Next, 2 ≦ 1000 × Sn × (2 × P + Cu + N
i) Describe the reason for the limitation of ≦ 20. This limitation was clarified by the following experiment. The composition of components below is% by weight. C: 0.002 to 0.01%, Si: 1% or less, Mn: 0.05 to 1%, P:
0.02 to 0.1%, S: 0.01% or less, sol.Al: 0.1% or less, N:
0.004% or less, B: 0.0005 to 0.002%, Cu: 0.2 to 0.5%, N
i: 0.1 to 0.5%, Sn: 0.002 to 0.05%, and there is a relationship that satisfies 2 ≤ 1000 x Sn x (2 x P + Cu + Ni) ≤ 20 between the above compositions, Ti: 0.005 to 0.1%, Nb: 0.002 to 0.05% of any one or two kinds, and the balance of at least one surface of the steel sheet consisting of iron and unavoidable impurities, Fe-N
The corrosion resistance of cold-rolled steel sheet having a diffusion alloy layer containing iP as a main component and containing one or more of W, Mo, Cr and Cu was investigated.

The corrosion resistance was evaluated by measuring the corrosion depth of the uncoated steel sheet after 60 days in a corrosive environment in which dry and wet cycles were combined with salt spray. As a parameter showing the relationship between the average corrosion depth and the composition of steel, 1000 × Sn × (2 × P + Cu +
Ni), the average corrosion depth of steel sheet and Rankford value
Figure 1 shows the relationship with (rm). As is clear from Figure 1,
It can be seen that the corrosion resistance and deep drawability strongly depend on the contents of Sn, P, Cu, and Ni.

According to FIG. 1, 1000 × Sn × (2 × P + Cu + Ni)
It can be seen that when the value is 2 or more, the corrosion resistance is good regardless of the annealing method. However, when it exceeds 20, the Rankford value deteriorates because the added amount of the element imparting corrosion resistance increases. Therefore, it becomes impossible to satisfy both corrosion resistance and deep drawability. Therefore, the Sn content is 2 ≤ 1000 × Sn ×
It is limited to the relational expression represented by (2 × P + Cu + Ni) ≦ 20.

As described above, since the contents of Sn, P, Cu, and Ni greatly affect the corrosion resistance regardless of the type of annealing, S
It was found that an appropriate and balanced combination of n, P, Cu, and Ni contents contributes to excellent corrosion resistance.

Although the steel composition as described above has sufficient corrosion resistance in the steel sheet itself, it is still insufficient for automobile steel sheets used in a severe environment. Therefore, in order to impart further corrosion resistance to the above steel sheet, in the present invention, a Fe-Ni-P diffusion alloy plating layer is formed on the above steel sheet. P
Ni-P alloy plating containing 8 to 18% by weight has a structure close to amorphous, and heat treatment of a steel sheet with such a plating layer results in a more uniform diffusion alloy layer than in the case of general crystalline plating film. Are formed in a short period of time. Such a diffusion layer protects the base steel from corrosion and makes the corrosion products of iron formed once the corrosion of the base steel begins to be quick and dense. As a result, it is possible to obtain excellent corrosion resistance that cannot be obtained by the conventional techniques.

When P is less than 8% by weight, the Ni-P alloy plating is crystalline and the P distribution is not uniform. For this reason, the composition of the diffusion alloy region formed when subjected to heat treatment is not uniform, and the contribution of the above-described rust generated underlayer to the denseness is not sufficient.
It is not possible to obtain excellent corrosion resistance. On the other hand, P is 18% by weight
If it exceeds the range, Ni-P alloy plating becomes brittle and its adhesion decreases. For this reason, plating peeling is likely to occur during heat treatment and the like. Therefore, the P content of the plating layer formed on the steel sheet according to the present invention was set to 8 to 18% by weight. The preferred range is 8 to 15% by weight, and the more preferred range is 10 to
13% by weight.

It is also possible to use Ni-P as a Ni-P alloy plating in which one or more of W, Mo, Cr, and Cu are compounded in the range of 15% by weight or less. Each of W, Mo, Cr, and Cu has an inhibitory role for steel corrosion, and at the same time, has a synergistic effect with Ni and P to further improve the denseness and stability of initial rust. The total content of W, Mo, Cr and Cu is preferably 15% by weight or less. Corrosion resistance improves as the total content of W, Mo, Cr, and Cu increases, but if the total content exceeds 15% by weight, its adhesion decreases and plating peeling easily occurs in the subsequent process. Therefore, the total content of W, Mo, Cr, and Cu was set to 15% by weight. In order to exert the W, Mo, Cr, Cu content effect, the lower limit is preferably 0.5% by weight or more.

The plating amount of this Ni-P alloy plating layer is not particularly specified, but is preferably in the range of 0.1 to 8 g / m ² . If it is less than 0.1 g / m ² , the effect of improving corrosion resistance is not sufficient, and if it exceeds 8 g / m ² , the workability of the plating layer deteriorates and peeling easily occurs, and the line speed must be slowed down to increase the plating amount. It is a disadvantage in terms of efficiency. Even if it is left as it is, the puncture resistance is good, but the effect of suppressing the generation of red rust from external coating flaws due to smashing stones is insufficient.

Therefore, in order to further impart corrosion resistance after coating to the above steel sheet, Zn or Zn is used as a matrix and Ni, Fe,
Plating containing one or more kinds of metals or oxides of Co, Cr, Mn, Ti, Mo, Si and Al as an alloy or dispersed particles is performed. All of these platings contribute to the corrosion resistance during the plating corrosion process due to the sacrificial anticorrosion effect of the plating, but even during the corrosion of the base, the synergistic effect of the components present in the Zn matrix and the diffusion layer components such as Ni and P This has the effect of stabilizing the rust and densifying the base iron. The amount of zinc-based plating applied is preferably 5 to 60 g / m ² . If the adhered amount is too small, good corrosion resistance cannot be obtained, and if the adhered amount is too large, the workability of the plating layer deteriorates and the cost increases. The most desirable coverage range is 5 to 45 g / m ² .

Next, the manufacturing conditions in the present invention will be described. Although the present invention has its effects regardless of the hot rolling conditions and the annealing conditions, the manufacturing method using continuous annealing with high productivity is the invention of claim 7. In the hot rolling process, the high-temperature slab directly sent from the continuous casting machine, the high-temperature slab obtained by heating, or the slab obtained by slab-rolling a steel ingot is subjected to Ar ₃ transformation of its composition. Hot rolling is carried out at a temperature above the point. Below the Ar ₃ transformation point, the Rankford value after annealing deteriorates, so the range was limited to this range. However, the application of hot rolling in the ferrite region does not impair the characteristics of the steel of the present invention under conditions such as sufficient hot rolling lubrication.

The coiling temperature for hot rolling is 610-2000.
× Sn ≤ CT (° C) ≤ 710 −2000 Wind at the temperature specified by Sn. Sn is known as an element that tends to segregate at grain boundaries due to its properties, and it is necessary to wind Sn at a temperature that depends on the amount of Sn added in order to prevent it from segregating significantly at grain boundaries. Figure 2
The relationship with the grain boundary segregation index was investigated using CT + 2000 × Sn as a parameter, and the grain boundary segregation index tends to increase as CT + 2000 × Sn increases.

Here, the grain boundary segregation index represents the ratio of Sn segregated at the grain boundaries to the amount of added Sn. When CT + 2000 × Sn is less than 610, the grain boundary segregation index is small and the grain boundary segregation is suppressed, but conversely the Rankford value is small. When the value exceeds 710, the Rankford value increases, but the grain boundary segregation index also increases. In any of the above cases, the characteristics of the steel sheet are inadequate, and
2000 × Sn ≤ CT (° C) ≤ 710 − It is important to wind in the temperature range specified by 2000 × Sn.

In cold rolling after coiling at the above hot rolling temperature and pickling, the Rankford value after annealing increases with an increase in the rolling reduction, but it is high when the rolling reduction is less than 70%. Since it is difficult to obtain the Rankford value, and its effect is small at a reduction rate of 90% or more, it was limited to this reduction range.

The Ni-P system plating process is carried out before annealing, but it may be carried out before cold rolling following pickling on the pickling line outlet side, or after pickling cold pressure plating. I don't mind if you go. In particular, when this plating is before cold rolling, it is advantageous because cleaning before plating and pickling as an activation treatment before plating are unnecessary.

Although various methods of forming the Ni-P alloy plating layer are conceivable, electroplating or electroless plating (chemical plating) is preferable in terms of simplicity and film quality to be obtained. Next, the steel sheet with the Ni-P alloy plating layer is heat-treated in a non-oxidizing atmosphere to form a diffusion alloy region containing Fe-Ni-P as the main component at the interface between the steel sheet substrate and the plating layer. The heat treatment for diffusion can be carried out in normal annealing equipment after cold rolling. A method using continuous annealing, which has a particularly high productivity, is desirable. As the continuous annealing described here, a general continuous annealing equipment for cold-rolled steel sheets and an annealing equipment as a pretreatment equipment for a hot dip coating line can be used. The maximum temperature reached at this time is 500 ° C to 880 ° C, preferably 800 ° C to 880 ° C. 50
Below 0 ° C, the diffusion layer between the NiP-based alloy plating layer and the steel surface is not sufficiently formed, and the formation of dense rust during the corrosion process is not sufficient, so the effect of improving corrosion resistance is small. In order to obtain a higher Rankford value, 800 ° C or higher is desirable, and the lower limit is preferably 820 ° C. On the other hand, if the temperature exceeds 880 ° C, pick-up of the plated metal on the roll in the heat treatment furnace is likely to occur, and as a result, surface scratches are likely to occur. 88 more
When annealed at a temperature above 0 ° C, roughening of the ferrite grains tends to cause rough skin after press forming. In addition, the holding time at this maximum ultimate temperature depends on the temperature, but is preferably 1 to 120 seconds. If it is too short, a sufficient diffusion region will not be formed, and the effect of improving corrosion resistance will not appear, and if it exceeds 120 seconds, the interface layer will become brittle due to excessive diffusion alloying, and the adhesion and workability of the plating layer will deteriorate. Further, during the heat treatment, an overaging treatment may be performed at a temperature of about 300 to 400 ° C for about several minutes. A suitable diffusion region formed by heat treatment has a depth of about 0.1 to 20 μm.

Further, it is preferable to use a direct-fired heating furnace to heat at a heating rate of 50 ° C./sec or more when performing heat treatment. When the Ni-P alloy plating layer is heat-treated, a part of it forms a diffusion alloy layer to form a steel plate / diffusion alloy region / Ni-P alloy plating layer, and all of them are diffusion alloy layers. In some cases, the present invention includes both of the above cases, although a layer may be formed to form a steel plate / diffusion alloy region.

After the heat treatment, temper rolling is performed under appropriate conditions if necessary. The steel sheet thus treated is further subjected to zinc-based electroplating or zinc-based hot dip plating in a zinc-based plating line.

As the zinc-based electroplating bath, a widely used sulfuric acid bath, chloride bath or the like can be used. Furthermore, when higher corrosion resistance is required, it is possible to further perform chromate treatment on the zinc-based plating layer and add the organic composite resin thereon. At this time, as the chromate treatment method, any of reaction type, electrolytic type, and coating type can be applied. Further, the chromate film may contain organic substances such as acrylic resin, oxide colloids such as silica and alumina, acids such as molybdic acid, salts, and other rustproofing components. The organic resin film formed on the chromate film can use an epoxy resin as the base resin, and further contains about 10 to 60% by weight of silica, chromate or other rust preventive additives. desirable. A cold-rolled steel sheet having both such corrosion resistance and deep drawability is a very useful steel sheet as a material for automobiles.

[0039]

EXAMPLES Specific examples of the present invention will be described below, but it goes without saying that the present invention is not limited to these examples. The evaluation of corrosion resistance and paintability is as follows.
In each of the examples, the prepared test materials were evaluated by the methods described below. (Evaluation methods / standards) (1) Corrosion resistance: A corrosion test was performed for 1 cycle per day in a corrosive environment in which salt water spray was combined with repeated dry and wet tests, and the corrosion depth after the test was measured and evaluated according to the following criteria.

○ Maximum erosion depth is less than 0.1 mm △ Maximum erosion depth is over 0.1 mm, less than 0.2 mm × Maximum erosion depth is over 0.2 mm (2) Paintability: Phosphate treated A steel knife coated with electrodeposition was scratched with a cutter knife to reach the substrate and exposed to the same corrosive environment as in (1) for 100 days.
The swelling of the coating from this scratch was observed and evaluated according to the following criteria.

○ Maximum blistering width on one side is 1 mm or less △ Maximum blistering width on one side is more than 1 mm and 3 mm or less × Maximum blistering width on one side is more than 3 mm (3) Workability: 180 ° bending test bend tip The damage condition of the plating film of the part was observed and evaluated according to the following criteria.

○ Degree of zero damage or generation of fine cracks △ Large cracks or partial peeling of plated pieces × Exfoliation of plating is observed in a wide range Example 1 A steel having the chemical composition shown in Table 1 is melted The slab was then hot-rolled under the conditions of a heating temperature of 1200 ° C, a finishing temperature of 900 ° C, and a coiling temperature of 650 ° C to form a 4.0 mm thick hot-rolled sheet.

Then, after pickling and cold rolling 0.8 mm, Ni-P plating with a P content of 12% by weight and an adhesion amount of 1 g / m ² was applied as an annealing method. Box annealing is 700 ℃,
Two types of continuous annealing were carried out at 850 ° C. Next, after 0.5% temper rolling, a specimen was taken and a tensile test was conducted. Furthermore, the zinc-based plating (No. I) shown in Table 6 was applied to investigate the corrosion resistance shown above. The results of the example are shown in the table.
Shown in 2. Table 2 shows that the steel of the present invention has a higher Rankford value than the comparative steel and has excellent corrosion resistance.

Example 2 With respect to the steels of the present invention (steel No .: 4,9,15,19) shown in Table 1,
Table 3 shows various hot-rolling temperatures, cold rolling rates, and Ni-P plating with a P content of 12% by weight and an adhesion of 1 g / m2.
It was manufactured under the conditions of annealing temperature, and the material and corrosion resistance of the steel sheet were investigated. The results are shown in Table 4. From Table 4, the steel sheet manufactured by the manufacturing method of the present invention has a Rank Ford value of 1.
Excellent corrosion resistance is exhibited at 6 or more.

Example 3 The steel of the present invention (steel number: 4) shown in Table 1 was melted to form a slab, which had a heating temperature of 1200 ° C., a finishing temperature of 900 ° C., and a winding temperature.
A hot rolled sheet with a thickness of 4.0 mm was finished by hot rolling under the condition of 650 ° C.

Next, after pickling and cold rolling to 0.8 mm, Ni-P plating was performed within the range shown in Table 5 to 800 mm.
After continuous annealing in the temperature range of up to 880 ° C, 0.5% temper rolling was performed and the zinc-based plating shown in Table 6 was applied to prepare test pieces. The results are shown in Tables 7-9. The steel sheets of the present invention all exhibit excellent corrosion resistance, paintability, and workability.

Example 4 The steel of the present invention (steel No. 4) shown in Table 1 was melted and made into a slab. The heating temperature was 1200 ° C, the finishing temperature was 900 ° C, and the winding temperature was
A hot rolled sheet with a thickness of 4.0 mm was finished by hot rolling under the condition of 650 ° C.

Next, after pickling, Ni-P plating (No .: A, B, C, M, N, O, T) was performed in the range shown in Table 5, and then cold rolling was performed. A 0.8 mm piece was continuously annealed in the temperature range of 800 to 880 ° C and temper-rolled at 0.5% to prepare a test piece. The results are shown in Table 10. The steel sheets of the present invention all exhibit excellent corrosion resistance, paintability, and workability.

[0049]

[Effects of the Invention] IF steel (steel without interstitial solid solution element) is used as a steel sheet, and as an element for improving corrosion resistance,
Ni-P alloy plating layer was added to at least one surface of the deep-drawing steel sheet with excellent corrosion resistance, in which Sn was added, with particular attention paid to Sn as an element that adds elements of P, Cu, and Ni Alternatively, by further forming a Ni-P alloy plating layer containing one or more of W, Mo, Cr, and Cu and performing heat treatment in a non-oxidizing atmosphere, the Fe- After forming a diffusion alloy region containing Ni-P as the main component, Zn plating or Zn is used as a matrix, and Ni, Fe, C
By forming a zinc-based plating layer containing one or more of metals or oxides of o, Cr, Mn, Ti, Mo, Si, Al as an alloy or dispersed particles, very high corrosion resistance with a thin weight is achieved. You can secure enough.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

[0059]

[Table 10]

[Brief description of drawings]

[Figure 1] Diagram showing the relationship between 1000 × Sn × (2 × P + Cu + Ni) and the average corrosion depth of steel sheet and Rankford value (rm)

FIG. 2 is a diagram showing the relationship between CT + 2000 × Sn and the grain boundary segregation index (%) and Rankford value (rm).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical indication C25D 15/02 Q // C23C 18/34 (72) Inventor Masaya Morita 1-chome, Marunouchi, Chiyoda-ku, Tokyo No. 1-2 Nihon Steel Pipe Co., Ltd. (72) Inventor Toyofumi Watanabe 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Steel Pipe Co., Ltd. (72) Inventor, Yumitsu Shiobara 1-1-Chome, Marunouchi, Chiyoda-ku, Tokyo No. 2 Nihon Steel Pipe Co., Ltd.

Claims (6)

[Claims] 1. C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less,
sol.Al: 0.1% or less, N: 0.004% or less, B: 0.0005 to 0.00
2%, Cu: 0.2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.
05%, and 2 ≤ 1000 × Sn × (2 × P
+ Cu + Ni) ≦ 20, Ti: 0.005〜
A diffusion alloy region containing Fe-Ni-P as the main component on at least one surface of a steel sheet containing 0.1%, Nb: 0.002 to 0.05%, and the balance consisting of iron and inevitable impurities. With a Zn plating layer or
With a thin basis weight having a zinc-based plating layer containing Zn as a matrix and containing one or more metals or oxides of Ni, Fe, Co, Cr, Mn, Ti, Mo, Si and Al as alloys or dispersed particles Surface-treated steel sheet with excellent corrosion resistance and deep drawability. 2. C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less,
sol.Al: 0.1% or less, N: 0.004% or less, B: 0.0005 to 0.00
2%, Cu: 0.2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.
05%, and 2 ≤ 1000 × Sn × (2 × P
+ Cu + Ni) ≦ 20, Ti: 0.005〜
0.1%, Nb: 0.002-0.05% on at least one surface,
Fe-Ni-P is the main component, and there is a diffusion alloy layer region containing one or more of W, Mo, Cr, and Cu.
The plating layer or Zn is used as a matrix, and Ni, Fe, Co, Cr,
A surface-treated steel sheet having a thin coating weight, excellent corrosion resistance, and deep drawability, having a zinc-based plating layer containing one or more of metals or oxides of Mn, Ti, Mo, Si, and Al as an alloy or dispersed particles. 3. C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less,
sol.Al: 0.1% or less, N: 0.004% or less, B: 0.0005 to 0.00
2%, Cu: 0.2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.
05%, and 2 ≤ 1000 × Sn × (2 × P
+ Cu + Ni) ≦ 20, Ti: 0.005〜
Steel sheets containing 0.1%, Nb: 0.002 to 0.05%, one or two, and the balance iron and unavoidable impurity components are pickled to remove scale and before annealing or cold pickling. After rolling and before annealing, P is applied to at least one surface of the steel sheet by electroplating or electroless plating.
Ni-P alloy plating containing ~ 18 wt% is applied and diffusion heat treatment is performed at 500-880 ° C in a non-oxidizing atmosphere to form a diffusion alloy region mainly composed of Fe-Ni-P on the surface of the steel sheet substrate. ，
Furthermore, by electroplating or hot dip plating, Zn plating or Zn as a matrix, Ni, Fe, C
Excellent in thin coating, characterized by forming a zinc-based plating layer containing one or more metals or oxides of o, Cr, Mn, Ti, Mo, Si, Al as alloys or dispersed particles. A method for producing a surface-treated steel sheet having corrosion resistance and deep drawability. 4. C: 0.002 to 0.01% by weight%, Si: 1% or less, Mn: 0.05 to 1%, P: 0.02 to 0.1%, S: 0.01% or less,
sol.Al: 0.1% or less, N: 0.004% or less, B: 0.0005 to 0.00
2%, Cu: 0.2 to 0.5%, Ni: 0.1 to 0.5%, Sn: 0.002 to 0.
05%, and 2 ≤ 1000 × Sn × (2 × P
+ Cu + Ni) ≦ 20, Ti: 0.005〜
Steel sheets containing 0.1%, Nb: 0.002 to 0.05%, one or two, and the balance iron and unavoidable impurity components are pickled to remove scale and before annealing or cold pickling. After rolling and before annealing, P is applied to at least one surface of the steel sheet by electroplating or electroless plating.
~ 18 wt%, Ni, P alloy plating containing one or more of W, Mo, Cr, Cu in the range of 15 wt% or less, and diffusion heat treatment at 500 ~ 880 ℃ in non-oxidizing atmosphere. Then, a diffusion alloy region containing Fe-Ni-P as a main component and containing one or more of W, Mo, Cr, and Cu is formed on the surface of the steel sheet substrate, and further electroplating or hot dipping By
Zn plating or Zn as a matrix, Ni, Fe, Co, Cr,
Excellent corrosion resistance and deep drawing with a thin weight, characterized by forming a zinc-based plating layer containing one or more metals or oxides of Mn, Ti, Mo, Si, Al as alloys or dispersed particles. Of a surface-treated steel sheet having heat resistance. 5. When preparing a steel sheet according to claim 3 or 4 by hot rolling a slab, hot pressing is performed at ₃ or more points of Ar, and the coiling temperature (CT; ° C) is 610-2000 x Sn ≤ CT (° C) ≤710
Winding process of hot rolled steel sheet in the range of −2000 × Sn, 70 ~ 90%
5. The method for producing a surface-treated steel sheet having excellent corrosion resistance and deep drawability according to the thinning according to claim 3, which has a step of cold rolling at a reduction ratio of. 6. Forming a diffusion alloy region containing Fe-Ni-P as a main component at the interface between the steel sheet substrate and the plating layer by heating in a continuous annealing furnace when heat treating the steel sheet in a non-oxidizing atmosphere. A method for producing a surface-treated steel sheet having excellent corrosion resistance and deep drawability according to claim 3 or 4, characterized by: