JP2007092134A - Cold-rolled steel sheet excellent in chemical conversion treatment, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-carbon cold-rolled steel sheet which is excellent in workability, and can be manufactured without using a multistage annealing technique that needs a long period of time. <P>SOLUTION: The cold-rolled steel sheet has Fe oxide controlled to 10 mg/m<SP>2</SP>or less and Mn oxide in an amount of 1.0 or more by a mass ratio to the total oxides amount of Al, Ti and Si, on the surface of the steel sheet. The method for manufacturing the cold-rolled steel sheet includes controlling an atmosphere gas in the step of batch annealing carried out after having cold-rolled a hot-rolled steel plate , so as to contain 80% or higher hydrogen, have a dew point controlled to 30°C or lower when the coldest point of a coil in an annealing furnace is 200°C or higher, and further have a dew point controlled to -20°C or lower when the coldest point of the coil in the annealing furnace is 600°C or higher. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cold-rolled steel sheet excellent in chemical conversion treatment and a method for producing the same.

  Cold-rolled steel sheets are mainly used after being processed, assembled and painted as parts for automobiles and electrical equipment. Therefore, moldability and chemical conversion treatment are essential material characteristics.

  Accordingly, in order to achieve high formability, the cold-rolled steel sheet is usually annealed after cold rolling the hot-rolled steel sheet to a predetermined thickness. This annealing treatment is roughly classified into a batch annealing method and a continuous annealing method, and the batch annealing method has a feature that it can be implemented with relatively small equipment, that is, with a small capital investment.

  The history of batch annealing is old, and traditionally HNX and AN gas were the mainstream as atmospheric gases. However, in recent years, as described in Non-Patent Document 1, atmospheric gases having a high hydrogen concentration are generally used for efficiency improvement, temperature uniformity, surface quality improvement, energy saving, decarburization / nitriding prevention, and the like. It's getting on.

  Surface characteristic control is given as an important technical issue for steel sheets when annealed in a hydrogen atmosphere, and research and technical disclosure have been made so far. In particular, several methods are known for controlling the surface quality of the appearance called temper color, which is dominated by a thick oxide film of several hundreds of liters or more. On the other hand, compared to the thick oxide film of temper color, no effective solution has been shown for chemical conversion processability affected by the thin oxide film, and steel sheets annealed in a hydrogen atmosphere have chemical conversion processability. The current situation is generally not excellent.

  On the other hand, Patent Document 1 discloses a method of annealing ultra-low carbon steel in an atmosphere of almost 100% hydrogen. However, Patent Document 1 is exclusively related to improvement of mechanical test value characteristics, does not describe any dew point of the atmosphere, and does not give any suggestion regarding improvement of chemical conversion treatment.

  Patent Document 2 discloses a method for producing a cold-rolled steel sheet excellent in chemical conversion treatment property by batch annealing with a mixed gas having a hydrogen concentration of 80% or more and an oxygen concentration of 100 ppm or less. However, in Patent Document 2, although a certain effect can be obtained with respect to the chemical conversion processability improvement compared with the prior art annealing using a mixed gas atmosphere with hydrogen having a high nitrogen ratio, it is effective for improving the moldability. In the case of high-temperature annealing or ultra-low carbon steel, the chemical conversion processability is significantly deteriorated.

  Patent Document 3 discloses a method of preventing the generation of an oxide film, so-called temper color, by removing oxygen and moisture in the furnace gas, that is, by lowering the dew point. As an example, the temper color is improved by setting the dew point at the end of annealing to -60 ° C. However, in Patent Document 3, the chemical conversion processability is significantly deteriorated in the case of high-temperature annealing effective for improving formability or in the case of extremely low carbon steel.

  Patent Document 4 discloses a method of box annealing ultra low carbon steel in a temperature range of 730 to 850 ° C. in a 100% hydrogen atmosphere having a dew point of −20 ° C. or less. However, the method described in Patent Document 4 significantly deteriorates the chemical conversion processability.

  Patent Document 5 discloses a method for lowering the dew point and oxygen concentration of the atmosphere by substitution after evacuation to prevent temper color.

  Patent Document 6 discloses a method of installing a deoxidizing material in a furnace to prevent temper color.

  Patent Document 7 discloses a method of setting the dew point to −40 to 0 ° C. to prevent an oxide film, so-called temper color. In general, in batch annealing, the dew point once rises due to deposits on the steel sheet surface at the initial stage of heating, and then decreases. In Patent Document 7, the dew point at the initial stage of heating is reduced to 0 ° C. or less to prevent the formation of an oxide film, but the dew point at the end of annealing is not described. Moreover, the chemical conversion processability is not considered.

  Patent Document 8 discloses a method of annealing at a dew point of 20 ° C. using 20% hydrogen and 80% nitrogen gas as an atmospheric gas. The technique of Patent Document 8 is a method of decarburizing a hot-rolled steel sheet with an open coil, and the technical idea is completely different from the present invention. In addition, there is no description of atmospheric gas mainly composed of hydrogen, and no consideration is given to chemical conversion treatment.

To summarize the above, in the prior art, there are problems of temper color and chemical conversion as main technical problems of batch annealing. The former, that is, the temper color problem, has been improved by reducing the dew point, that is, the water concentration or the oxygen concentration, but the latter chemical conversion treatment problem is not considered at all, or It was not enough. Therefore, when annealing is performed in an atmosphere mainly composed of hydrogen gas, the efficiency and temperature uniformity are excellent, but there is a problem that the chemical conversion property is inevitably deteriorated.
Japanese Unexamined Patent Publication No. 4-168228 JP 7-97616 A JP 2000-104123 A JP-A-6-172868 JP-A-5-59456 JP 2000-45038 A JP-A-8-27523 JP 2001-234250 A NKK Technical Review No. 145 (1994), 47

  As described above, when annealing is performed in an atmosphere mainly composed of hydrogen gas, the efficiency and temperature uniformity are excellent, but there is a problem that the chemical conversion processability is deteriorated.

  An object of this invention is to provide the cold-rolled steel plate excellent in chemical conversion property, and its manufacturing method, using the batch annealing method by the atmosphere mainly of hydrogen gas in view of said situation.

The inventors of the present invention have intensively studied to clarify the cause of the chemical conversion treatment failure and the surface state excellent in chemical conversion treatment when the cold-rolled steel sheet is batch-annealed in an atmosphere mainly composed of hydrogen gas. As a result, the following knowledge was obtained.
When batch annealing is performed in an atmosphere mainly composed of hydrogen gas, the reducibility of the gas is very high, so the most easily oxidized Al, Ti, and Si among the elements contained in the steel sheet are concentrated as oxides, resulting in chemical conversion treatment. I found for the first time that it is deteriorating. And since these oxides were chemically stable with respect to an acid, it thought that the chemical reaction of chemical conversion treatment was prevented and chemical conversion treatment property was deteriorated. Therefore, as a result of further detailed research on the surface state of the steel sheet for improving chemical conversion, the ratio of the sum of the Mn oxide amount on the steel sheet surface and each of the oxide amounts of Al, Ti, Si was increased to 1.0 or more by mass ratio. By controlling, it discovered that the chemical conversion property of a cold-rolled steel plate was remarkably effective.

  In addition, when producing a cold-rolled steel sheet having excellent chemical conversion properties, the dew point is controlled when the coil coldest point is 200 ° C or higher, and the coil coldest point in the annealing furnace is 600 ° C or higher. It was also found that it is important to appropriately control the temperature in a higher temperature range than the prior art.

  Furthermore, the present inventors have found that the formability is improved by setting the chemical components and annealing temperature of steel to appropriate values, thereby completing the present invention.

The present invention has been made based on the above findings, and the gist thereof is as follows.
[1] The Fe oxide amount on the steel sheet surface is 10 mg / m ² or less, and the ratio of the Mn oxide amount to the sum of the oxide amounts of Al, Ti, and Si is 1.0 or more by mass ratio. Cold-rolled steel sheet with excellent chemical conversion.
[2] In the above [1], in mass%, C: 0.0030% or less, Si: 0.1% or less, Mn: 0.2% or less, P: 0.02% or less, S: 0.02% or less, Sol.Al: 0.01 ~ 0.1%, N: 0.0040% or less, B: 0 ~ 0.002%, Ti: 0 ~ 0.1%, Nb: 0 ~ 0.05% and Ti / 48 + Nb / 93> 2 (C / 12 + N / 14) A cold-rolled steel sheet excellent in chemical conversion treatment, characterized in that it is contained so as to satisfy the above condition, and the balance is composed of Fe and inevitable impurities.
[3] A cold-rolled steel sheet excellent in chemical conversion property, characterized in that in [1] or [2], the structure is a ferrite single phase and the average crystal grain size is 15 to 20 μm.
[4] When the hot-rolled steel sheet is subjected to batch annealing after cold rolling, the hydrogen concentration of the atmospheric gas is 80% or more,
The dew point of the atmospheric gas when the coil coldest point in the annealing furnace is 200 ° C or higher is set to 30 ° C or lower, and the dew point of the atmospheric gas when the coil coldest point in the annealing furnace is 600 ° C or higher is set to -20 ° C or higher. The manufacturing method of the cold-rolled steel plate excellent in the chemical conversion processability characterized by the above-mentioned.
[5] In the above [4], as the hot-rolled steel sheet, in mass%, C: 0.0030% or less, Si: 0.1% or less, Mn: 0.2% or less, P: 0.02% or less, S: 0.02% or less , Sol.Al: 0.01 to 0.1%, N: 0.0040% or less, B: 0 to 0.002%, Ti: 0 to 0.1%, Nb: 0 to 0.05% and Ti / 48 + Nb / 93> A method for producing a cold-rolled steel sheet excellent in chemical conversion property, characterized by using a hot-rolled steel sheet containing 2 (C / 12 + N / 14) and the balance being Fe and inevitable impurities.
[6] The method for producing a cold-rolled steel sheet having excellent chemical conversion property, wherein the temperature at the coldest point of the coil in batch annealing is 700 ° C. or higher in [4] or [5].

  In the present specification, “%” indicating the components of steel is all “% by mass”, and it means that the case where the lower limit of the chemical component is 0 is not included.

  In addition, the coil coldest point in the annealing furnace is the position where the temperature of the product coil is lowest during the annealing operation, but in the normal annealing operation, the coldest point is located between the lowermost coil and the hearth. Since it is known that the temperature is around ½ of the circumference and the circumference, the temperature measured at the position can be used as the coldest spot temperature.

  According to the present invention, a cold-rolled steel sheet having excellent chemical conversion properties and further formability can be obtained. And in this invention, the said cold-rolled steel plate can be manufactured with a highly efficient and uniform material. Moreover, since the cold-rolled steel sheet of the present invention is excellent in energy efficiency in the annealing process at the time of production, it is optimal as a steel sheet for automobiles from the viewpoint of low environmental load.

  The invention will be described in detail below. In the present invention, the cold-rolled steel sheet refers to a steel sheet that has been annealed after cold rolling.

First, an important requirement of the present invention, the amount of Fe oxide on the steel sheet surface is 10 mg / m ² or less, and the ratio of the Mn oxide amount to the sum of the respective oxide amounts of Al, Ti, and Si will be described in terms of a mass ratio of 1.0 or more. .

In the annealing operation of the steel sheet, when Fe becomes an oxide on the surface of the steel sheet, not only the appearance is deteriorated but also the chemical conversion property is deteriorated. At this time, when the amount of Fe oxide exceeds 10 mg / m ² , the adverse effect becomes significant. Therefore, the amount of Fe oxide must be 10 mg / m ² or less. For this reason, in the annealing operation, the atmosphere and temperature conditions under which Fe is reduced are selected. However, even if annealing is performed in a reducing atmosphere of Fe, elements such as Al, Ti, Si, and Mn that are more easily oxidized than Fe are selectively oxidized and become oxides on the surface of the steel sheet. At this time, if the amount of Mn oxide is large, the chemical conversion processability is improved, and if the amount of oxide of Al, Ti, Si is large, it is deteriorated. FIG. 1 is a diagram showing the relationship between the amount of Mn oxide on the surface, the sum of the amounts of oxides of surface Al, Ti, and Si and chemical conversion properties. In addition, in FIG. 1, the used test material is the cold-rolled steel plate batch-annealed in various atmospheres, and the chemical conversion treatment performed the spray type zinc phosphate process using the commercially available chemical | medical solution. And with respect to the obtained test material after the chemical conversion treatment, the density of the chemical conversion crystal grains is visually observed from an electron microscope image, and × (poor), Δ (a level causing no practical problem), ○ (excellent) The chemical conversion processability was determined in three stages. FIG. 1 clearly shows that the chemical conversion treatment property is good when the ratio of the Mn oxide amount to the sum of the Al, Ti, and Si oxide amounts is 1.0 or more. Therefore, the ratio of the Mn oxide amount on the steel sheet surface to the sum of the respective oxide amounts of Al, Ti, and Si is set to 1.0 or more in terms of mass ratio. In addition, although the steel plate shown by (triangle | delta) in FIG. 1 has a chemical conversion property in a practicable level, it was a little inferior in the uniformity of the chemical conversion crystal compared with the other invention example. Therefore, in order to further improve the chemical conversion property, the ratio of the Mn oxide amount to the sum of the respective oxide amounts of Al, Ti, and Si is desirably 1.5 or more in terms of mass ratio.

  Next, the reasons for limiting the chemical composition and structure of steel will be described.

C: 0.0030% or less
C is contained as an impurity in the steel sheet. When C exceeds 0.0030%, the elongation and the r value are remarkably lowered. Therefore, C needs to be 0.0030% or less.

Si: 0.1% or less
Si is contained as an impurity in the steel sheet. If Si exceeds 0.1%, the elongation decreases. Therefore, Si needs to be 0.1% or less.

Mn: 0.2% or less
Mn is contained as an impurity in the steel sheet. When Mn exceeds 0.2%, the elongation and the r value are remarkably lowered. Therefore, Mn needs to be 0.2% or less.

P: 0.02% or less
P is contained as an impurity in the steel sheet. When P exceeds 0.02%, the elongation is significantly reduced. Therefore, P needs to be 0.02% or less.

S: 0.02% or less
S is contained as an impurity in the steel sheet. When S exceeds 0.02%, the elongation is significantly reduced. Therefore, S needs to be 0.02% or less.

Sol.Al:0.01-0.1%
Al is added for the purpose of deoxidation. If it is less than 0.01%, the effect is not sufficient. On the other hand, if it exceeds 0.1%, the elongation is deteriorated. Therefore, Sol.Al needs to be 0.01% or more and 0.1% or less.

N: 0.0040% or less
N is contained as an impurity in the steel sheet. When N exceeds 0.0040%, the elongation is significantly reduced. Therefore, N needs to be 0.0040% or less.

B: 0 to 0.002% or less
B is an element that improves the resistance to secondary work embrittlement, and may be contained if necessary. On the other hand, if it exceeds 0.002%, the elongation and the deterioration of the r value become remarkable. Therefore, when it contains, it is necessary to make it 0.002% or less.

Ti: 0-0.1%, Nb: 0-0.05% and Ti / 48 + Nb / 93> 2 (C / 12 + N / 14)
Ti and Nb precipitate C and N as compounds and remove harmful solid solution C and N, thereby improving elongation and r value. Therefore, Ti and Nb may be contained if necessary. In order to exert a sufficient effect, it is necessary that the sum of Ti and Nb is more than twice the sum of C and N by atomic ratio. That is, it is necessary that Ti / 48 + Nb / 93> 2 (C / 12 + N / 14). On the other hand, if Ti exceeds 0.1%, not only the above effect is saturated, but also the frequency of occurrence of surface defects increases, so Ti needs to be 0.1% or less. Further, if Nb exceeds 0.05%, not only the above effect is saturated, but also the elongation decreases due to excessively dissolved Nb, so Nb needs to be 0.05% or less.

  The remainder other than the above consists of Fe and inevitable impurities. As an inevitable impurity, in a range not deteriorating the chemical conversion properties, for example, Cu: 0.1% or less, Ni: 0.1% or less, Sn: 0.01% or less, Mo: 0.01% or less, Cr: 0.1% or less, Sb: 0.01 % Or less, O: 0.003% or less, Zr: 0.01% or less.

Next, the structure of the cold-rolled steel sheet excellent in chemical conversion property of the present invention will be described.
It is preferable that the structure is a ferrite single phase and the average crystal grain size is 15 to 20 μm.
In order to achieve good elongation and r value, the structure is preferably a ferrite single phase. Furthermore, when the average crystal grain size is less than 15 μm, the elongation and the r value may deteriorate. On the other hand, when the average crystal grain size exceeds 20 μm, rough press-formed surface defects may occur when press molding. Therefore, the average crystal grain size of ferrite is preferably 15 to 20 μm. In addition, the average crystal grain size in the present invention refers to a value measured by a cutting method defined in JISG0552.

Next, the manufacturing method of the cold-rolled steel plate excellent in the chemical conversion property of this invention is demonstrated.
Until the hot rolling process, it is manufactured by a conventional method. Casting may be a continuous casting method or a mold casting method. In the case of continuous casting, it may be rolled as it is, or it may be cooled and reheated for rolling. In the case of reheating, the extraction temperature is preferably 1100 to 1200 ° C. in order to improve the elongation and the r value. In addition, it does not specifically limit about the chemical component of a hot-rolled steel plate (steel). However, in the present invention, the amount of Fe oxide on the steel sheet surface is 10 mg / m ² or less, and the ratio of the amount of Mn oxide to the sum of the amounts of oxides of Al, Ti, Si may be 1.0 or more in terms of mass ratio. For this reason, as described later, the manufacturing conditions are defined with a focus on the atmosphere and dew point during annealing. From this point, in order to obtain a steel sheet with even better chemical conversion treatment, the chemistry of Mn: 0.2% or less, Sol. Al: 0.01 to 0.1%, Ti: 0 to 0.1%, Si: 0.1% or less It is preferable to use a hot-rolled steel sheet (steel) having a composition.

  After hot rolling, cold rolling is performed. Further, pickling may be performed before cold rolling. In order to improve the r value, the rolling rate of cold rolling is desirably 75% or more.

  Annealing is performed after cold rolling. Electrolytic cleaning may be performed before annealing. Annealing is performed by a batch annealing method. Tight coil annealing or open coil annealing does not change the effect, but tight coil annealing is desirable from the cost standpoint. The batch annealing may be either a bell-type annealing furnace or a furnace that continuously anneals in a coil shape, and is not limited. The so-called continuous annealing method in which the coil is unwound and annealed in a strip shape is out of the scope of the present invention because the behavior of oxide formation on the steel sheet surface during annealing is completely different from that of batch annealing.

Atmosphere in batch annealing: hydrogen concentration is 80% or more The atmosphere in batch annealing is a very important requirement in order to improve the efficiency of annealing work and the uniformity of product characteristics. When the hydrogen concentration is less than 80%, the thermal conductivity of the atmospheric gas and the steel sheet is remarkably lowered, the heating and cooling are prolonged, and the work efficiency is remarkably deteriorated. Further, the infiltration of the atmospheric gas into the gap between the coils wound in the coil shape becomes insufficient, and the uniformity of the surface characteristics and mechanical characteristics in the coil width direction is remarkably deteriorated. Therefore, the atmosphere in batch annealing is set to a hydrogen concentration of 80% or more. The balance may be anything as long as it is an inert gas or a reducing gas, but nitrogen gas is desirable in consideration of cost.

When the coil coldest point in the annealing furnace is 200 ° C or higher, the dew point of the atmospheric gas is 30 ° C or lower. The dew point is an important requirement for the amount of Fe oxide to be 10 mg / m ² or lower. It is also important to obtain a good material. That is, when the dew point of the atmospheric gas exceeds 30 ° C. during annealing, Fe is oxidized and becomes an oxide, so that the chemical conversion property is deteriorated. The reason why the coldest spot of the coil is defined as 200 ° C. or more is that when the coldest spot of the coil is less than 200 ° C., a redox reaction on the steel sheet does not substantially occur. Further, when the dew point of the atmosphere gas in the annealing furnace exceeds 30 ° C. particularly in a high temperature range, decarburization occurs, mechanical characteristics become uneven, crystal grains become coarse, and rough skin occurs after molding. Therefore, the dew point of the atmospheric gas when the coil coldest point in the annealing furnace is 200 ° C. or higher needs to be 30 ° C. or lower. The atmospheric gas is continuously replaced by supplying a gas whose composition and dew point are controlled, and the dew point of the atmospheric gas is measured by the waste gas at this time.

When the coil coldest point in the annealing furnace is 600 ° C or higher, the dew point of the atmospheric gas is -20 ° C or higher.
The regulation of dew point at 600 ° C or higher is the most important for producing steel sheets with good chemical conversion properties by setting the ratio of the amount of Mn oxide to the sum of the amounts of oxides of Al, Ti, and Si to 1.0 or more by mass ratio. It is a requirement.
When annealing is performed in a highly reducing atmosphere gas, Fe and Mn in steel are easily reduced, while Al, Ti, and Si that are easily oxidized with elements in steel are easily oxidized. Since Al, Ti, and Si oxides are chemically stable to acids, the oxides on the steel sheet surface hinder the chemical reaction. Since this selective oxidation is remarkable in a high temperature range where Fe oxide is likely to be reduced, it is necessary to control the atmosphere at a coil coldest point of 600 ° C. or higher. If the dew point is less than -20 ° C, Fe and Mn are reduced, and only Al, Ti, and Si in the steel, which are harmful to the chemical conversion treatment, are selectively oxidized, and the chemical conversion treatment is extremely deteriorated. Therefore, the dew point of the atmospheric gas when the coil coldest point is 600 ° C. or higher must be −20 ° C. or higher. Furthermore, in order to further enhance this effect and improve the chemical conversion treatment property, it is desirable that the temperature is −10 ° C. or higher.

As described above, when batch annealing is performed after cold rolling of a hot-rolled steel sheet, the hydrogen concentration of the atmosphere gas is 80% or more, and the dew point of the atmosphere gas when the coil coldest point in the annealing furnace is 200 ° C. or more is 30. ℃ or less,
Furthermore, by setting the dew point of the atmospheric gas at the coil coldest point in the annealing furnace to 600 ° C. or more to -20 ° C. or more, the amount of Fe oxide on the steel sheet surface is 10 mg / m ² or less, and the amount of Mn oxide is A cold-rolled steel sheet excellent in chemical conversion treatment with a ratio by mass ratio of 1.0, or more, to the sum of the amounts of oxides of Al, Ti, and Si is obtained.

If the ultimate temperature at the coil coldest point is 700 ° C. or higher and the ultimate temperature at the coil coldest point is less than 700 ° C., the elongation and the r value may decrease. Therefore, in order to make the moldability particularly excellent, in addition to the above manufacturing conditions, the ultimate temperature of the coil coldest point is preferably 700 ° C. or higher.

  In the present invention, skin pass rolling may be further performed for adjusting the shape and surface roughness. Moreover, since the cold-rolled steel sheet of the present invention has good electroplating properties, it may be used as various plating original sheets.

A slab having the chemical composition and composition shown in Table 1 was melted, reheated to 1150 ° C., and hot-rolled to a plate pressure of 3.6 mm to obtain a hot-rolled sheet. Next, after removing the oxide scale by hydrochloric acid pickling on the obtained hot rolled sheet, cold rolling to 0.7 mm, electrolytic cleaning, and batch annealing in various gas atmospheres shown in Table 2 were performed. It was. In this batch annealing, the time from the start of heating to reaching the maximum temperature was about 24 hours. The cooling time until the furnace was opened was about 24 hours. FIG. 2 shows a history example of the temperature and dew point of the coil coldest point in the annealing process, together with an example of the present invention and a comparative example. As shown in FIG. 2, at the beginning of heating, the dew point was lowered due to the steel sheet surface deposits of batch annealing in both the inventive examples and the comparative examples. In the comparative example, the dew point decreased with the passage of time, and reached -40 ° C or lower at the end. On the other hand, in the example of the present invention, after the dew point decreased to the target value, the dew point was controlled before and after reaching the maximum temperature, and was set to a substantially constant value (0 ° C.). The dew point was controlled by bubbling atmospheric gas into water with controlled temperature and mixing a certain amount of water vapor.
After batch annealing, skin pass rolling was further performed at an elongation rate of 0.6%.
With respect to the cold-rolled steel sheet obtained as described above, the surface oxide amount and structure were analyzed, and chemical conversion property and mechanical characteristics were evaluated. Table 2 shows the results of analysis of surface oxide amount and structure, chemical conversion properties, and mechanical characteristics, together with manufacturing conditions.

  The amount of oxide on the surface of the steel plate was chemically quantitatively analyzed for Mn oxide by eluting only the acid-soluble oxide film with hydrochloric acid to which an inhibitor was added. Al, Ti, and Si oxides use the oxide layer formed on the ground iron (metal Fe) as the surface (layer), and after mechanically separating the surface layer, the metal Fe and acid are concentrated with concentrated sulfuric acid. The soluble oxide was dissolved, and the amounts of Al, Ti and Si in the dissolved residue were quantitatively analyzed.

  The structure (average crystal grain size) was measured by a cutting method (JISG0552) in the rolling direction and the plate thickness direction from an optical micrograph.

  The chemical conversion treatment is performed using a commercially available chemical solution, and a spray-type zinc phosphate treatment is performed. The density of the chemical conversion crystal grains is visually observed from an electron microscopic image, x (poor), Δ (a level that causes no problem in practice), ○ Judgment was made in three stages (excellent).

  For mechanical properties, JIS No. 5 test piece (JISZ2201) was taken in parallel with the rolling direction and tested according to JISZ2241. The r value was based on JISZ2254 and the average r value was measured. The target value of the mechanical characteristic value is an elongation of 50% or more and an average r value of 2.0 or more.

  As is clear from Table 2, the present invention example (reference symbols A to E, G, and M to S) has a mass ratio of 1.0 or more by mass ratio of the Mn oxide amount on the steel sheet surface to the sum of the respective oxide amounts of Al, Ti, and Si. ) Is excellent in chemical conversion treatment. The example of the present invention with the symbol I is also at a level that causes no problem in practice. In addition, because of the atmosphere mainly composed of hydrogen gas, the efficiency in consideration of temperature uniformity, heating and cooling time was also good.

  However, although the examples of the present invention with the symbols D and M are at a level that does not cause any problem in practice, since the ultimate temperature is low, the crystal grain size is small, so that the elongation and the r value are lower than those of other examples of the present invention. Although the examples of the present invention with the symbols R and S are at a level that causes no problem in practice, the amount of C in the steel is high, so that the elongation and the r value are lower than those of other examples of the present invention. Although the present invention example with the symbol Q is at a level where there is no problem in practical use, the amount of Si in the steel is high, and the elongation and r value are low due to solid solution strengthening by Si. Other examples of the present invention with the symbols A to C, E, G, I, and N to P are excellent in mechanical properties in addition to chemical conversion treatment.

  On the other hand, since the maximum value of the dew point is 40 ° C. when the coil coldest point in the annealing furnace is 200 ° C. or higher and the surface Fe oxide is generated, the symbol F has poor chemical conversion treatment. The code H has a low dew point of 50 ° C. when the coil coldest point in the annealing furnace is 200 ° C. or more, and surface Fe oxide is formed, so that the chemical conversion treatment is not good. Furthermore, since the dew point in the high temperature range was high, decarburization during annealing, the ferrite crystal grains became coarse and non-uniform, and the elongation deteriorated significantly. Since the dew point at the coil coldest point in the annealing furnace is low at 600 ° C. or higher in the comparative examples of the signs J to L, the ratio of the sum of the Mn oxide amount on the steel sheet surface and the respective oxide amounts of Al, Ti, Si is 1. It was less than 0, and when the chemical conversion treatment was performed, remarkable uneven unevenness occurred in the chemical conversion film.

  Due to the excellent characteristics of the present invention, the cold-rolled steel sheet of the present invention is extremely effective mainly for automobile applications.

It is a figure which shows the relationship between the amount of surface Mn oxides, the sum of each oxide amount of surface Al, Ti, and Si, and chemical conversion treatment property. It is a figure which shows the log | history example of temperature and a dew point in an annealing process. Example 1

Claims (6)

Chemical conversion treatment characterized in that the amount of Fe oxide on the steel sheet surface is 10 mg / m ² or less, and the ratio of the amount of Mn oxide to the sum of the amounts of oxides of Al, Ti, and Si is 1.0 or more by mass ratio Cold-rolled steel sheet with excellent properties.   In mass%, C: 0.0030% or less, Si: 0.1% or less, Mn: 0.2% or less, P: 0.02% or less, S: 0.02% or less, Sol. Al: 0.01 to 0.1%, N: 0.0040% or less , B: 0 to 0.002%, further containing Ti: 0 to 0.1%, Nb: 0 to 0.05% and satisfying Ti / 48 + Nb / 93> 2 (C / 12 + N / 14), The cold-rolled steel sheet having excellent chemical conversion properties according to claim 1, wherein the balance is made of Fe and unavoidable impurities.   The cold-rolled steel sheet having excellent chemical conversion properties according to claim 1 or 2, wherein the structure is a ferrite single phase and the average crystal grain size is 15 to 20 µm. When batch-annealing a hot-rolled steel sheet after cold rolling,
Over 80% hydrogen concentration in the atmosphere gas,
The dew point of the atmosphere gas when the coil coldest point in the annealing furnace is 200 ° C or higher is 30 ° C or lower,
Furthermore, the manufacturing method of the cold-rolled steel plate excellent in the chemical conversion property characterized by making the dew point of atmospheric gas into -20 degreeC or more when the coil coldest point in an annealing furnace is 600 degreeC or more.   As the hot-rolled steel sheet, in mass%, C: 0.0030% or less, Si: 0.1% or less, Mn: 0.2% or less, P: 0.02% or less, S: 0.02% or less, Sol. Al: 0.01 to 0.1% N: 0.0040% or less, B: 0 to 0.002%, Ti: 0 to 0.1%, Nb: 0 to 0.05%, and Ti / 48 + Nb / 93> 2 (C / 12 + N / 14) The method for producing a cold-rolled steel sheet having excellent chemical conversion property according to claim 4, wherein the hot-rolled steel sheet is contained so as to satisfy the balance and the balance is Fe and inevitable impurities.   The method for producing a cold-rolled steel sheet excellent in chemical conversion treatment property according to claim 4 or 5, wherein an ultimate temperature of the coil coldest point in batch annealing is 700 ° C or higher.

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