Patent Application
20250066625
The present invention relates to a steel sheet excellent in terms of slidability when press forming is performed and a method for manufacturing the steel sheet. In particular, aspects of the present invention relate to a steel sheet which has a lubrication film that is excellent in terms of formability even when intense drawing is performed and a method for manufacturing the steel sheet.
Cold rolled steel sheets and hot rolled steel sheets, which have a wide range of industrial applications in fields including automotive body applications, are generally subjected to press forming when used in such applications. Nowadays, since there are demands for integrated parts, which are intended to reduce the number of processes, and improvement in design effect, it is necessary to realize complex forming at a higher level. In the case where an attempt is made to realize complex press forming at a higher level, there is a risk of significant negative effects on the productivity of automobiles, such as steel sheet fracture caused by the degree of forming which exceeds the capacity of the steel sheet, die galling occurring when continuous press forming is performed, or the like. Therefore, it is necessary to improve the press formability of the steel sheets.
Examples of a method for improving the press formability of cold rolled steel sheets and hot rolled steel sheets include a method involving surface treatment of a die. Although this method is widely used, in the case of this method, it is not possible to adjust the die after surface treatment has been performed. In addition, there is also a problem of high cost. Therefore, there is a strong demand for improving the press formability of a steel sheet itself.
Examples of a method for improving press formability without performing surface treatment on a die include a method utilizing high-viscosity lubricant. However, in the case of this method, there may be a case of poor degreasing after press forming, and there is a risk of a deterioration in paintability.
Therefore, as a technique for realizing press forming without utilizing the surface treatment of a die or high-viscosity lubricant, investigations are being conducted regarding various kinds of steel sheets having a lubrication-treated surface.
Patent Literature 1 describes a technique in which a lubrication film obtained by adding synthesized resin powder to an acrylic resin coating film is formed on the surface of a galvanized steel sheet.
Patent Literature 2 describes a technique in which a lubrication film having lithium silicate as the constituent of a coating film and a wax and a metallic soap added as lubricants to the coating film is formed on the surface of a steel sheet.
Patent Literature 3 describes a metal product having a lubrication-treated surface coated with a film which is formed by adding a lubricant to a polyurethane resin and which has a thickness of 0.5 μm to 5 μm and having excellent press formability.
Patent Literature 4 describes a technique in which an alkali-soluble organic coating film obtained by adding a lubricant to an epoxy resin is formed on the surface of a steel sheet.
PTL 1: Japanese Unexamined Patent Application Publication No. 9-170059
PTL 2: Japanese Unexamined Patent Application Publication No. 2002-307613
PTL 3: Japanese Unexamined Patent Application Publication No. 2000-309747
PTL 4: Japanese Unexamined Patent Application Publication No. 2000-167981
However, in the case of Patent Literature 1 to Patent Literature 4, although lubrication performance was achieved due to the lubrication effect of the added lubricants or the like, press formability was not always sufficient when complex forming was performed.
Aspects of the present invention have been completed in view of the situation described above, and an object of aspects of the present invention is to provide a steel sheet that is to be subjected to complex forming in which press forming is difficult, the steel sheet having low sliding resistance in a portion at risk of cracking when press forming is performed and excellent press formability in a portion in which die galling is considered to occur due to high contact pressure, and to provide a method for manufacturing the steel sheet.
In addition, in the case where the steel sheet is used as an automobile steel sheet, the steel sheet is also required to have sufficient film removability in an alkaline degreasing process in a painting process and to further have excellent weldability. In the case of such an application, desirably the steel sheet further has good film removability and weldability.
To solve the problems described above, the present inventors diligently conducted investigations. As a result, the inventors found that it is possible to solve the problems described above by forming an organic coating film on the surface of a steel sheet to improve press formability. The organic coating film has an indentation hardness of 0.5 GPa or higher and 1.5 GPa or lower in the case where the coating film has an indentation reduced Young's modulus of 20 GPa or higher and 50 GPa or lower or the coating film has an indentation hardness of 0.2 GPa or higher and 0.5 GPa or lower in the case where the coating film has an indentation reduced Young's modulus of 10 GPa or higher and lower than 20 GPa.
Moreover, it was also found that there is a significant improvement in lubrication performance in the case where a combination of a specified organic coating film and a specified wax is selected.
Aspects of the present invention have been completed on the basis of the knowledge described above, and the subject matter of aspects of the present invention is as follows.
In accordance with aspects of the present invention, the meaning of the term “steel sheet” includes a cold rolled steel sheet and a hot rolled steel sheet.
According to aspects of the present invention, it is possible to obtain a steel sheet excellent in terms of press formability. Since there is a marked decrease in the friction coefficient between the steel sheet and a die or the like, it is possible to provide excellent press formability stably to a steel sheet having comparatively low strength, which is subjected to complex forming. In addition, in the case of a high strength steel sheet where there is an increase in the contact pressure when press forming is performed, it is possible to obtain a steel sheet having low sliding resistance in a portion at risk of cracking when press forming is performed and excellent press formability in a portion in which die galling is considered to occur due to high contact pressure. Moreover, it is possible to achieve a condition in which there is no impediment to subsequent processes such as a welding process, a degreasing process, a chemical conversion process, a painting process, and the like.
In the description above, the expression “high strength” denotes the assumption that tensile strength (TS) is 440 MPa or higher, and the expression “comparatively low strength” denotes the assumption that TS is lower than 440 MPa.
Hereafter, embodiments of the present invention will be described.
First, the indentation reduced Young's modulus and indentation hardness of the coating film after drying will be described.
The term “indentation reduced Young's modulus of a coating film” denotes a physical property value which is determined, when a coating film sample is indented by an indenter and then unloaded, from the line tangent to a load-displacement curve at the maximum load point and the projected contact area of the indenter. It indicates a level of force with which the coating film pushes back when a displacement is applied to the coating film. Although the indentation reduced Young's modulus of an organic resin coating film varies in accordance with the constituents, thickness, condensation degree, and the like of the coating film, the indentation reduced Young's modulus is 8 GPa to 40 GPa in general cases.
It is possible to determine the indentation reduced Young's modulus of a coating film by using, for example, a nanoindenter or the like.
In the case of an organic resin coating film after drying having an indentation reduced Young's modulus of 20 GPa or higher and 50 GPa or lower and an indentation hardness of 0.5 GPa or higher and 1.5 GPa or lower, since the deformation amount of the constituents of the organic resin coating film which enters the interface between the steel sheet and the die is small, the steel sheet has low sliding resistance in a portion at risk of cracking when press forming is performed and has excellent press formability in a portion in which die galling is considered to occur due to high contact pressure.
In addition, also in the case of an organic resin coating film after drying having an indentation reduced Young's modulus of 10 GPa or higher and less than 20 GPa, when the indentation hardness is 0.2 GPa or higher and 0.5 GPa or lower, since shear deformation tends to occur in the constituents of the organic resin coating film which enters the interface between the steel sheet and the die, the steel sheet has low sliding resistance in a portion at risk of cracking when press forming is performed and has excellent press formability in a portion in which die galling is considered to occur due to high contact pressure.
The term “indentation hardness of a coating film” denotes hardness which is determined, when a coating film sample is indented by an indenter and then unloaded, by dividing the maximum load point by the projected contact area of the indenter, and it is possible to determine such indentation hardness by using, for example, a nanoindenter or the like.
The coating weight after drying of the organic resin coating film is set to be 0.2 g/m2 or more and 2.0 g/m2 or less. It is not possible to achieve sufficient press formability in the case where the coating weight after drying of the organic resin coating film is less than 0.2 g/m2, and there may be a deterioration in weldability and film removability in the case where such a coating weight is more than 2.0 g/m2.
It is preferable that the organic resin coating film contain one, two, or more selected from an acrylic resin, a urethane resin, a phenol resin, an epoxy resin, and a mixture thereof. With this, the die and the steel sheet are inhibited from coming into direct contact with each other when press forming is performed and lubrication performance is achieved. In addition, since there is high affinity between the organic resin and a wax, when a hydrocarbon-based wax is added to the organic resin coating film, further improved lubrication performance is achieved due to a uniform mixture of the organic resin and the wax being formed when sliding occurs.
It is preferable that the organic resin coating film contains the wax in an amount of 50 mass % or less with respect to 100 mass % of resin constituents, because this results in further improved lubrication performance. In the case where the wax content is more than 50 mass % with respect to 100 mass % of resin constituents, since there is a decrease in the indentation reduced Young's modulus and indentation hardness, there may be a case where it is not possible to achieve sufficient press formability. In addition, in the case where the steel sheet is used as an automobile steel sheet, there may be a case where it is not possible to achieve sufficient degreasing capability in an alkaline degreasing process in a painting process, and, even in the case where an alkali-soluble organic resin is used, there may be a deterioration in paintability due to a residual coating film because the coating film is not sufficiently removed in the alkaline degreasing process.
The term “proportion of a wax in an organic resin coating film” denotes the ratio of the mass of the solid wax in the organic resin coating film with respect to the sum of the mass of the solid organic resin in the organic resin coating film and the mass of the solid wax in the organic resin coating film.
Regarding a specific method for determining the mass fraction of the wax, a test specimen of a steel sheet for which the coating weight of each of the organic resin and the wax is known is prepared, the infrared absorption spectrum of the test specimen is measured by using a FT-IR measuring apparatus, and the calibration curve for the coating weight of each of the organic resin and the wax is produced from the relevant peak intensity. Subsequently, the infrared absorption spectrum of a target steel sheet having an organic resin coating film is measured, and the coating weight of each of the organic resin and the wax is determined on the basis of the relevant calibration curve, which makes it possible to determine the mass fraction of the wax in the organic resin coating film.
It is preferable that the wax be a hydrocarbon-based wax. This is because a hydrocarbon-based wax has a comparatively high melting temperature, low viscosity, and high hardness, which makes it possible to achieve good lubrication performance. In addition, regarding the hydrocarbon-based wax, in the case of a polyolefin wax, it is possible to control the melting temperature to be 120° C. or higher and 140° C. or lower comparatively easily by controlling its density and molecular weight.
In the case where the melting temperature of the wax is 120° C. or higher and 140° C. or lower, it is possible to achieve an excellent lubrication effect, because it is possible for the wax to deliver self-lubrication performance, and because it is possible for the constituents of the lubrication film, formed of a mixture of the organic resin and the wax which is in a semi-molten state due to sliding when press forming is performed, to cover the surface of the die and it is thus possible to inhibit the die and the steel sheet from coming into direct contact with each other. In the case where such a melting temperature is lower than 120° C., since the wax is completely melted due to frictional heat generated by sliding when press forming is performed, it is not possible for the wax to realize a sufficient lubrication effect, and it is not possible for the constituents of the lubrication film to realize the effect of covering the die described above either. In addition, in the case where such a melting temperature is higher than 140° C., since the wax is not melted when sliding is performed, it is not possible to realize a sufficient lubrication effect, and it is not possible to realize the effect of covering the die described above either.
It is considered that, in the case where the melting temperature of the wax is 120° C. or higher and 140° C. or lower, since the wax in the organic resin coating film efficiently adheres to the die in a sliding state when press forming is performed, the wax is less likely to be detached, which results in a high lubrication effect. In the case where such a melting temperature is lower than 120° C., even in the case where the organic resin coating film adheres to the die, since there is a weak adhesion force, the coating film is more likely to be detached when sliding is performed. In the case where such a melting temperature is higher than 140° C., the organic resin coating film is less likely to adhere to the die. Moreover, it is preferable that such a melting temperature be 125° C. or higher and 135° C. or lower.
Here, the term “melting temperature” with respect to the wax denotes the melting temperature measured in accordance with JIS K 7121:1987 “Testing Methods for Transition Temperatures of Plastics”.
Regarding the polyolefin wax, it is preferable that a polyethylene wax be used, because this makes it possible to realize the highest lubrication effect.
It is preferable that the average particle diameter of the wax be 4 μm or less. In the case where the average particle diameter of the wax is more than 4 μm, since the wax is less likely to be mixed with the organic resin when sliding is performed, it is not possible to realize the above-described effect of covering the die, which results in sufficient lubrication performance not being achieved. It is more preferable that the average particle diameter of the wax be 1.5 μm or less, even more preferably 0.5 μm or less, or even much more preferably 0.3 μm or less.
It is preferable that the average particle diameter of the wax be 0.01 μm or more. In the case where the average particle diameter of the wax is less than 0.01 μm, since the wax is more likely to be dissolved in a lubricant when sliding is performed, there may be a case where it is not possible to realize a sufficient effect of improving lubrication performance. In addition, in the case where the average particle diameter of the wax is less than 0.01 μm, since the wax is more likely to be aggregated in a paint for forming the organic resin coating film, there is low paint stability. It is more preferable that such an average diameter be 0.03 μm or more.
The term “average particle diameter of the wax” denotes the median diameter of a volume average particle diameter, which is determined by using a laser diffraction/scattering method. It is possible to obtain the average particle diameter of the wax by observing a sample which is diluted with pure water by using, for example, a laser diffraction/scattering-type particle size distribution measuring device, that is, a Partica (registered trademark) LA-960V2 (produced by HORIBA, Ltd.).
The method for manufacturing a steel sheet according to aspects of the present invention is a method for manufacturing a steel sheet having an organic resin coating film formed of an organic resin or an organic resin containing a wax on the surface thereof. After having applied a solution, which is prepared by dissolving or dispersing an organic resin in an aqueous solvent, or a solution, which is prepared by adding a wax to the solution of the organic resin, to the surface of a steel sheet, the solution is dried. With this method, a lubrication film having a coating weight per side after drying of 0.2 g/m2 or more and 2.0 g/m2 or less is formed on the steel sheet. Although there is no particular limitation on the coating method, examples of the coating method include a method utilizing a roll coater or a bar coater and a method involving spraying, dipping, or brushing. The coated steel sheet may be dried by using a common method. Examples of the drying method include a method utilizing hot air, an induction heater, or an infrared heater.
To realize such a condition in which the organic resin coating film after drying has an indentation reduced Young's modulus of 20 GPa or higher and 50 GPa or lower and an indentation hardness of 0.5 GPa or higher and 1.5 GPa or lower, candidate organic resin coating films are manufactured under assumed manufacturing conditions (film coating weight, drying conditions, and the like), and the indentation reduced Young's modulus and the indentation hardness are determined for selection.
To realize such a condition in which the organic resin coating film after drying has an indentation reduced Young's modulus of 10 GPa or higher and less than 20 GPa and an indentation hardness of 0.2 GPa or higher and 0.5 GPa or lower, candidate organic resin coating films are manufactured under assumed manufacturing conditions (film coating weight, drying conditions, and the like), and the indentation reduced Young's modulus and the indentation hardness are determined for selection.
It is preferable that the maximum end-point temperature of the steel sheet when drying is performed be 60° C. or higher and 150° C. or lower. In the case where the maximum end-point temperature of the steel sheet when drying is performed is lower than 60° C., it takes a long time to dry the steel sheet, and there may be a deterioration in antirust capability. Moreover, since there is insufficient polymerization of the organic resin, the reduced Young's modulus becomes less than 10 GPa, which results in sufficient lubrication performance not being achieved. In the case where the maximum end-point temperature of the steel sheet when drying is performed is 150° C. or higher, since the polymerization and dehydration of the organic resin progress, it is possible to achieve sufficient lubrication performance due to an increase in the reduced Young's modulus. However, there may be a deterioration in film removability. In addition, in the case where a wax having a melting temperature of 150° C. or lower is contained in the organic resin coating film, since the wax is melted to be mixed with the resin, there is a decrease in the indentation reduced Young's modulus and the indentation hardness, which may result in a deterioration in press formability.
Although aspects of the present invention have been described above in accordance with the embodiments of the present invention, the present invention includes, but is not limited to, the descriptions and figures of the present embodiments, which form a part of the disclosure of the present invention. That is, other embodiments, working examples, operational techniques, and the like, which are performed on the basis of the present embodiments by, for example, those ordinarily skilled in the art are all within the scope of the present invention.
Hereafter, aspects of the present invention will be described in accordance with examples. Here, the present invention is not limited to the examples below. In addition, the organic resin coating film may also be simply referred to as “coating film”.
A steel sheet having a size of 350 mm×230 mm which was taken from a cold rolled steel sheet (TS: 270 MPa) having a thickness of 0.8 mm was used as a base material for an organic resin coating film. After the taken steel sheet had been subjected to an ultrasonic cleaning process of being immersed in a 50 vol % toluene-50 vol % ethanol solvent for 5 minutes, the cleaned steel sheet was dried by using a blower, and the dried steel sheet was subjected to a degreasing treatment utilizing an alkaline degreasing agent, that is, FINE CLEANER (registered trademark) E6403 (produced by Nihon Parkerizing Co., Ltd.). In such a treatment, after the test specimen had been immersed in a degreasing solution containing the degreasing agent having a degreasing agent concentration of 20 g/L at a temperature of 40° C. for 2 minutes, the immersed test specimen was rinsed in tap water, and then dried by using a blower. After each of the paints given in Table 1 had been applied to the surface of the steel sheet prepared as described above by using a bar coater, the painted steel sheet was baked and dried by using an induction heater (IH) to manufacture a steel sheet having a lubrication organic coating film given in Table 2. Here, the temperature at which each of the samples was baked to form the coating film is given in Table 2. These samples were evaluated by using the methods described below, and the results are given in Table 2.
The indentation reduced Young's modulus and indentation hardness of the coating film were determined by using the following method.
A piece having a size of 10 mm square which was taken from each of the lubrication organic resin-coated steel sheets was used as a sample material. For measurement, a nanoindenter produced by HYSITRON Inc., that is, a TI Premier Multi Scale, was used. Regarding the indenter, a cube corner-type indenter made of diamond was used. In the measurement, the indenter was impressed for 5 seconds, held thereafter at the maximum load (30 μN to 150 μN) for 10 seconds, and then unloaded in 5 seconds. At each of five randomly selected positions in the vicinity of the central position of each of the sample materials, an indentation depth-load curve was taken under such measurement conditions, and the indentation reduced Young's modulus Er and the indentation hardness H were calculated by using the equations below. The average values of the indentation reduced Young's modulus and the indentation hardness of the five points were defined as the average values of the indentation reduced Young's modulus and the indentation hardness, respectively, of each of the sample materials.
Here, A denotes the projected contact area of the residual indentation, dP/dh denotes the line tangent to the unloading curve at the maximum load point, and Pmax denotes the maximum load.
On the basis of the average values of the indentation reduced Young's modulus and the indentation hardness of each of the samples, a case of an organic resin coating film after drying having an indentation reduced Young's modulus of 20 GPa or higher and 50 GPa or lower and an indentation hardness of 0.5 GPa or higher and 1.5 GPa or lower or a case of an organic resin coating film after drying having an indentation reduced Young's modulus of 10 GPa or higher and less than 20 GPa and an indentation hardness of 0.2 GPa or higher and 0.5 GPa or lower was judged as a case of an organic resin coating film having the mechanical properties according to aspects of the present invention and denoted by ∘, and other cases were judged as unsatisfactory and denoted by ×.
To evaluate the press formability, the friction coefficient of each of the sample materials was measured by using the method described below.
The test for measuring the friction coefficient was performed by using the bead illustrated in
To determine the film removability of the organic resin-coated steel sheet, the test specimens were first subjected to a degreasing treatment by using an alkaline degreasing agent FINE CLEANER (registered trademark) E6403 (produced by Nihon Parkerizing Co., Ltd.). In such a treatment, the test specimen was immersed for a predetermined time in a degreasing solution having a degreasing agent concentration of 20 g/L and a temperature of 40° C., washed with tap water, and then dried by using a blower. The surface carbon intensity of the test specimen which had been subjected to such a treatment was measured by using an X-ray fluorescence spectrometer, and a film removal ratio was calculated by using the following equation from the measured value of such a surface carbon intensity, a surface carbon intensity which had been measured in advance before degreasing was performed, and the surface carbon intensity of the steel sheet before the lubrication treatment was performed.
The film removability of the organic resin-coated steel sheet was evaluated in accordance with the evaluation criteria below on the basis of an immersion time for which the sample had been immersed in the alkaline degreasing solution until the film removal ratio defined as above reached 98% or higher.
Each of the test specimens was subjected to a welding test for investigating consecutive spot weldability by using a DR-type Cr—Cu electrode under the conditions of a welding force of 150 kgf, an energizing time of 10 cycles/60 Hz, and a welding current of 7.5 kA, and the weldability was evaluated on the basis of the consecutive spot number. The evaluation criteria are as follows.
The results obtained by using the methods described above are given in Table 2.
From the results given in Table 2, it was clarified that, according to aspects of the present invention, it is possible to obtain a steel sheet having excellent press formability. In addition, it is also possible to optionally obtain a steel sheet further having film removability and weldability which are at a practicable level.
Since the steel sheet according to aspects of the present invention has excellent press formability, it is possible to use the steel sheet in a wide range of fields of industrial applications including applications in which particularly intense drawing is performed. In addition, since it is possible to optionally manufacture a steel sheet having excellent film removability and weldability, it is also possible to use such a steel sheet for automotive body applications.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-054830 | Mar 2022 | JP | national |
This is the U.S. National Phase application of PCT/JP2023/002151, filed Jan. 24, 2023, which claims priority to Japanese Patent Application No. 2022-054830, filed Mar. 30, 2022, the disclosures of these applications being incorporated herein by reference in their entireties for all purposes.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/002151 | 1/24/2023 | WO |
