CN110506135B - Steel sheet, method for producing same, bottle cap, and DRD can - Google Patents
Steel sheet, method for producing same, bottle cap, and DRD can Download PDFInfo
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- CN110506135B CN110506135B CN201880021500.XA CN201880021500A CN110506135B CN 110506135 B CN110506135 B CN 110506135B CN 201880021500 A CN201880021500 A CN 201880021500A CN 110506135 B CN110506135 B CN 110506135B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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Abstract
The present invention is characterized by comprising, in mass%, C: more than 0.0060% and 0.0100% or less, Si: 0.05% or less, Mn: 0.05% or more and 0.60% or less, P: 0.050% or less, S: 0.050% or less, Al: 0.020% or more and 0.050% or less, and N: 0.0070% to 0.0140% inclusive, and the balance Fe and inevitable impurities, and a ferrite phase structure having a standard deviation of ferrite grain diameter of 7.0 [ mu ] m or less in a region from 1/4 depth of the sheet thickness to the central portion of the sheet thickness, and having a yield strength of 560MPa or more, and providing a steel sheet having sufficient strength and excellent formability even when the steel sheet is thinned.
Description
Technical Field
The present invention relates to a steel sheet, particularly a high-strength thin steel sheet excellent in formability, and a method for producing the same. Typical examples of such steel sheets include thin steel sheets supplied as materials for DRD (Drawing and Redrawing) cans formed by combining Drawing and Redrawing, and caps used as caps for glass bottles and the like. The present invention also relates to a bottle cap and a DRD can obtained by forming the steel sheet.
Background
Conventionally, glass bottles have been used in many cases as containers for beverages such as soft drinks and alcoholic beverages. In particular, a metal cap called a bottle cap is widely used for a narrow-mouth glass bottle. Generally, a bottle cap is manufactured by press forming a thin steel plate as a material, and is composed of a disk-shaped portion that closes a mouth of a bottle and a pleated portion provided around the disk-shaped portion, and the bottle cap is sealed by fastening the pleated portion to the mouth of the bottle.
Many bottles using caps are filled with contents that generate high internal pressure, such as beer and carbonated beverages. Therefore, the bottle cap needs high pressure resistance so that the bottle cap does not deform and the seal of the bottle is not broken even when the internal pressure is increased by a change in temperature or the like. In addition, even if the strength of the material is sufficient, if the uniformity of the material of the steel plate used for the bottle cap is low, the shape of the bottle cap is irregular and the bottle cap deviates from the product specification. Since sufficient sealing performance cannot be obtained even when a bottle cap having such a poor shape is fastened to a bottle mouth, a steel plate as a material of the bottle cap is required to have excellent material uniformity.
As the thin steel plate used as a material of the bottle cap, SR (Single Reduced) steel plate is mainly used. The steel sheet is obtained by performing cold rolling to thin the steel sheet, annealing the steel sheet, and temper rolling. Conventional steel sheets for bottle caps generally have a sheet thickness of 0.22mm or more, and by applying SR materials made of mild steel used for cans of foods and beverages, etc., sufficient compressive strength and formability can be ensured.
In recent years, as with steel sheets for cans, there has been an increasing demand for thinner steel sheets for bottle caps for the purpose of cost reduction. When the thickness of the steel sheet for bottle caps is less than 0.22mm, particularly 0.20mm or less, the compressive strength of the conventional bottle caps made of SR material is insufficient. In order to secure the compressive strength as a steel sheet for a bottle cap, it is necessary to compensate for the strength reduction accompanying the thinning, and a DR (Double Reduced) steel sheet is used which is subjected to cold rolling again after annealing and work hardening.
In the bottle cap, the central portion is drawn to some extent at the initial stage of forming, and then the outer edge portion is formed into a pleated shape. Here, when the material of the bottle cap is a steel plate having low material uniformity, the bottle cap made of the steel plate may have irregular outer diameter and height and may deviate from the product specifications. There is a problem that, when the outer diameter and the height of the bottle cap are irregular and deviate from the product specification, the yield is lowered when the bottle cap is manufactured in large quantities. Further, there are also problems as follows: the cap having an outside diameter and a height that deviate from the specifications is likely to cause leakage of contents during transportation after the cap is sealed on a bottle, and cannot function as a cap. In addition, even if the outer diameter and height of the cap are within the product specifications, the cap may come off due to insufficient compressive strength when the strength of the steel plate is low.
Further, when a steel sheet having low uniformity of material quality is used as a material of the DRD can, there is a possibility that a shape defect such as a wrinkle generated in a flange portion of the can at the time of forming the DRD can may be caused. This DRD can has the same problem as the above-mentioned bottle cap, in which, even when the DRD can deviates from the product specification due to a defective shape, the yield is lowered when the DRD can is manufactured in large quantities.
As for the high-strength thin steel sheet for bottle caps based on the above-mentioned aspect, for example, patent document 1 discloses a steel sheet for bottle caps containing, in mass%, C: 0.0010% or more and 0.0060% or less, Si: 0.005% to 0.050% and Mn: 0.10% or more and 0.50% or less, P: 0.040% or less, S: 0.040% or less, Al: 0.1000% or less, N: 0.0100% or less, and the minimum value of r values in the direction of 25 to 65 DEG relative to the rolling direction, the average value of r values in all directions, and the yield strength are appropriately controlled, thereby satisfying sufficient cap pressure resistance even when the thickness is small.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6057023
Disclosure of Invention
Problems to be solved by the invention
In the steel sheet described in patent document 1, a steel containing 0.0060% or less of C is used, and the r value (direction and size) suitable for the bottle cap processing is obtained by setting the inter-stand tension and the annealing temperature in the secondary cold rolling to a predetermined relationship. Since this method does not control the hot rolling process that affects the formation of the metal structure, the fluctuation in the material quality of the obtained steel sheet becomes large, and it is difficult to put the method into practical use.
The present invention has been made in view of the above problems, and an object thereof is to provide a steel sheet having sufficient strength and excellent formability even when the steel sheet is made thin, and a method for manufacturing the same. Further, an object of the present invention is to provide a bottle cap and a DRD can which are adjusted to a predetermined size and shape and are excellent in shape stability.
Means for solving the problems
The present inventors have conducted intensive studies on a method for solving the above problems, and as a result, have found that high strength and excellent formability can be imparted by restricting the texture at a predetermined composition. The present invention is based on this finding, and its gist is as follows.
(1) A steel sheet having a composition containing, in mass%, C: more than 0.0060% and 0.0100% or less, Si: 0.05% or less, Mn: 0.05% or more and 0.60% or less, P: 0.050% or less, S: 0.050% or less, Al: 0.020% or more and 0.050% or less, and N: 0.0070% to 0.0140% inclusive, and the balance Fe and inevitable impurities,
a ferrite phase in a region from 1/4 mm in thickness to the central part of the thickness, wherein the standard deviation of ferrite grain diameter in the ferrite phase is 7.0 μm or less,
the yield strength is 560MPa or more.
(2) The steel sheet according to the above (1), wherein the thickness is 0.20mm or less.
(3) A bottle cap comprising the steel plate according to the above (1) or (2).
(4) A DRD can comprising the steel sheet according to (1) or (2).
(5) A method for producing a steel sheet according to the above (1) or (2), comprising:
a hot rolling step of heating a steel material at 1200 ℃ or higher, rolling the heated material at a finish rolling temperature of 870 ℃ or higher and a reduction ratio of 10% or higher in a final stand, and coiling the rolled material at a temperature of 550 to 750 ℃;
a pickling step of pickling the hot-rolled sheet after hot rolling;
a primary cold rolling step of cold rolling the hot-rolled sheet after pickling at a reduction of 88% or more;
an annealing step of keeping the cold-rolled sheet after the primary cold rolling at a temperature of 660 to 760 ℃ for 60 seconds or less, cooling the cold-rolled sheet at an average cooling rate of 10 ℃/s or more to a temperature of 450 ℃ or less, and then cooling the cold-rolled sheet at an average cooling rate of 5 ℃/s or more to a temperature of 140 ℃ or less; and
and a secondary cold rolling step of cold rolling the annealed sheet at a reduction ratio of 10% to 40%.
Effects of the invention
According to the present invention, a steel sheet having sufficient strength and excellent material uniformity even when the steel sheet is made thin, and an advantageous manufacturing method thereof can be provided. Further, when the steel sheet of the present invention is used for, for example, a bottle cap or a DRD can having no deformation in shape can be formed.
Detailed Description
The steel sheet of the present invention contains, in mass%, C: more than 0.0060% and 0.0100% or less, Si: 0.05% or less, Mn: 0.05% or more and 0.60% or less, P: 0.050% or less, S: 0.050% or less, Al: 0.020% to 0.050% and N: 0.0070% to 0.0140% inclusive, and the balance being Fe and unavoidable impurities, and having a ferrite phase in a region from 1/4 depth in the thickness of the sheet to the central part of the sheet, and a standard deviation of ferrite grain size in the ferrite phase being 7.0 [ mu ] m or less.
First, the reasons for limiting the amounts of the respective components in the composition of the steel sheet will be described in order. The expression "%" of a component means "% by mass" unless otherwise specified.
C: more than 0.0060% and less than 0.0100%
When the content of C is 0.0060% or less, ferrite of a steel sheet after secondary cold rolling described later becomes coarse, formability is deteriorated, and when the steel sheet is used for, for example, a bottle cap, the outer diameter of the formed bottle cap and the height of the bottle cap become uneven. Similarly, when the can is used for, for example, a DRD can, wrinkles are generated in the flange portion at the time of forming the DRD can, and the can has a defective shape. On the other hand, if the C content exceeds 0.0100%, the ferrite of the steel sheet after the secondary cold rolling becomes too fine, the strength of the steel sheet increases excessively, and the formability deteriorates, and when the steel sheet is used for, for example, a bottle cap, the outer diameter and height of the formed bottle cap become uneven. Similarly, when the can is used for, for example, a DRD can, wrinkles are generated in the flange portion at the time of forming the DRD can, and the can has a defective shape. Therefore, the content of C is set to more than 0.0060% and 0.0100% or less. The content of C is preferably set to 0.0065% to 0.0090%.
Si: less than 0.05%
When Si is contained in a large amount, for the same reason as C, uniformity of the outer diameter and height of the cap is impaired when the cap is used for, for example, a bottle cap, and when the cap is used for, for example, a DRD can, a shape defect in which wrinkles are generated in a flange portion at the time of forming the DRD can is caused. Therefore, the content of Si is set to 0.05% or less. Further, since excessive reduction of Si leads to an increase in steel-making cost, the content of Si is preferably set to 0.004% or more. More preferably 0.01% or more and 0.03% or less.
Mn: 0.05% to 0.60% inclusive
When the Mn content is less than 0.05%, it is difficult to avoid thermal embrittlement even if the S content is reduced, and problems such as surface cracking occur during continuous casting. Therefore, the Mn content is set to 0.05% or more. On the other hand, when Mn is contained in a large amount, for the same reason as C, uniformity of the outer diameter and height of the cap is impaired when it is used for, for example, a cap, and when it is used for, for example, a DRD can, a shape defect in which wrinkles are generated in the flange portion at the time of forming the DRD can is caused. Therefore, the Mn content is set to 0.60% or less. The Mn content is preferably 0.10% or more and 0.50% or less.
P: 0.050% or less
If the content of P exceeds 0.050%, the steel sheet becomes hard and the corrosion resistance is reduced. Further, the standard deviation of the ferrite grain size after annealing becomes larger than 7.0 μm, the formability is deteriorated, uniformity of the outer diameter and height of the bottle cap is impaired in the case of application to, for example, a bottle cap, and the shape defect that wrinkles are generated at the flange portion in the case of application to, for example, a DRD can is caused. Therefore, the upper limit of the content of P is set to 0.050%. In addition, in order to make P less than 0.001%, the cost for removing P becomes excessive, and therefore, the content of P is preferably set to 0.001% or more.
S: 0.050% or less
S combines with Mn in the steel sheet to form MnS, and when a large amount of S precipitates, the hot ductility of the steel sheet decreases. When the content of S exceeds 0.050%, the effect becomes remarkable. Therefore, the upper limit of the S content is set to 0.050%. In addition, since the cost for removing S becomes excessive so that S is less than 0.005%, the content of S is preferably set to 0.004% or more.
Al: 0.020% or more and 0.050% or less
Al is an element contained as a deoxidizer, and forms AlN with N in the steel to reduce the amount of N dissolved in the steel. If the Al content is less than 0.020%, the effect as a deoxidizer becomes insufficient, solidification defects occur, and the steel-making cost increases. If the Al content is less than 0.020%, an appropriate amount of AlN cannot be secured at the time of recrystallization of ferrite during annealing, and therefore, the standard deviation of the ferrite grain size after annealing becomes large, and ferrite of the steel sheet after secondary cold rolling becomes coarse, and formability deteriorates. Therefore, when the bottle cap is used for, for example, a bottle cap, uniformity of the outer diameter and height of the bottle cap is impaired, and when the bottle cap is used for, for example, a DRD can, a shape defect in which wrinkles are generated in a flange portion at the time of forming the DRD can is caused. On the other hand, when the Al content exceeds 0.050%, AlN formation increases, and the amount of N contributing to the strength of the steel sheet in the form of solid-solution N described later decreases, and the strength of the steel sheet decreases, so the Al content is set to 0.050% or less. The Al content is preferably 0.030% or more and 0.045% or less.
N: 0.0070% or more and 0.0140% or less
If the content of N is less than 0.0070%, ferrite of the steel sheet after the secondary cold rolling becomes coarse, and formability is deteriorated, and when the steel sheet is used for, for example, a bottle cap, the outer diameter and height of the formed bottle cap become uneven, and the amount of N contributing to the strength of the steel sheet in the form of solid solution N described later is reduced, and the strength of the steel sheet is lowered. Similarly, when the can is used for, for example, a DRD can, wrinkles are generated in the flange portion at the time of forming the DRD can, and the can has a defective shape. On the other hand, if the N content exceeds 0.0140%, ferrite of the steel sheet after the secondary cold rolling becomes too fine, the strength of the steel sheet increases excessively, the formability deteriorates, uniformity of the outer diameter and height of the bottle cap is impaired when the steel sheet is used for, for example, bottle cap applications, and the steel sheet is used for, for example, DRD can applications, which causes a shape defect in which wrinkles are generated in the flange portion when the DRD can is formed. The content of N is preferably set to 0.0085 or more and 0.0125% or less. More preferably, it is set to more than 0.0100%.
The balance other than the above components is Fe and inevitable impurities.
Next, it is important that the microstructure of the steel sheet of the present invention has a ferrite phase at least in a region from a depth of 1/4 in the sheet thickness to the center of the sheet thickness, and that the standard deviation of the ferrite grain size in the ferrite phase is 7.0 μm or less.
First, the microstructure of the steel sheet of the present invention is mainly composed of a ferrite phase, and the balance is cementite, and the ferrite phase is preferably 85 vol% or more. More preferably 90% by volume or more. That is, if the ferrite phase is less than 85 vol%, the hard cementite is likely to break at the time of working, and the formability is deteriorated.
In the above microstructure, the standard deviation of ferrite grain diameters in ferrite phases in a region at least from the depth of 1/4 in the thickness to the central portion of the thickness is 7.0 μm or less.
That is, when the standard deviation of the ferrite grain size is more than 7.0 μm, formability is deteriorated, and when the composition is used for, for example, a bottle cap, the outer diameter and height of the formed bottle cap become uneven, compressive strength is lowered, and the yield in manufacturing the bottle cap is lowered. Similarly, when the can is used for, for example, a DRD can, wrinkles are generated in the flange portion at the time of forming the DRD can, and the can has a defective shape. The standard deviation of the ferrite grain size is preferably 6.5 μm or less.
Here, regarding the metal structure of ferrite, a cross section in the plate thickness direction parallel to the rolling direction of the steel sheet was ground, then etched with an etching solution (3 vol% nitric acid ethanol solution), a region from a depth position of 1/4 depths in the plate thickness (a position in the cross section from 1/4 where the surface is the plate thickness in the plate thickness direction) to a position of 1/2 thicknesses was observed in 10 fields of view at a magnification of 400 times with an optical microscope, ferrite was identified by visual judgment using a structural photograph taken with the optical microscope, and the grain size of ferrite was determined by image analysis. The grain size distribution of the ferrite grain size was obtained in each visual field, the standard deviation was calculated, the standard deviations of 10 visual fields were averaged, and the obtained value was taken as the standard deviation of the ferrite grain size. Image analysis the image analysis software "Stream essences" from olympus corporation was used.
The desired metal structure can be obtained by adjusting the composition, the heating temperature in the hot rolling step, the finish rolling temperature, the reduction ratio and the coiling temperature of the final stand, the reduction ratio in the primary cold rolling, the cooling rate in the continuous annealing step, and the reduction ratio in the secondary cold rolling step. The details of the production conditions are as described later.
The steel sheet having the above composition and structure can secure a high strength, specifically a yield strength of 560MPa or more, even with a sheet thickness of 0.20mm or less, for example.
That is, the steel sheet of the present invention is required to have a compressive strength for the purpose of preventing a bottle cap fastened to a bottle mouth from falling off due to internal pressure when applied to, for example, a bottle cap. The steel sheet for bottle caps used in the past has a thickness of 0.22mm or more, and when the thickness is reduced to 0.20mm or less, particularly 0.18mm or less, higher strength than the conventional one is required. When the yield strength of the steel sheet is less than 560MPa, sufficient compressive strength cannot be imparted to the thin-walled bottle cap as described above. Therefore, the yield strength needs to be 560MPa or more. In order to ensure a sufficient compressive strength, the yield strength is preferably 600MPa or more. When the yield strength is too high, the bottle cap height is reduced during bottle cap formation, and the bottle cap shape becomes uneven, so the yield strength in the rolling direction is preferably 700MPa or less. More preferably 600MPa or more and 680MPa or less.
The yield strength can be measured by a metal material tensile test method shown in JIS Z2241.
Next, a method for manufacturing a steel sheet according to the present invention will be described.
The steel sheet of the present invention is produced by the following steps: a hot rolling step of heating a steel material (billet) composed of the above components at 1200 ℃ or higher, a finish rolling temperature of 870 ℃ or higher, a reduction ratio of a final stand of 10% or higher, and coiling the steel material at 550 to 750 ℃; a pickling step of pickling after the hot rolling; a primary cold rolling step of performing cold rolling at a reduction of 88% or more after the pickling step; a continuous annealing step in which, after the primary cold rolling, the holding time is set to 60 seconds or less in a temperature range of 660 to 760 ℃, the steel sheet is cooled to a temperature range of 450 ℃ or less at an average cooling rate of 10 ℃/s or more, and the steel sheet is cooled to a temperature range of 140 ℃ or less at an average cooling rate of 5 ℃/s or more; and performing secondary cold rolling at a reduction ratio of 10% to 40%.
In the following description, the temperature is defined based on the surface temperature of the steel sheet. The average cooling rate is set to a value calculated based on the surface temperature. For example, the average cooling rate from the soaking temperature to the temperature range of 450 ℃ or less is represented by ((soaking temperature- (temperature range of 450 ℃) or less)/cooling time from the soaking temperature to (temperature range of 450 ℃ or less)). The "temperature range of 450 ℃ or lower" in the above formula refers to a cooling stop temperature within the temperature range.
In the production of the steel sheet of the present invention, the molten steel is adjusted to the above-described chemical components by a known method using a converter or the like, and thereafter, a billet is produced as a steel material by, for example, a continuous casting method.
(heating temperature of the raw Steel: 1200 ℃ or higher)
The heating temperature of the steel material in the hot rolling step is set to 1200 ℃ or higher. When the heating temperature is less than 1200 ℃, the amount of dissolved N required for securing strength is reduced and the strength is lowered in the present invention, and therefore, the heating temperature is set to 1200 ℃ or higher. In the steel composition of the present invention, N is considered to be present mainly as AlN, and therefore (Ntotal- (NasAlN)) obtained by subtracting the amount of N present as AlN (NasAlN) from the total amount of N (Ntotal) is considered as the amount of solid-solution N. The amount of solid solution N is preferably 0.0071% or more so that the yield strength of the steel sheet in the rolling direction is 560MPa or more, and can be ensured by setting the heating temperature of the steel material to 1200 ℃ or more. The amount of dissolved N is more preferably 0.0090% or more, and for this reason, the heating temperature of the steel material is preferably 1220 ℃ or more. The effect is saturated even if the heating temperature of the steel material exceeds 1300 ℃, and therefore 1300 ℃ or lower is preferable.
(finishing temperature: 870 ℃ C. or higher)
When the finish rolling temperature in the hot rolling step is less than 870 ℃, part of the ferrite in the steel sheet becomes fine, the standard deviation of the ferrite grain size becomes larger than 7.0 μm, and the formability is deteriorated. Therefore, when the bottle cap is used for, for example, a bottle cap application, the shape of the bottle cap becomes uneven, and when the bottle cap is used for, for example, a DRD can application, a shape defect in which wrinkles are generated in a flange portion at the time of forming the DRD can is caused. Therefore, the finish rolling temperature is set to 870 ℃ or higher. On the other hand, increasing the finish rolling temperature more than necessary may make the production of the steel sheet difficult. Specifically, the finish rolling temperature is preferably set to a temperature range of 870 ℃ to 950 ℃.
(final reduction ratio of frame: 10% or more)
The reduction ratio of the final stand in the hot rolling step is set to 10% or more. When the rolling reduction of the final stand is less than 10%, ferrite of the steel sheet is partially coarsened, the standard deviation of ferrite becomes larger than 7.0 μm, and the formability is deteriorated. Therefore, when the bottle cap is used for, for example, a bottle cap application, the shape of the bottle cap becomes uneven, and when the bottle cap is used for, for example, a DRD can application, a shape defect in which wrinkles are generated in a flange portion at the time of forming the DRD can is caused. Therefore, the final reduction ratio of the frame is set to 10% or more. In order to reduce the standard deviation of the ferrite grain size, the rolling reduction of the final stand is preferably set to 12% or more. From the viewpoint of rolling load, the upper limit of the reduction ratio of the final stand is preferably set to 15% or less.
(coiling temperature: 550 to 750 ℃ C.)
When the coiling temperature in the hot rolling step is less than 550 ℃, part of the ferrite in the steel sheet becomes fine, the standard deviation of the ferrite grain size becomes larger than 7.0 μm, and the formability is deteriorated. Therefore, when the bottle cap is used for, for example, a bottle cap application, the shape of the bottle cap becomes uneven, and when the bottle cap is used for, for example, a DRD can application, a shape defect in which wrinkles are generated in a flange portion at the time of forming the DRD can is caused. Therefore, the winding temperature is set to 550 ℃ or higher. On the other hand, when the coiling temperature is higher than 750 ℃, a part of ferrite of the steel sheet is coarsened, the standard deviation of the ferrite becomes larger than 7.0 μm, the bottle cap shape becomes uneven when used for, for example, bottle cap applications, and the shape defect that wrinkles occur in the flange portion when used for, for example, DRD can applications is caused. Therefore, the coiling temperature is set to 750 ℃ or less. Preferably 600 ℃ or higher and 700 ℃ or lower.
(Pickling)
Then, preferably, acid washing is performed. The pickling is not particularly limited as long as it can remove the surface scale.
Subsequently, cold rolling was performed in two passes with annealing.
(first cold rolling reduction: 88% or more)
First, the reduction ratio in the primary cold rolling step is set to 88% or more. When the reduction ratio in the primary cold rolling step is less than 88%, the strain imparted to the steel sheet in the cold rolling is reduced, so that recrystallization in the continuous annealing step becomes nonuniform, the standard deviation of ferrite becomes larger than 7.0 μm, and formability is deteriorated. Therefore, when the bottle cap is used for, for example, a bottle cap application, the shape of the bottle cap becomes uneven, and when the bottle cap is used for, for example, a DRD can application, a shape defect in which wrinkles are generated in a flange portion at the time of forming the DRD can is caused. Therefore, the reduction ratio in the primary cold rolling step is set to 88% or more. More preferably 89 to 94%.
In the annealing step after the primary cold rolling, the steel sheet is held at a temperature of 660 to 760 ℃ for 60 seconds or less, and then is subjected to a first stage cooling in which the steel sheet is cooled to a temperature of 450 ℃ or less at an average cooling rate of 10 ℃/s or more, and a second stage cooling in which the steel sheet is subsequently cooled to a temperature of 140 ℃ or less at an average cooling rate of 5 ℃/s or more.
(soaking temperature: 660-760 ℃ C.)
Namely, the soaking temperature in the continuous annealing step is 660 to 760 ℃. When the soaking temperature exceeds 760 ℃, a pass-through failure such as thermal buckling is likely to occur in the continuous annealing, which is not preferable. Further, the ferrite grain size of the steel sheet is partially coarsened, the standard deviation of ferrite becomes larger than 7.0 μm, the bottle cap shape becomes uneven when used for, for example, bottle cap applications, and a shape defect in which wrinkles are generated at the flange portion when used for, for example, DRD cans is caused when used for, for example, DRD cans. On the other hand, when the annealing temperature is less than 660 ℃, recrystallization becomes incomplete, ferrite grain size of the steel sheet becomes partially fine, standard deviation of ferrite grain size becomes larger than 7.0 μm, and in the case of application to, for example, a bottle cap, the shape of the bottle cap becomes uneven, and in the case of application to, for example, a DRD can, a shape defect in which wrinkles are generated in the flange portion at the time of forming the DRD can is caused. Therefore, the soaking temperature is set to 660 to 760 ℃. Preferably at a temperature of 680 to 730 ℃.
The holding time in the temperature range of 660 to 760 ℃ is set to 60 seconds or less. When the holding time exceeds 60 seconds, C contained in the steel sheet segregates to ferrite grain boundaries, precipitates as carbides during cooling in the continuous annealing step, contributes to a decrease in the amount of solid-solution C in the steel sheet strength, and lowers the yield strength. Further, when the steel sheet is used for, for example, a DRD can, a shape defect in which wrinkles are generated in the flange portion at the time of forming the DRD can is caused. Therefore, the holding time in the temperature range of 660 to 760 ℃ is set to 60 seconds or less. When the holding time is less than 5 seconds, the stability of the steel sheet passing through the rolls in the soaking zone is impaired, and therefore, it is preferable to set the holding time to 5 seconds or more.
(first-stage cooling: cooling to 450 ℃ or lower at an average cooling rate of 10 ℃/s or higher)
After the soaking, the steel sheet is cooled to a temperature range of 450 ℃ or lower at an average cooling rate of 10 ℃/s or higher. When the average cooling rate is less than 10 ℃/s, precipitation of carbides is promoted during cooling, the amount of solid solution C contributing to the strength of the steel sheet is reduced, and the yield strength is lowered. Further, when the steel sheet is used for, for example, a DRD can, a shape defect in which wrinkles are generated in the flange portion at the time of forming the DRD can is caused. Since the above-described effect is saturated when the average cooling rate exceeds 50 ℃/s, the average cooling rate is preferably set to 50 ℃/s or less.
When the cooling stop temperature in the preceding cooling after soaking exceeds 450 ℃, precipitation of carbides is promoted after the preceding cooling, which contributes to a decrease in the amount of solid solution C in the steel sheet strength and a decrease in the yield strength. Further, when the steel sheet is used for, for example, a DRD can, a shape defect in which wrinkles are generated in the flange portion at the time of forming the DRD can is caused. When the cooling stop temperature in the preceding stage cooling after soaking is lower than 300 ℃, the carbide precipitation suppressing effect is saturated, and not only does this deteriorate the shape of the steel sheet during passing, and the steel sheet cannot be uniformly cooled, and in the case of application to, for example, a bottle cap, the shape of the bottle cap becomes nonuniform, but also in the case of application to, for example, a DRD can, a shape defect occurs in which wrinkles are generated in the flange portion during forming of the DRD can, and therefore, the cooling stop temperature after soaking is preferably set to 300 ℃ or higher.
(latter stage cooling: cooling to 140 ℃ or lower at an average cooling rate of 5 ℃/s or higher)
In the subsequent cooling after the preceding cooling, the cooling is performed at an average cooling rate of 5 ℃/s or more from the cooling stop temperature at the preceding cooling to a temperature range of 140 ℃ or less. When the average cooling rate is less than 5 ℃/s, the amount of solid solution C contributing to the strength of the steel sheet is reduced, and the yield strength is lowered. Further, when the steel sheet is used for, for example, a DRD can, a shape defect in which wrinkles are generated in the flange portion at the time of forming the DRD can is caused. When the average cooling rate exceeds 30 ℃/s, the effect is saturated and the cost of the cooling equipment is excessive, and therefore, the average cooling rate in the subsequent stage cooling is preferably 30 ℃/s or less. More preferably 25 ℃/s or less.
In the latter stage cooling, the temperature is cooled to below 140 ℃. When the temperature exceeds 140 ℃, the amount of solid solution C contributing to the strength of the steel sheet is reduced, and the yield strength is lowered. Further, when the steel sheet is used for, for example, a DRD can, a shape defect in which wrinkles are generated in the flange portion at the time of forming the DRD can is caused. When the cooling stop temperature is less than 100 ℃, the effect is saturated and the cooling facility costs excessively, and therefore, it is preferably 100 ℃ or more. More preferably 120 ℃ or higher.
(reduction ratio of secondary cold rolling of 10% or more and 40% or less)
The steel sheet of the present invention can obtain high yield strength by the second cold rolling after annealing. That is, when the reduction ratio of the secondary cold rolling is less than 10%, sufficient yield strength cannot be obtained. When the reduction ratio of the secondary cold rolling exceeds 40%, uniformity of the shape of the bottle cap is impaired when the steel sheet is used for a bottle cap, for example. Further, when the steel sheet is used for, for example, a DRD can, a shape defect in which wrinkles are generated in a flange portion at the time of forming the DRD can is caused. Therefore, the reduction ratio of the secondary cold rolling is preferably set to 10% or more and 40% or less. More preferably, the reduction ratio of the secondary cold rolling is more than 15% and 35% or less.
The cold-rolled steel sheet obtained as described above may be subjected to plating treatment such as tin plating, chromium plating, and nickel plating on the surface of the steel sheet by plating, if necessary, to form a plated steel sheet, and then the plated steel sheet may be used. Since the film thickness of the surface treatment such as plating is sufficiently small relative to the sheet thickness, the influence on the mechanical properties of the steel sheet is negligible.
As described above, the steel sheet of the present invention can have sufficient strength and excellent material uniformity even when the steel sheet is made thin. Therefore, the steel sheet of the present invention is most suitable as a material for bottle caps or DRD cans in particular.
The bottle cap of the present invention is formed by using the steel plate. The bottle cap is mainly composed of a disk-shaped part for blocking a bottle mouth and a pleated part arranged around the disk-shaped part. The bottle cap of the present invention may be formed by punching the steel plate of the present invention into a circular blank and then press-forming the circular blank. The bottle cap of the present invention has sufficient yield strength and is manufactured from a steel sheet having excellent uniformity of material quality, and therefore, even when the bottle cap is made thin, the bottle cap has excellent compressive strength as a bottle cap, and the uniformity of the outer diameter and height of the bottle cap is excellent, and therefore, the bottle cap has the effect of improving the yield in the bottle cap manufacturing process and reducing the amount of waste discharged accompanying the bottle cap manufacturing.
Similarly, the DRD can of the present invention is formed using the steel sheet. The DRD can is formed by punching the steel sheet of the present invention into a circular blank, and then drawing and redrawing the blank. The DRD can using the steel sheet of the present invention as a raw material has a uniform shape and does not deviate from product specifications, and therefore, the yield in the DRD can manufacturing process is improved, and the effect of reducing the amount of waste generated in the DRD can manufacturing process is also obtained.
Example 1
Steels containing the compositions shown in table 1 and the balance consisting of Fe and unavoidable impurities were smelted in a converter and continuously cast to obtain billets. The slabs thus obtained were hot-rolled at slab heating temperatures, finish rolling temperatures, and coiling temperatures shown in table 2. This hot rolling is followed by pickling. Next, the first cold rolling was performed at the reduction ratios shown in table 2, the continuous annealing was performed under the continuous annealing conditions shown in table 2, and the second cold rolling was performed at the reduction ratios shown in table 2. The obtained steel sheet was continuously subjected to electrolytic chromic acid treatment to obtain tin-free steel.
[ TABLE 1] (Mass%)
| Steel No. | C | Si | Mn | P | S | AI | N | Remarks for note |
| 1 | 0.0072 | 0.01 | 0.16 | 0.018 | 0.006 | 0.036 | 0.0103 | Examples of the invention |
| 2 | 0.0098 | 0.01 | 0.14 | 0.019 | 0.010 | 0.044 | 0.0117 | Examples of the invention |
| 3 | 0.0061 | 0.02 | 0.15 | 0.018 | 0.009 | 0.038 | 0.0102 | Examples of the invention |
| 4 | 0.0089 | 0.02 | 0.13 | 0.026 | 0.026 | 0.031 | 0.0096 | Examples of the invention |
| 5 | 0.0065 | 0.02 | 0.12 | 0.031 | 0.017 | 0.040 | 0.0104 | Examples of the invention |
| 6 | 0.0083 | 0.04 | 0.26 | 0.015 | 0.013 | 0.047 | 0.0129 | Examples of the invention |
| 7 | 0.0064 | 0.01 | 0.58 | 0.019 | 0.011 | 0.028 | 0.0083 | Examples of the invention |
| 8 | 0.0093 | 0.01 | 0.06 | 0.017 | 0.015 | 0.025 | 0.0135 | Examples of the invention |
| 9 | 0.0067 | 0.03 | 0.48 | 0.022 | 0.030 | 0.041 | 0.0108 | Examples of the invention |
| 10 | 0.0080 | 0.02 | 0.11 | 0.018 | 0.027 | 0.036 | 0.0116 | Examples of the invention |
| 11 | 0.0063 | 0.03 | 0.16 | 0.034 | 0.009 | 0.046 | 0.0078 | Examples of the invention |
| 12 | 0.0086 | 0.02 | 0.53 | 0.008 | 0.028 | 0.032 | 0.0103 | Examples of the invention |
| 13 | 0.0064 | 0.03 | 0.27 | 0.019 | 0.046 | 0.029 | 0.0075 | Examples of the invention |
| 14 | 0.0075 | 0.01 | 0.38 | 0.021 | 0.004 | 0.043 | 0.0118 | Examples of the invention |
| 15 | 0.0091 | 0.01 | 0.42 | 0.016 | 0.016 | 0.049 | 0.0134 | Examples of the invention |
| 16 | 0.0062 | 0.02 | 0.25 | 0.023 | 0.042 | 0.020 | 0.0081 | Examples of the invention |
| 17 | 0.0079 | 0.01 | 0.36 | 0.024 | 0.009 | 0.045 | 0.0124 | Examples of the invention |
| 18 | 0.0081 | 0.02 | 0.44 | 0.012 | 0.023 | 0.030 | 0.0087 | Examples of the invention |
| 19 | 0.0064 | 0.02 | 0.13 | 0.031 | 0.033 | 0.046 | 0.0139 | Examples of the invention |
| 20 | 0.0095 | 0.02 | 0.22 | 0.011 | 0.036 | 0.023 | 0.0072 | Examples of the invention |
| 21 | 0.0084 | 0.03 | 0.35 | 0.016 | 0.018 | 0.044 | 0.0125 | Examples of the invention |
| 22 | 0.0087 | 0.03 | 0.17 | 0.027 | 0.024 | 0.038 | 0.0085 | Examples of the invention |
| 23 | 0.0106 | 0.02 | 0.20 | 0.018 | 0.009 | 0.036 | 0.0107 | Comparative example |
| 24 | 0.0118 | 0.01 | 0.17 | 0.011 | 0.010 | 0.030 | 0.0105 | Comparative example |
| 25 | 0.0141 | 0.01 | 0.19 | 0.015 | 0.008 | 0.037 | 0.0109 | Comparative example |
| 26 | 0.0052 | 0.02 | 0.22 | 0.019 | 0.007 | 0.041 | 0.0106 | Comparative example |
| 27 | 0.0045 | 0.02 | 0.16 | 0.017 | 0.009 | 0.032 | 0.0104 | Comparative example |
| 28 | 0.0034 | 0.02 | 0.14 | 0.012 | 0.010 | 0.042 | 0.0108 | Comparative example |
| 29 | 0.0078 | 0.01 | 0.78 | 0.025 | 0.039 | 0.039 | 0.0076 | Comparative example |
| 30 | 0.0065 | 0.03 | 0.33 | 0.013 | 0.025 | 0.083 | 0.0132 | Comparative example |
| 31 | 0.0072 | 0.03 | 0.14 | 0.027 | 0.014 | 0.007 | 0.0107 | Comparative example |
| 32 | 0.0085 | 0.01 | 0.16 | 0.014 | 0.009 | 0.033 | 0.0181 | Comparative example |
| 33 | 0.0081 | 0.02 | 0.22 | 0.010 | 0.007 | 0.038 | 0.0168 | Comparative example |
| 34 | 0.0077 | 0.02 | 0.21 | 0.019 | 0.008 | 0.042 | 0.0156 | Comparative example |
| 35 | 0.0083 | 0.01 | 0.15 | 0.013 | 0.010 | 0.035 | 0.0066 | Comparative example |
| 36 | 0.0079 | 0.01 | 0.17 | 0.020 | 0.008 | 0.044 | 0.0052 | Comparative example |
| 37 | 0.0084 | 0.01 | 0.19 | 0.014 | 0.005 | 0.036 | 0.0044 | Comparative example |
| 38 | 0.0092 | 0.02 | 0.21 | 0.068 | 0.009 | 0.038 | 0.0105 | Comparative example |
| 39 | 0.0075 | 0.96 | 0.19 | 0.022 | 0.011 | 0.042 | 0.0118 | Comparative example |
Note) underline portion: outside the scope of the invention
For the steel sheet obtained by the above steps, heat treatment equivalent to paint-sintering was performed at 210 ℃ and 15 minutes, and then a tensile test was performed. In the tensile test, a tensile test piece having a JIS5 standard was used, and the yield strength in the rolling direction was measured in accordance with "JIS Z2241". The heat treatment corresponding to the coating sintering does not affect the steel sheet material before the heat treatment.
The obtained steel sheet was molded into a bottle cap, and the bottle cap formability was evaluated. That is, 20 (N-20) caps were formed for each steel sheet by press working using a circular blank having a diameter of 37 mm. The height of the cap (distance from the top surface of the cap to the lower end of the skirt) is measured using a micrometer, and the cap shape is determined to be excellent when the standard deviation of the cap height of N-20 is 0.09mm or less, and the cap shape difference is determined to be when the standard deviation of the cap height of N-20 is greater than 0.09 mm. The obtained results are shown in table 2.
Further, using the obtained steel sheet, heat treatment equivalent to paint sintering was performed at 210 ℃ for 15 minutes, and then a DRD can was formed, and the formability of the DRD can was evaluated. Namely, a circular blank having a diameter of 158mm was subjected to drawing and redrawing to form a DRD can having an inner diameter of 82.8mm and a flange diameter of 102mm, and the formability of the DRD can was evaluated. In the evaluation, a sample in which 3 or more minute wrinkles were visually observed in the flange portion was set to x, and a sample in which 2 or less minute wrinkles were observed in the flange portion was set to o. The evaluation results are shown in table 2.
As is clear from Table 2, the steel sheets No.1 to No. 22, which are examples of the present invention, had yield strength of 560MPa or more in the rolling direction and a standard deviation of the bottle cap height of 0.09mm or less, and the bottle cap formability was good. In addition, the number of wrinkles generated in the DRD can forming is 2 or less, and the DRD can formability is also good.
On the other hand, it is found that the steel sheets of nos. 23 to 25 as comparative examples have an excessive C content, and therefore, the standard deviation of ferrite grain size is more than 7.0 μm, the standard deviation of cap height is more than 0.09mm, and the cap formability is deteriorated and the DRD can formability is also deteriorated. It is found that the steel sheets of Nos. 26 to 28 had an excessively small C content, and therefore had a standard deviation of ferrite grain size of more than 7.0 μm and a standard deviation of cap height of more than 0.09mm, and deteriorated cap formability. It is found that the steel sheet of No.29 has an excessive Mn content, and therefore, the standard deviation of ferrite grain size is larger than 7.0. mu.m, the standard deviation of cap height is larger than 0.09mm, the cap formability is deteriorated, and the DRD can formability is also deteriorated. It is found that in the steel sheet of No.30, the amount of N contributing to the strength of the steel sheet as solid-solution N is decreased due to the increase in the formation of AlN because of the excessive Al content, and the strength of the steel sheet is decreased. In addition, the DRD can formability is also deteriorated. In the steel sheet of No.31, the Al content was too small, and therefore, the effect as a deoxidizer was insufficient, solidification defects occurred, and the steel-making cost increased. Further, it is found that since an appropriate amount of AlN cannot be secured at the time of recrystallization of ferrite during annealing, the standard deviation of ferrite grain size after annealing becomes large, the ferrite grain size of the steel sheet after secondary cold rolling becomes coarse, the standard deviation of ferrite grain size is larger than 7.0 μm, the standard deviation of bottle cap height is larger than 0.09mm, the bottle cap formability is deteriorated, and the DRD can formability is also deteriorated. It is found that the steel sheets of nos. 32 to 34 had an excessive N content, and therefore the ferrite grain size of the steel sheet after the secondary cold rolling was very fine, the standard deviation of the ferrite grain size was more than 7.0 μm, the standard deviation of the bottle cap height was more than 0.09mm, the bottle cap formability was deteriorated, and the DRD can formability was also deteriorated. It is found that the steel sheets of nos. 35 to 37 had too small content of N, and therefore had coarse ferrite grain size, standard deviation of ferrite grain size of more than 7.0 μm, standard deviation of bottle cap height of more than 0.09mm, and also had poor bottle cap formability and DRD can formability, and that the amount of N contributing to steel sheet strength reduction in the form of solid solution N decreased the steel sheet strength. Further, it is found that, in the steel sheet of No.38, since the content of P is too large, the standard deviation of ferrite grain size is more than 7.0 μm, the standard deviation of cap height is more than 0.09mm, the cap formability is deteriorated, and the DRD can formability is also deteriorated. It is found that the steel sheet of No.39 has an excessive Si content, and therefore, the standard deviation of ferrite grain size is larger than 7.0. mu.m, the standard deviation of cap height is larger than 0.09mm, the cap formability is deteriorated, and the DRD can formability is also deteriorated.
Example 2
Steels containing the composition of steel nos. 5, 9, 18, 21, 28, 29, and 31 shown in table 1 and the balance of Fe and inevitable impurities were smelted in a converter and continuously cast to obtain billets. The slabs thus obtained were hot-rolled at slab heating temperatures, finish rolling temperatures, and coiling temperatures shown in table 3. Pickling is performed after hot rolling. Next, the first cold rolling was performed at the reduction ratios shown in table 3, and the continuous annealing was performed at the soaking holding temperature, soaking holding time, front stage cooling average speed, front stage cooling stop temperature, rear stage cooling average speed, and rear stage cooling stop temperature shown in table 3, followed by the second cold rolling at the reduction ratios shown in table 3. The obtained steel sheet was continuously subjected to electrolytic chromic acid treatment to obtain tin-free steel.
The steel sheet obtained in the above procedure was subjected to a tensile test in the same manner as described above, and further evaluated for bottle cap formability and DRD can formability. The obtained results are shown in table 3.
According to table 3, the steel sheets of steel sheets nos. 40, 43, 45, 47, 48, 52 to 55, 58, 59, 63, 64, 66, 69, 70, 71, which are examples of the present invention, had yield strengths in the rolling direction of 560MPa or more, standard deviations of the cap heights of 0.09mm or less, and good cap formability and DRD can formability.
On the other hand, it is found that the steel sheets of steel sheets nos. 41, 49, 50, 56, 61, 68 and 72 as comparative examples have reduced yield strength in the rolling direction because the slab heating temperature, soaking holding time, average speed of first-stage cooling, reduction ratio of second cold rolling, average speed of second-stage cooling, stop temperature of first-stage cooling and stop temperature of second-stage cooling are out of the range of the present invention. It is found that the steel sheet of steel sheet No.62 as a comparative example has an excessively high secondary cold reduction ratio, and therefore the anisotropy of the steel sheet is increased, the standard deviation of the cap height is more than 0.09mm, the cap formability is deteriorated, and the DRD can formability is also deteriorated. It is found that, in the steel sheets of steel sheet nos. 42, 44, 46, 51, 57, 60, 65, 67, 73 and 74 as comparative examples, since any one of the slab heating temperature, the final stand reduction of hot rolling, the coiling temperature, the primary cold rolling reduction, the soaking holding temperature, the primary cooling stop temperature, the secondary cooling average speed, the secondary cooling stop temperature and the secondary cold rolling reduction is out of the range of the present invention, the yield strength in the rolling direction is reduced or the standard deviation of the ferrite grain diameter is more than 7.0 μm, the standard deviation of the cap height is more than 0.09mm, the cap formability is deteriorated and the DRD can formability is also deteriorated.
Claims (5)
1. A steel sheet having a composition containing, in mass%, C: more than 0.0060% and 0.0100% or less, Si: 0.05% or less, Mn: 0.05% or more and 0.60% or less, P: 0.050% or less, S: 0.050% or less, Al: 0.020% or more and 0.050% or less, and N: 0.0070% to 0.0140% inclusive, and the balance Fe and inevitable impurities,
a ferrite phase in a region from 1/4 mm in thickness to the central part of the thickness, wherein the standard deviation of ferrite grain diameter in the ferrite phase is 7.0 μm or less,
the yield strength is 560MPa or more.
2. The steel sheet according to claim 1, which has a sheet thickness of 0.20mm or less.
3. A bottle cap made of the steel plate according to claim 1 or 2.
4. A DRD can constructed from the steel sheet of claim 1 or 2.
5. A method for manufacturing a steel sheet according to claim 1 or 2, comprising:
a hot rolling step of heating a steel material at 1200 ℃ or higher, rolling the heated material at a finish rolling temperature of 870 ℃ or higher and a reduction ratio of 10% or higher in a final stand, and coiling the rolled material at a temperature of 550 to 750 ℃;
a pickling step of pickling the hot-rolled sheet after hot rolling;
a primary cold rolling step of cold rolling the hot-rolled sheet after pickling at a reduction of 88% or more;
an annealing step of keeping the cold-rolled sheet after the primary cold rolling at a temperature of 660 to 760 ℃ for 60 seconds or less, cooling the cold-rolled sheet at an average cooling rate of 10 ℃/s or more to a temperature range of 450 ℃ or less and 300 ℃ or more, and then cooling the cold-rolled sheet at an average cooling rate of 5 ℃/s or more and 30 ℃/s or less to a temperature range of 140 ℃ or less; and
and a secondary cold rolling step of cold rolling the annealed sheet at a reduction ratio of 10% to 40%.
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| CN102766800A (en) * | 2011-05-05 | 2012-11-07 | 上海梅山钢铁股份有限公司 | Steel for hard tinplate bottle caps and production method thereof |
| CN103649353A (en) * | 2011-07-12 | 2014-03-19 | 杰富意钢铁株式会社 | Steel sheet for can and process for producing same |
| TW201631177A (en) * | 2014-12-26 | 2016-09-01 | 新日鐵住金股份有限公司 | Manufacturing method of steel sheet for crown cap and steel sheet for crown cap |
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| US9090960B2 (en) * | 2010-11-22 | 2015-07-28 | Nippon Steel and Sumitomo Metal Corporation | Strain aging hardening steel sheet excellent in aging resistance, and manufacturing method thereof |
| BR112016019612A2 (en) * | 2014-02-25 | 2018-10-23 | Jfe Steel Corp | steel sheet for crown cap, method for manufacturing crown cap and crown cap |
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| CN102766800A (en) * | 2011-05-05 | 2012-11-07 | 上海梅山钢铁股份有限公司 | Steel for hard tinplate bottle caps and production method thereof |
| CN103649353A (en) * | 2011-07-12 | 2014-03-19 | 杰富意钢铁株式会社 | Steel sheet for can and process for producing same |
| TW201631177A (en) * | 2014-12-26 | 2016-09-01 | 新日鐵住金股份有限公司 | Manufacturing method of steel sheet for crown cap and steel sheet for crown cap |
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