Title of the invention: Steel sheet and its manufacturing method
Technical field
[0001]
　The present invention relates to a steel sheet and a method for manufacturing the same.
　The present application claims priority based on Japanese Patent Application No. 2019-185996 filed in Japan on October 9, 2019, the contents of which are incorporated herein by reference.
Background technology
[0002]
　In order to reduce the amount of carbon dioxide emitted from automobiles, attempts are being made to reduce the weight of automobile bodies while ensuring safety by using high-strength steel plates. However, in general, when the strength of the steel sheet is increased, the formability is lowered. In high-strength steel sheets, it is difficult to achieve both strength and formability, and several means have been proposed to solve this problem.
[0003]
　For example, Patent Document 1 describes in terms of mass%, C: 0.15 to 0.35%, Si: 0.5 to 3.0%, Mn: 0.5 to 1.5%, Al: 0.001. Each contains ~ 0.10%, the balance is composed of iron and unavoidable impurities, the content of the predetermined composition among the unavoidable impurities is limited, and martensite: 90% or more remains in the area ratio to the whole structure. Austenite: A region having a structure consisting of 0.5% or more and having a local Mn concentration of 1.2 times or more the Mn content of the entire steel plate exists in an area ratio of 1% or more and a tensile strength of 1470 MPa. As described above, an ultra-high strength steel plate characterized in that the yield ratio is 0.75 or more and the total elongation is 10% or more is disclosed.
[0004]
　Patent Document 2 describes a hot-dip galvanized steel sheet having a hot-dip galvanized layer on the surface of the steel sheet, wherein the component composition of the steel sheet is C: 0.03 to 0.70%, Si: 0. 25 to 2.50%, Mn: 1.00 to 5.00%, P: 0.0005 to 0.100%, S: 0.010% or less, sol. Al: 0.001 to 2.500%, N: 0.020% or less, B: 0 to 0.0200%, Ti: 0 to 0.30%, Nb: 0 to 0.30%, V: 0 to 0.30%, Cr: 0 to 2.00%, Mo: 0 to 2.00%, Cu: 0 to 2.00%, Ni: 0 to 2.00%, Ca: 0 to 0.010%, It contains Mg: 0 to 0.010%, REM: 0 to 0.10%, and Bi: 0 to 0.050%, the balance is Fe and unavoidable impurities, and the metal structure of the steel plate is by volume%. Retained austenite: more than 5.0% and tempered martensite: more than 5.0%, the retained austenite contained C: 0.85% by mass or more, and the old in the metal structure of the steel plate. Ratio of C segregation amount (number of atoms / nm 2 ): [C] γgb and P segregation amount (number of atoms / nm 2 ): [P] γgb at the austenite grain boundary: [C] γgb / [P] γgb is 4 A hot-dip zinc-plated steel sheet characterized by being .0 or more is disclosed.
Prior art literature
Patent documents
[0005]
Patent Document 1: Japanese Patent Application Laid-Open No. 2019-2078
Patent Document 2: Japanese Patent Application Laid-Open No. 6421903
Outline of the invention
Problems to be solved by the invention
[0006]
　In Patent Document 1 and Patent Document 2, a general yield strength (yield ratio) is examined, but in view of recent demands for weight reduction of automobile bodies, it is required to have more suitable characteristics. There is. Specifically, it is preferable to increase the elastic limit and widen the elastic deformation range because the absorption performance of the impact energy of the steel sheet is improved.
　In view of the above, the present invention provides a steel sheet having a tensile strength of 1310 MPa or more and maintaining a work hardening rate of more than 180 GPa up to a region where the true stress value in the stress-strain curve is 600 MPa or more, and a method for manufacturing the same. The purpose is.
Means to solve problems
[0007]
　The present invention has been made based on the above findings, and the gist thereof is as follows.
[0008]
[1] The steel plate according to one aspect of the present invention has a chemical composition of% by mass,
　C: 0.20 to 0.40%,
　Si: 0.10% to 1.0%,
　Al: 0.20%. ~ 1.0%,
　Mn: 0.1 ~ 4.0%,
　P: 0.0200% or less,
　S: 0.0200% or less,
　N: 0.0200% or less,
　O: 0.0200% or less,
　Ni : 0 to 1.00%,
　Mo: 0 to 1.00%,
　Cr: 0 to 2.000%,
　Ti: 0 to 0.500%,
　B: 0 to 0.0100%,
　Nb: 0 to 0. 500%,
　V: 0 to 0.500%,
　Cu: 0 to 0.500%,
　W: 0 to 0.10%,
　Ta: 0 to 0.10%,
　Sn: 0 to 0.050%,
　Co: 0 to 0.50%,
　Sb: 0 to 0.050%,
　As: 0 to 0.050%,
　Mg: 0 to 0.050%,
　Ca: 0 to 0.040%,
　Y: 0 to 0.050%,
　Zr: 0 to 0.050%, and
　La: 0 to 0.050%
, the balance is composed of iron and impurities, and
　Si + Al is 0.30 to 1.4%. Filled,
　the metallographic structure at 1/4 part of the plate thickness is
　　ferrite, bainite and pearlite: 0-10% in total,
　　retained austenite: 1-15%, the
　　balance is martensite, in the
　old austenite grain boundaries. The proportion of martensite or retained austenite having a width of 50 nm to 2 μm is 70% or more.
[2] In the steel sheet according to the above [1], the chemical composition is, in mass%,
　Ni: 0.01 to 1.00%,
　Mo: 0.01 to 1.00%,
　Cr: 0.001 to. 2,000%,
　Ti: 0.001 to 0.500%,
　B: 0.0001 to 0.0100%,
　Nb: 0.001 to 0.500%,
　V: 0.001 to 0.500%,
　Cu : 0.001 to 0.500%,
　W: 0.001 to 0.10%,
　Ta: 0.001 to 0.10%,
　Sn: 0.001 to 0.050%,
　Co: 0.001 to 0.50%,
　Sb: 0.001 to 0.050%,
　As: 0.001 to 0.050%,
　Mg: 0.0001 to From 0.050%,
　Ca: 0.001 to 0.040%,
　Y: 0.001 to 0.050%,
　Zr: 0.001 to 0.050%,
　La: 0.001 to 0.050%
. It may contain one or more selected from the group.
[3] The steel sheet according to the above [1] or [2] may have a hot-dip galvanized layer on the surface.
[4] The steel sheet according to the above [1] or [2] may have an alloyed hot-dip galvanized layer on the surface.
[5] In the steel sheet according to any one of [1] to [4] above, the grain boundary thickness of the old austenite may be 50 nm to 2 μm.
[0009]
[6] The method for producing a steel plate according to another aspect of the present invention includes a hot rolling step of hot rolling a slab having the chemical composition according to [1] or [2] into a hot rolled steel plate.
　It has a cold rolling step of pickling the hot-rolled steel sheet and then cold-rolling to obtain a cold-rolled steel sheet, and an
　annealing step of annealing the 　cold 　　-rolled steel sheet. The temperature range starting from 830 ° C and ending at T ° C, which is a temperature of 840 ° C to 900 ° C, is heated at a heating rate of 1.0 ° C / s or less, 　and {T / 13- (100 ×) at the T ° C. Si) Hold for 0.8 − (70 × Al) 0.5 } seconds or more, and 　　after the holding, cool to an average cooling rate of 20 ° C./s to 60 ° C./s to a cooling stop temperature of 300 ° C. or lower. [7] In the method for manufacturing a steel sheet according to the above [6], the cold-rolled steel sheet after the baking step is controlled in a temperature range of (zinc plating bath temperature −40) ° C. to (zinc plating bath temperature +50) ° C. Then, hot-dip galvanizing may be formed by immersing in a hot-dip galvanizing bath. [8] In the method for producing a steel sheet according to the above [7], the hot dip galvanizing may be alloyed in a temperature range of 300 to 500 ° C.

The invention's effect
[0010]
　According to the present invention, it is possible to provide a steel sheet having a tensile strength of 1310 MPa or more and maintaining a work hardening rate of more than 180 GPa up to a region where the true stress value in the stress-strain curve is 600 MPa or more, and a method for manufacturing the same. can.
A brief description of the drawing
[0011]
[Fig. 1] Fig. 1 is a schematic view showing a state of a test in which two steel plates are spot welded and the embrittlement crack resistance of a molten metal is evaluated.
Embodiment for carrying out the invention
[0012]
　Hereinafter, the steel sheet and the manufacturing method thereof according to the present embodiment will be described with reference to the drawings as appropriate.
　The steel plate according to this embodiment has a chemical composition of% by mass,
　C: 0.20 to 0.40%,
　Si: 0.10% to 1.0%,
　Al: 0.20% to 1.0%. ,
　Mn: 0.1 to 4.0%,
　P: 0.0200% or less,
　S: 0.0200% or less,
　N: 0.0200% or less,
　O: 0.0200% or less,
　Ni: 0 to 1. 00%,
　Mo: 0 to 1.00%,
　Cr: 0 to 2.000%,
　Ti: 0 to 0.500%,
　B: 0 to 0.0100%,
　Nb: 0 to 0.500%,
　V: 0 to 0.500%,
　Cu: 0 to 0.500%,
　W: 0 to 0.10%,
　Ta: 0 to 0.10%,
　Sn: 0 to 0.050%,
　Co: 0 to 0.50 %,
　Sb: 0 to 0.050%,
　As: 0 to 0.050%,
　Mg: 0 to 0.050%,
　Ca: 0 to 0.040%,
　Y: 0 to 0.050%,
　Zr: 0 to 0.050%, and
　La: 0 to 0.050%
, the balance Is composed of iron and impurities,
　Si + Al fills 0.30 to 1.4%, and
　the metallographic structure at 1/4 part of the plate thickness is
　　ferrite, bainite and pearlite: 0 to 10% in total,
　　retained austenite . 1: 15%, the
　　balance is martensite, and
　the proportion of martensite or retained austenite having a width of 50 nm to 2 μm in the former austenite grain boundaries is 70% or more.
[0013]
　Hereinafter, the steel sheet according to one aspect of the present invention will be described.
[0014]
　First, the metal structure of the steel sheet according to the present embodiment will be described. Hereinafter, since the tissue fraction is measured by image processing, it is displayed as an area ratio, but the area ratio here may be regarded as a volume ratio. Therefore, the unit "%" of the tissue fraction shall mean volume%.
[0015]
　Metallic structure
　Ferrite, bainite and pearlite: 0 to 10% ferrite in total
　is a soft structure, so that it is easily deformed and contributes to the improvement of elongation. However, in order to obtain suitable strength, it is necessary to limit the area ratio of ferrite.
　Bainite is a phase obtained by keeping bainite at 350 ° C. or higher and 450 ° C. or lower for a certain period of time after annealing. Since bainite is soft to martensite, it has an effect of improving ductility, but in order to obtain suitable strength, it is necessary to limit the area ratio as in ferrite.
　Pearlite is a structure containing hard cementite, which becomes a starting point of void generation during hole expansion and deteriorates hole expansion property. Therefore, it is necessary to limit the area ratio as in ferrite and bainite.
　Therefore, in the steel sheet according to the present embodiment, the area ratio of ferrite, bainite and pearlite is 10% or less in total. Ferrite, bainite and pearlite may not be included, so the lower limit is 0%.
[0016]
　Residual austenite: 1-15%
　retained austenite improves ductility due to the TRIP effect and contributes to improved uniform elongation. Therefore, the area ratio of retained austenite is set to 1% or more.
　On the other hand, when the area ratio of retained austenite becomes excessive, the particle size of retained austenite becomes large. Retained austenite having such a large particle size becomes coarse and hard martensite after deformation. In this case, it is not preferable because it tends to be a starting point of cracking and the hole expanding property is deteriorated. Therefore, the area ratio of retained austenite is 15% or less, preferably 12% or less, and more preferably 10% or less.
[0017]
　Remaining : Martensite
　The structure of the remnants other than ferrite, bainite, pearlite and retained austenite is martensite. Here, martensite is a general term for so-called fresh martensite and tempered martensite.
　Since fresh martensite is a hard structure with a high dislocation density, it is a structure that contributes to the improvement of tensile strength.
　Tempering martensite is a collection of lath-shaped crystal grains, similar to fresh martensite. On the other hand, unlike fresh martensite, it is a hard structure containing fine iron-based carbides inside due to tempering. Tempering martensite is obtained by tempering martensite produced by cooling after annealing by heat treatment or the like.
　Bainite is also a structure containing fine iron-based carbides, but tempered martensite has multiple variants of iron-based carbides, and bainite can be distinguished by a single variant of iron-based carbides.
[0018]
　In the former austenite grain boundaries, the proportion of martensite or retained austenite having a width of 50 nm to 2 μm is 70% or more
　. If the percentage of sites or retained austenite present is less than 70%, the area free of martensite or retained austenite is widened. Micro-surrection preferentially occurs in regions where martensite and retained austenite are absent. Therefore, it is difficult to inhibit the motion of dislocations, and it is difficult to suppress micro-yield during tensile deformation, which is not preferable. Therefore, in the steel sheet according to the present embodiment, the ratio of martensite or retained austenite having a width of 50 nm to 2 μm in the old austenite grain boundaries is 70% or more, preferably 80% or more.
　In the former austenite grain boundaries, the proportion of martensite or retained austenite having a width of 50 nm to 2 μm is ideally 100%, but the actual upper limit is about 98%.
　When the width of martensite or retained austenite is less than 50 nm, the effect of suppressing micro-yield is insufficient. Therefore, in this embodiment, the width of martensite or retained austenite is set to 50 nm or more.
　On the other hand, when the width of martensite or retained austenite is more than 2 μm, the portion becomes too hard, a difference in strength from the surrounding soft phase occurs, and it becomes easy to become a starting point of void generation, which is not preferable. Therefore, in this embodiment, the width of martensite or retained austenite is set to 2 μm or less.
　As long as the proportion of martensite or retained austenite having a width of 50 nm to 2 μm in the former austenite grain boundaries, that is, the grain boundary coverage is 70% or more, other requirements for martensite or retained austenite covering the former austenite grain boundaries are Not particularly limited. For example, if the grain boundary coverage is 70% or more, even if martensite or retained austenite having a width of less than 50 nm or more than 2 μm is present at the former austenite grain boundaries, it inhibits the movement of dislocations and undergoes tensile deformation. It is possible to suppress the micro-yield of. Therefore, it is permissible for martensite or retained austenite having a width of less than 50 nm or more than 2 μm to be present at the prior austenite grain boundaries.
　On the other hand, in addition to the grain boundary coverage, the grain boundary thickness of the old austenite may be limited to the range of 50 nm to 2 μm. The grain boundary thickness of the former austenite is an average value of the widths of martensite or retained austenite covering the former austenite grain boundaries. In measuring the grain boundary thickness, the width of the old austenite grain boundaries not covered with martensite or retained austenite is regarded as 0 nm. By limiting the grain boundary thickness to the range of 50 nm to 2 μm, the effect of suppressing micro-yielding is further enhanced.
[0019]
　Next, the identification of ferrite, bainite, pearlite, retained austenite, and martensite and the calculation of the area ratio will be described.
[0020]
　The identification of each metal structure and the calculation of the area ratio are performed by EBSD (Electron Backscattering Diffraction), X-ray measurement, corrosion using a nital reagent or a repera solution, and scanning electron microscopy of the steel plate at 1/4 part of the plate thickness. A 100 μm × 100 μm region of a cross section along the rolling direction and perpendicular to the plate surface can be observed at a magnification of 1000 to 50,000 times.
[0021]
　The volume fraction of retained austenite can be calculated by measuring the diffraction intensity using X-rays.
[0022]
　In the measurement using X-rays, the sample from the plate surface to the depth 1/4 position is removed by mechanical polishing and chemical polishing, and at the plate thickness 1/4 position, MoKα rays are used to remove the bcc phase (200). ), (211), and the integrated intensity ratio of the diffraction peaks of the (200), (220), and (311) of the fcc phase, it is possible to calculate the tissue fraction of retained austenite. The 5-peak method is used as a general calculation method.
[0023]
　The area ratio of martensite is calculated by the following procedure. The observation surface of the sample is etched with a repera solution, and a region of 100 μm × 100 μm is observed by FE-SEM within the range of 1/8 to 3/8 of the plate thickness centered on 1/4 part of the plate thickness. Since martensite and retained austenite are not corroded by repera corrosion, the area ratio of the uncorroded area is the total area ratio of martensite and retained austenite. The area ratio of martensite can be calculated by subtracting the area ratio of retained austenite measured by X-ray from the area ratio of this uncorroded region. As the area ratio of martensite, the average value of the area ratio measured at three places is used.
[0024]
　Martensite can be distinguished from other tissues in the electron channeling contrast image by scanning electron microscopy. In the above image, the region having a high dislocation density and having a substructure such as a block or a packet in the crystal grain is martensite.
　Tempered martensite can also be distinguished from bainite in that cementite within the tissue has multiple variants.
[0025]
　A structure not identified as retained austenite or martensite by the above method is judged to be ferrite, bainite or pearlite.
[0026]
　The proportion of martensite or retained austenite having a width of 50 nm to 2 μm in the former austenite grain boundaries is measured as follows.
　The observation surface of the sample is corroded with a nital reagent, and a region of 100 μm × 100 μm is observed using FE-SEM within the range of 1/8 to 3/8 of the plate thickness centered on the plate thickness of 1/4. Residual γ and martensite with concentrated carbon are slowly corroded and appear white. Those that appear white on the edges are judged to be martensite or retained austenite existing at the old γ grain boundaries. Since the old γ grains can be identified by the inverse analysis of the EBSD measurement results, the grain boundary length L of 10 old γ grains arbitrarily extracted in the region of 100 μm × 100 μm is obtained by image analysis. Further, by image analysis of the SEM photograph of the corresponding portion, the length l of the portion covered with martensite and / or retained austenite having a width of 50 nm to 2 μm in the old γ grain boundary can be obtained. .. By dividing l by L, the proportion of martensite or retained austenite having a width of 50 nm to 2 μm in the old γ grain boundaries is determined.
　A more specific method for measuring the length l is as follows.
(1) The old γ grains in the FE-SEM photograph are identified by the inverse analysis of the EBSD measurement result, and 10 old γ grains to be measured are extracted from the old γ grains.
(2) Identify a tissue (tissue that stands out white) that is determined to be martensite or retained austenite that overlaps the grain boundaries of 10 old γ grains.
(3) For 10 old γ grains, lines perpendicular to the old γ grain boundaries are described at 100 nm intervals. Due to these lines, the image of the structure overlapping the old γ grain boundaries shows the appearance of being sliced ​​at 100 nm intervals perpendicular to the old γ grain boundaries.
(4) The shape of each of the sliced ​​tissues is regarded as a rectangle having a width of 100 nm, and the length x along the direction perpendicular to the old γ grain boundaries of each of the tissues is calculated. Specifically, the area of ​​each of the tissues (unit: nm 2 ) is first measured by image analysis, and then the value x of the area of ​​each of the tissues divided by 100 nm is calculated. This length x corresponds to the width of martensite or retained austenite at the old γ grain boundaries.
(5) Among the sliced ​​tissues, those having a length x in the range of 50 nm to 2 μm along the direction perpendicular to the old γ grain boundaries are extracted.
(6) The length of the old γ grain boundaries covered by the extracted tissue was measured, and this was measured as the length of the portion covered with martensite and / or austenite having a width of 50 nm to 2 μm described above. It is regarded as "sa l".
　The grain boundary thickness is the average value of the length x along the direction perpendicular to the old γ grain boundary of all the tissues sliced ​​at 100 nm intervals by the above method for measuring the length l. Here, in calculating the grain boundary thickness, the "length x of each sliced ​​structure along the direction perpendicular to the old γ grain boundary" in the old γ grain boundary where martensite or retained austenite does not exist is 0 nm. Consider it as. In other words, the grain boundary thickness also takes into account the old γ grain boundaries not coated with martensite or retained austenite and the old γ grain boundaries coated with martensite or retained austenite having a width greater than 2 μm or less than 50 nm. , The average value of the width of the old gamma grain boundaries.
　In a normal steel sheet, carbon segregation to the old γ grain boundaries does not proceed, so that the amount of martensite and / or retained austenite at the old γ grain boundaries is small. Therefore, even when the corroded observation surface of a normal steel sheet is observed by FE-SEM, the old γ grain boundaries that are raised in white are often not recognized. Therefore, with a normal steel sheet, the old γ grain boundaries may not be clearly determined based on the FE-SEM photograph. However, since the old γ grains can be identified by the inverse analysis of the EBSD measurement results as described above, the grain boundary thickness and the grain boundary coverage of a normal steel sheet can also be measured according to the above method.
[0027]
　Next, the reason for limiting the chemical composition of the steel sheet according to the present embodiment will be described. Hereinafter,% related to the component composition means mass%. Further, the numerical range represented by using "-" means a range including the numerical values ​​before and after "-" as the lower limit value and the upper limit value unless otherwise specified. That is, 0.20 to 0.40% means that it is 0.20% or more and 0.40% or less.
[0028]
　Chemical composition
　C: 0.20 to 0.40%
　C is an element that secures a predetermined amount of martensite and improves the strength of the steel sheet. If the C content is less than 0.20%, it is difficult to obtain a predetermined amount of martensite and the desired tensile strength cannot be secured. Therefore, the C content is set to 0.20% or more. The C content is preferably 0.25% or more.
[0029]
　On the other hand, when the C content exceeds 0.40%, the weldability deteriorates and the hole widening property deteriorates. The hydrogen embrittlement resistance also deteriorates. Therefore, the C content is set to 0.40% or less. The C content is preferably 0.35% or less.
[0030]
　Si: 0.10% to 1.0%
　Si is an element useful for increasing the strength of a steel sheet by solid solution strengthening. Further, since Si suppresses the formation of cementite, it is an effective element for promoting the concentration of C in austenite and forming retained austenite after annealing. Further, Si has an effect of segregating carbon (C) on the γ grain boundary in the annealing step described later. If the Si content is 0.10% or less, it is difficult to obtain the effect of the above action, it is difficult to achieve uniform elongation, and hydrogen embrittlement resistance is deteriorated, which is not preferable. Therefore, the Si content is 0.10% or more, preferably 0.50% or more, and more preferably 0.60% or more.
　On the other hand, when the Si content is more than 1.0%, LME cracking (also referred to as liquid metal embrittlement cracking) is likely to occur during welding. Further, the chemical conversion treatment property and the plating property are significantly deteriorated. Therefore, the Si content is 1.0% or less, preferably 0.90% or less, and more preferably 0.80% or less.
[0031]
　Al: 0.20% to 1.0%
　Al is an element having an action of deoxidizing molten steel. Further, Al also has an effect of segregating carbon (C) on the γ grain boundary in the annealing step described later. As a result, in the steel sheet according to the present embodiment, the old γ grain boundaries are coated with martensite or retained austenite, and a desired tensile strength and a wide elastic deformation region can be obtained. When the Al content is less than 0.20%, these effects are not exhibited. Therefore, the Al content is 0.20% or more, preferably 0.30% or more, and more preferably 0.40% or more. .. From the viewpoint of further increasing the elastic limit by segregating more C on the grain boundaries, it is more preferable to set the Al content to more than 0.50%, and further to set it to 0.55% or more. It is preferable, preferably 0.60% or more, and particularly preferably 0.60% or more.
　On the other hand, if the Al content is too high, not only surface defects due to alumina are likely to occur, but also the transformation point is greatly increased, and the area ratio of ferrite is increased. In this case, it becomes difficult to obtain the above-mentioned metal structure, and sufficient tensile strength cannot be obtained. Furthermore, a high Al content deteriorates castability. Therefore, the Al content is 1.0% or less, preferably 0.80% or less, and more preferably 0.70% or less.
[0032]
　Si + Al: 0.30 to 1.4%
　As described above, both Si and Al are elements having an effect of segregating C at the γ grain boundary in the annealing step. When Si + Al (total of Si content and Al content) is less than 0.30%, the effect of segregating C at the γ grain boundaries cannot be sufficiently obtained in the annealing step, and the desired tensile strength can be obtained. It will be difficult. Therefore, Si + Al is set to 0.30% or more, preferably 0.80% or more, and more preferably 1.0% or more.
[0033]
　On the other hand, if Si + Al exceeds 1.4%, slab cracking occurs due to excessive addition of Si and / or Al, so Si + Al is set to 1.4% or less, preferably 1.3% or less, more preferably 1.2. % Or less.
[0034]
　Mn: 0.1 to 4.0%
　Mn has an effect of improving the hardenability of steel and is an effective element for obtaining the above-mentioned metal structure. If the Mn content is less than 0.1%, it becomes difficult to obtain the above metal structure. In this case, sufficient tensile strength cannot be obtained. Therefore, the Mn content is 0.1% or more, preferably 1.0% or more.
　On the other hand, when the Mn content is more than 4.0%, the effect of improving the hardenability is diminished due to the segregation of Mn, and the material cost is increased. Therefore, the Mn content is 4.0% or less, preferably 3.5% or less.
[0035]
　P: 0.0200% or less
　P is an impurity element, which segregates in the central portion of the thickness of the steel sheet to inhibit toughness and embrittle the welded portion. When the P content exceeds 0.0200%, the strength of the welded portion and the hole expandability are significantly reduced. Therefore, the P content is 0.0200% or less. The P content is preferably 0.0100% or less.
[0036]
　The smaller the P content is, the more preferable it is, but if P is reduced to less than 0.0001% in the practical steel sheet, the manufacturing cost is significantly increased, which is economically disadvantageous. Therefore, the lower limit of the P content may be 0.0001%.
[0037]
　S: 0.0200% or less
　S is an impurity element, which is an element that inhibits weldability and also inhibits manufacturability during casting and hot spreading. Further, S is also an element that forms coarse MnS and inhibits the hole-expanding property. When the S content exceeds 0.0200%, the weldability, the manufacturability, and the hole widening property are significantly reduced. Therefore, the S content is 0.0200% or less.
[0038]
　The smaller the S content is, the more preferable it is, but if the S content is reduced to less than 0.0001% in the practical steel sheet, the manufacturing cost is significantly increased, which is economically disadvantageous. Therefore, the lower limit of the S content may be 0.0001%.
[0039]
　N: 0.0200% or less
　N is an element that forms a coarse nitride, hinders bendability and hole widening property, and causes blowholes during welding. When the N content exceeds 0.0200%, the hole expanding property is lowered and the blow hole is remarkably generated. Therefore, the N content is 0.0200% or less.
[0040]
　The smaller the N content is, the more preferable it is, but if the N content is reduced to less than 0.0001% in the practical steel sheet, the manufacturing cost is significantly increased, which is economically disadvantageous. Therefore, the lower limit of the N content may be 0.0001% or more.
[0041]
　O: 0.0200% or less
　O is an element that forms a coarse oxide, hinders bendability and hole widening property, and causes blowholes during welding. When the O content exceeds 0.0200%, the hole expanding property is lowered and the blow hole is remarkably generated. Therefore, the O content is 0.0200% or less.
[0042]
　The smaller the O content is, the more preferable it is, but if the O content is reduced to less than 0.0005% in the practical steel sheet, the manufacturing cost is significantly increased, which is economically disadvantageous. Therefore, the lower limit of the O content may be 0.0005%.
[0043]
　The steel sheet according to this embodiment has Ni: 0.01 to 1.00%, Mo: 0.01 to 1.00%, Cr: 0.001 to 2.000%, Ti: 0.001 to 0.500. %, B: 0.0001 to 0.0100%, Nb: 0.001 to 0.500%, V: 0.001 to 0.500%, Cu: 0.001 to 0.500%, W: 0. 001 to 0.10%, Ta: 0.001 to 0.10%, Sn: 0.001 to 0.050%, Co: 0.001 to 0.50%, Sb: 0.001 to 0.050% , As: 0.001 to 0.050%, Mg: 0.0001 to 0.050%, Ca: 0.001 to 0.040%, Y: 0.001 to 0.050%, Zr: 0.001 It may contain one or more selected from the group consisting of ~ 0.050% and La: 0.001 ~ 0.050%. Since these elements do not have to be contained, the lower limit is 0%.
[0044]
　Ni: 0 to 1.00%
　Ni is an element effective for improving the strength of steel sheets. The Ni content may be 0%, but in order to obtain the above effect, the Ni content is preferably 0.01% or more. On the other hand, if the Ni content is too high, the ductility of the steel sheet may decrease, resulting in a decrease in formability. Therefore, the Ni content is preferably 1.00% or less.
[0045]
　Mo: 0 to 1.00%
　Mo is an element that contributes to increasing the strength of the steel sheet, like Cr. This effect can be obtained even in a trace amount. The Mo content may be 0%, but in order to obtain the above effect, the Mo content is preferably 0.01% or more. On the other hand, if the Mo content exceeds 1.00%, coarse Mo carbides may be formed and the cold formability of the steel sheet may be deteriorated. Therefore, the Mo content is preferably 1.00% or less.
[0046]
　Cr: 0 to 2.000%
　Cr is an element that improves the hardenability of steel and contributes to high strength, and is an effective element for obtaining the above-mentioned metal structure. Therefore, Cr may be contained. The Cr content may be 0%, but in order to sufficiently obtain the above effects, the Cr content is preferably 0.001% or more.
　However, even if Cr is excessively contained, the effect of the above action is saturated and it becomes uneconomical. Therefore, even when it is contained, the Cr content is 2.000% or less.
[0047]
　Ti: 0 to 0.500%
　Ti is an important element for controlling the morphology of carbides. Ti can promote an increase in the strength of ferrite. Further, Ti is an element that may form a coarse Ti oxide or TiN and reduce the formability of the steel sheet. Therefore, from the viewpoint of ensuring the formability of the steel sheet, the Ti content is preferably as low as possible, preferably 0.500% or less, and may be 0%. However, reducing the Ti content to less than 0.001% causes an excessive increase in refining cost, so the lower limit of the Ti content may be 0.001%.
[0048]
　B: 0 to 0.0100%
　B is an element that suppresses the formation of ferrite and pearlite in the cooling process from austenite and promotes the formation of low temperature transformation structures such as bainite or martensite. Further, B is an element useful for increasing the strength of steel. This effect can be obtained even in a trace amount. The content of B may be 0%, but in order to obtain the above effect, the content of B is preferably 0.0001% or more. However, if the content of B is too large, a coarse B oxide is generated, and the B oxide becomes a starting point for generating voids during press molding, which may reduce the formability of the steel sheet. Therefore, the content of B is preferably 0.0100% or less. Great attention should be paid to the analysis for the identification of B less than 0.0001%. If the B content is below the lower limit of detection of the analyzer, the B content may be considered to be 0%.
[0049]
　Nb: 0 to 0.500%
　Nb is an element that is effective in controlling the morphology of carbides like Ti, and is also an element that is effective in refining the structure and improving the toughness of the steel sheet. This effect can be obtained even in a trace amount. The Nb content may be 0%, but in order to obtain the above effect, the Nb content is preferably 0.001% or more. However, if the content of Nb is too large, a large amount of fine and hard Nb carbides are deposited, which increases the strength of the steel sheet and causes remarkable deterioration of ductility, which may reduce the formability of the steel sheet. Therefore, the content of Nb is preferably 0.500% or less.
[0050]
　V: 0 to 0.500%
　V is also an element effective for controlling the morphology of carbides, like Ti and Nb, and is also an element effective for refining the structure and improving the toughness of the steel sheet. The V content may be 0%, but in order to obtain the above effect, the V content is preferably 0.001% or more. However, if the V content is too large, a large amount of fine V carbides may be deposited, which may increase the strength of the steel material and reduce the ductility, resulting in a decrease in the formability of the steel sheet. Therefore, the V content is preferably 0.500% or less.
[0051]
　Cu: 0 to 0.500%
　Cu is an element that contributes to the improvement of the strength of the steel sheet. This effect can be obtained even in a trace amount. The Cu content may be 0%, but in order to obtain the above effect, the Cu content is preferably 0.001% or more. However, if the Cu content is too high, it may cause red-hot brittleness and reduce the productivity in hot rolling. Therefore, the Cu content is preferably 0.500% or less.
[0052]
　W: 0 to 0.10%
　W is an element effective for improving the strength of the steel sheet. The W content may be 0%, but in order to obtain the above effect, the W content is preferably 0.001% or more. On the other hand, if the W content is too large, a large amount of fine W carbides may be deposited, which may increase the strength and ductility of the steel sheet and reduce the cold workability of the steel sheet. Therefore, the W content is set to 0.10% or less.
[0053]
　Ta: 0 to 0.10%
　Ta is also an element effective for improving the strength of the steel sheet, like W. The Ta content may be 0%, but in order to obtain the above effect, the Ta content is preferably 0.001% or more. On the other hand, if the Ta content is too high, a large amount of fine Ta carbides may be deposited, which may increase the strength and ductility of the steel sheet and reduce the cold workability of the steel sheet. Therefore, the Ta content is 0.10% or less, more preferably 0.02% or less, and further preferably 0.010% or less.
[0054]
　Sn: 0 to 0.050%
　Sn is an element that can be contained in a steel sheet when scrap is used as a raw material for the steel sheet. Further, Sn may cause a decrease in cold formability of the steel sheet due to embrittlement of ferrite. Therefore, the smaller the Sn content, the more preferable. The Sn content is 0.050% or less, preferably 0.040%, and may be 0%. However, reducing the Sn content to less than 0.001% leads to an excessive increase in refining cost, so the Sn content may be 0.001% or more.
[0055]
　Co: 0 to 0.50%
　Co is an element effective for improving the strength of the steel sheet. The Co content may be 0%, but in order to obtain the above effect, the Co content is preferably 0.001% or more. On the other hand, if the Co content is too high, the ductility of the steel sheet may decrease, resulting in a decrease in formability. Therefore, the Co content is set to 0.50% or less.
[0056]
　Sb: 0 to 0.050%
　Like Sn, Sb is an element that can be contained in a steel sheet when scrap is used as a raw material for the steel sheet. Sb may be strongly segregated at the grain boundaries, resulting in embrittlement of the grain boundaries, deterioration of ductility, and deterioration of cold formability. Therefore, it is preferable that the content of Sb is small. The content of Sb is 0.050% or less, preferably 0.040%, and may be 0%. However, reducing the Sb content to less than 0.001% leads to an excessive increase in refining cost, so the Sb content may be 0.001% or more.
[0057]
　As: 0 to 0.050%
　As is an element that can be contained in a steel sheet when scrap is used as a raw material for the steel sheet, like Sn and Sb. As is an element that strongly segregates at the grain boundaries and may cause a decrease in cold formability. Therefore, it is preferable that the content of As is small. The content of As is 0.050% or less, preferably 0.040%, and may be 0%. However, reducing the As content to less than 0.001% leads to an excessive increase in refining cost, so the As content may be 0.001% or more.
[0058]
　Mg: 0 to 0.050%
　Mg controls the morphology of sulfides and oxides and contributes to the improvement of bend formability of steel sheets. This effect can be obtained even in a trace amount. The Mg content may be 0%, but in order to obtain the above effect, the Mg content is preferably 0.0001% or more. However, if the Mg content is too high, it may cause a decrease in cold formability due to the formation of coarse inclusions. Therefore, the Mg content is preferably 0.050% or less, preferably 0.040% or less.
[0059]
　Ca: 0 to 0.040%
　Ca is an element that can control the morphology of sulfide with a small amount, similar to Mg. The Ca content may be 0%, but in order to obtain the above effect, the Ca content is preferably 0.001% or more. However, if the Ca content is too high, coarse Ca oxide is generated, and the Ca oxide can be a starting point for cracking during cold molding. Therefore, the Ca content is preferably 0.040% or less, preferably 0.030% or less.
[0060]
　Y: 0 to 0.050%
　Y is an element that can control the morphology of sulfide in a trace amount like Mg and Ca. The Y content may be 0%, but in order to obtain the above effect, the Y content is preferably 0.001% or more. However, if the Y content is too high, a coarse Y oxide may be produced and the cold formability may be deteriorated. Therefore, the content of Y is set to 0.050% or less, and more preferably 0.040% or less.
[0061]
　Zr: 0 to 0.050%
　Zr is an element that can control the morphology of sulfide in a trace amount, like Mg, Ca, and Y. The Zr content may be 0%, but in order to obtain the above effect, the Zr content is preferably 0.001% or more. However, if the Zr content is too high, coarse Zr oxide may be produced and the cold formability may deteriorate. Therefore, the Zr content is preferably 0.050% or less, more preferably 0.040% or less.
[0062]
　La: 0 to 0.050%
　La is an element effective for morphological control of sulfide in a trace amount. The content of La may be 0%, but in order to obtain the above effect, the content of La is preferably 0.001% or more. However, if the La content is too large, La oxide may be generated and the cold formability may be deteriorated. Therefore, the La content is preferably 0.050% or less, preferably 0.040% or less.
[0063]
　In the composition of the steel sheet according to the present embodiment, the balance excluding the above elements is Fe and impurities. Impurities are elements that are allowed to exist as long as they are mixed from the steel raw material and / or in the steelmaking process and do not impair the characteristics of the steel sheet according to the present embodiment.
[0064]
　The steel sheet according to the present embodiment may have a hot-dip galvanized layer on its surface. The composition of the hot-dip galvanized layer of the steel sheet according to the present embodiment is not particularly limited. The plating of the steel plate according to the present embodiment may be hot-dip galvanizing or alloyed hot-dip galvanizing, or may be alloyed plating obtained by alloying these platings. Further, it is not hindered that the steel sheet according to the present embodiment has another plating (for example, aluminum plating).
[0065]
　The hot-dip galvanizing layer and the alloyed hot-dip galvanizing layer are preferably plated containing less than 7% by mass of Fe, and the alloyed plating is preferably plated containing 7% by mass or more and 15% by mass or less of Fe.
[0066]
　Characteristics
[Tensile strength: 1310 MPa or more] In
　the steel sheet according to the present embodiment, the target is to set the tensile strength (TS) to 1310 MPa or more as a strength that contributes to the weight reduction of the vehicle body of the automobile. From the viewpoint of shock absorption, the strength of the steel sheet is preferably 1400 MPa or more, more preferably 1470 MPa or more.
　The tensile strength is measured by collecting a JIS No. 5 tensile test piece described in JIS Z 2241: 2011 in a direction perpendicular to the rolling direction from the annealed steel sheet and performing a tensile test in accordance with JIS Z 2241: 2011.
[0067]
[Work hardening rate of more than 180 GPa up to the region where the true stress value in the stress-strain curve is 600 MPa or more] In the
　steel plate according to this embodiment, C is preferably segregated at the old austenite grain boundary, so that in the stress-strain curve. A work hardening rate of over 180 GPa is maintained up to a region where the true stress value is 600 MPa or more. By having this feature, the steel sheet according to the present embodiment has a wide elastic deformation range. As a result, the impact energy absorption performance of the high-strength steel sheet is improved, which is suitable for automobile bodies.
　When determining the work hardening rate, a tensile test is performed according to JIS Z 2241: 2011 in the same manner as when measuring the tensile strength. From the tensile test results, the nominal stress and nominal strain are obtained, and the work hardening rate is obtained from the inclination. The true stress is also calculated from the tensile test results in the same manner.
[0068]
　Next, a method for manufacturing a steel sheet according to the present embodiment will be described.
[0069]
　The method for producing a steel sheet according to the
　present embodiment includes a hot rolling step of hot rolling a slab having a chemical composition of a steel sheet according to the present embodiment into a
　hot-rolled steel sheet, and a cold rolling step after pickling the hot-rolled steel sheet. It has a cold rolling step of rolling to make a cold-
　rolled steel sheet and an annealing step of quenching the cold-rolled steel sheet
.
　In the annealing step, the
　　cold-rolled steel sheet is heated at a heating rate of 1.0 ° C./s or less in a temperature range starting from 830 ° C. and ending at T ° C., which is a temperature of 840 ° C. to 900 ° C., at
　　T ° C. Hold for {T / 13- (100 x Si) 0.8- (70 x Al) 0.5 } seconds or more, and
　　after holding, average 20 ° C / s to 60 ° C / s to a cooling stop temperature of 300 ° C or less. Cool at the cooling rate.
　Hereinafter, each process condition will be described.
[0070]
　[Hot Rolling Step]
　The method for manufacturing a steel sheet according to the present embodiment includes a hot rolling step of hot rolling a cast slab having a component composition of the steel sheet according to the present embodiment into a hot rolled steel sheet. The hot rolling process according to the present embodiment is not particularly limited and may be performed according to a conventional method.
[0071]
　[Cold-rolled step]
　The hot-rolled steel sheet is pickled and then subjected to cold-rolling to obtain a cold-rolled steel sheet.
　After hot rolling, it is subjected to pickling and cold rolling. There are no particular restrictions on these steps. For example, pickling may be performed once or may be divided into a plurality of times as needed. In cold rolling, the number of rolling passes and the rolling reduction rate for each pass may be appropriately set within a range in which a rolling reduction rate of about 20% or more and 80% or less can be secured.
[0072]
　[Annealing step]
　In the annealing step, the cold-rolled steel sheet is annealed. At this time, the cold-rolled steel sheet is heated at a heating rate of 1.0 ° C./s or less in a temperature range of 830 ° C. to a holding temperature T (840 ° C. to 900 ° C.), and the holding temperature T is {T / 13- (100 ° C.). × Si) Hold for 0.8 − (70 × Al) 0.5 } seconds or more, and after holding, cool at an average cooling rate of 20 ° C / s to 60 ° C / s to a cooling stop temperature of 300 ° C or lower.
[0073]
　(The temperature range starting from 830 ° C and ending at T ° C, which is a temperature of 840 ° C to 900 ° C, is heated at a heating rate of 1.0 ° C / s or less.) In the
　annealing step, 830 ° C is the starting point and 840 ° C. The temperature range ending from T ° C., which is a temperature of about 900 ° C., is heated at a heating rate of 1 ° C./s or less. That is, the range from 830 ° C to T ° C is heated at a heating rate not exceeding 1.0 ° C / s.
　In the present embodiment, it is necessary to sufficiently segregate C at the old γ grain boundaries in the annealing step so that the ratio of the presence of martensite or retained austenite having a width of 50 nm to 2 μm in the old austenite grain boundaries is 70% or more. There is. At this time, it is required to control the heat treatment conditions so that a C-concentrated region having a sufficient width can be formed even if the old γ grains grow due to heating. Therefore, the temperature range for limiting the heating rate in the annealing step is set to a temperature range starting from 830 ° C and ending at T ° C, which is a temperature of 840 ° C to 900 ° C. The T ° C. is preferably a temperature of 3 points or more of Ac in terms of organizational structure.
　When the heating rate exceeds 1.0 ° C./s in the temperature range of 830 ° C. to the holding temperature T, C is not sufficiently segregated at the old γ grain boundaries, which is not preferable. Further, in the case of a component system having a high Al content as in the present embodiment (0.20% to 1.0%), the Ac3 point increases. Therefore, in order to sufficiently segregate C at the old γ grain boundaries while sufficiently promoting austenite reverse transformation and γ growth during heating, it is continued over time from 830 ° C to T ° C while suppressing the heating rate. It is necessary to raise the temperature. Therefore, it is not preferable to set the heating rate in the temperature range of 830 ° C. to the holding temperature T ° C. to 1.0 ° C./s or less, and to perform heating exceeding 1.0 ° C./s or holding at a constant temperature in the temperature range. Therefore, the heating rate in the temperature range from 830 ° C. to the holding temperature T is 1.0 ° C./s or less, preferably 0.9 ° C./s or less, and more preferably 0.8 ° C./s or less.
　The lower limit of the heating rate in the temperature range is not particularly limited, but may be set to 0.4 ° C./s or higher from the viewpoint of productivity. Since "heating" does not include holding at a constant temperature, the heating rate is over 0 ° C./s.
　"Heating rate" is a different concept from "average heating rate". In the method for manufacturing a steel sheet according to the present embodiment, the heating rate of the temperature of the steel sheet must always be within the above range in the temperature range of 830 ° C. or higher and the holding temperature T ° C. or lower.
[0074]
　(Retained at T ° C for {T / 13- (100 × Si) 0.8- (70 × Al) 0.5 } seconds or more)
　To cover the old γ grain boundaries with martensite or retained austenite at a predetermined ratio. In order to generate the required amount of C-concentrated region, heat at the above-mentioned heating rate to concentrate C at the grain boundaries, and then hold the cold-rolled steel sheet at the soaking temperature for a sufficient time (soaking heat). )There is a need to. If the soaking temperature is low, austenite single-phase annealing does not occur and a desired metal structure cannot be obtained, which is not preferable. Therefore, the soaking temperature is 840 ° C. or higher, preferably 850 ° C. or higher. On the other hand, if the soaking temperature is too high, the manufacturing cost will be high, so the soaking temperature is 900 ° C. or lower, preferably 880 ° C. or lower.
　If the holding time in the temperature range of 840 ° C to 900 ° C is less than {T / 13- (100 × Si) 0.8- (70 × Al) 0.5 } seconds, the grains of austenite in the heating during annealing C does not sufficiently spread over the entire old γ grain boundaries that have expanded with growth (C does not sufficiently cover the old γ grain boundaries), and the old γ grain boundaries are covered at a predetermined ratio in the cooling step described later. It is not preferable because it does not produce martensite or retained austenite. Therefore, the holding time in the temperature range of 840 ° C to 900 ° C is set to {T / 13- (100 × Si) 0.8- (70 × Al) 0.5 } seconds or more.
　The upper limit of the holding time is not particularly limited, but if the holding time is long, the γ grains become mixed and the yield point is lowered due to the presence of the coarse grains. Therefore, the holding time may be set to 400 seconds or less.
　Si represents the Si content in the unit: mass%, and Al represents the Al content in the unit: mass%.
[0075]
　(After holding, the cold-rolled steel sheet is cooled to an average cooling rate of 20 ° C./s to 60 ° C./s to a cooling stop temperature of 300 ° C. or lower.)
　After holding the cold-rolled steel sheet in the above temperature range, the cold-rolled steel sheet is cooled. When the average cooling rate is less than 20 ° C./s, ferrite transformation, pearlite transformation and bainite transformation are likely to occur, so that the microstructure of the steel sheet according to the present embodiment cannot be obtained, which is not preferable. Therefore, the average cooling rate is 20 ° C./s or higher, preferably 25 ° C./s or higher. On the other hand, when the cooling rate exceeds 60 ° C./s, the temperature difference between the surface and the inside of the steel sheet is likely to occur in the plate thickness direction, so that the inside is delayed from the surface side and martensitic transformation occurs. As a result, the surface side that has been transformed into martensite first is distorted, and the old γ grain boundaries are distorted, which is not preferable. Therefore, the average cooling rate is 60 ° C./s or less, preferably 55 ° C./s or less. By setting the cooling shutdown temperature to 300 ° C. or lower, it becomes easy to obtain a desired amount of martensite. In the steel sheet according to the present embodiment, the tensile strength of the steel sheet can be 1310 MPa or more by securing a predetermined amount of martensite. The cooling shutdown temperature is preferably 250 ° C. or lower, preferably 200 ° C. or lower. On the other hand, if the cooling shutdown temperature is less than 25 ° C., many facilities are required and the manufacturing cost increases. Therefore, the cooling shutdown temperature is preferably 25 ° C. or higher. The cooling shutdown temperature is more preferably 100 ° C. or higher.
[0076]
　A hot-dip galvanizing step or an alloying step may be applied to the cold-rolled steel sheet after the annealing step. In this case, the hot-dip galvanizing method and the alloying method are not particularly limited, and a conventional method can be used. As a method of hot-dip galvanizing, for example, a cold-rolled steel plate after a baking step is controlled in a temperature range of (zinc plating bath temperature -40) ° C to (zinc plating bath temperature +50) ° C to form a hot dip galvanizing bath. Examples thereof include a method of forming hot dip galvanizing by immersion. Further, as an alloying method, for example, a method of alloying hot dip galvanizing in a temperature range of 300 to 500 ° C. can be mentioned.
Example
[0077]
　The present invention will be described in more detail with reference to examples.
[0078]
　
　A slab having the chemical composition shown in Table 1 was cast. The cast slab was heated to 1100 ° C., hot rolled to 2.8 mm, wound up and cooled to room temperature. After pickling, cold rolling was performed at a cold rolling rate of 50%. After cold rolling, the cold-rolled steel sheet was annealed under the conditions shown in Tables 2-1 and 2-2. In Example No .: 34, since the slab placement crack occurred, the steps after the annealing step could not be performed, and the metal structure and characteristics could not be measured.
[0079]
[table 1]

[0080] [0080]
[Table 2-1]

[0081]
[Table 2-2]

[0082]
　
　A test piece for SEM observation is collected from the obtained annealed steel sheet, the vertical cross section parallel to the rolling direction is polished, and then the metallographic structure at 1/4 of the plate thickness is observed and subjected to image processing. , The area ratio of each tissue was measured. The area ratio of each tissue is shown in Tables 3-1 and 3-2. In Tables 3-1 and 3-2, "the ratio of martensite or retained austenite having a width of 50 nm to 2 μm in the old austenite grain boundaries" is referred to as "grain boundary coverage". The method for measuring the grain boundary thickness and the grain boundary coverage is as described above.
[0083]
　
　(Tensile strength) The tensile strength was measured
　by collecting JIS No. 5 tensile test pieces from the annealed steel sheet in the direction perpendicular to the rolling direction and conducting a tensile test in accordance with JIS Z 2241: 2011.
　The measurement results of the tensile strength are shown in Tables 3-1 and 3-2.
[0084]
　(Work hardening rate and true stress)
　First, a tensile test was conducted according to JIS Z 2241: 2011 in the same manner as when measuring the tensile strength. The nominal stress and the nominal strain were obtained from the tensile test results, and the work hardening rate was obtained from the inclination. The true stress was also calculated from the tensile test results in the same manner. The measurement results of work hardening rate and true stress are shown in Tables 3-1 and 3-2. In Tables 3-1 and 3-2, the true stress at which the work hardening rate (abbreviated as WHR in the table) = 180 GPa is shown. When this value is 600 MPa or more, it can be said that the work hardening rate of more than 180 GPa is maintained up to the region where the true stress value in the stress-strain curve is 600 MPa or more.
[0085]
[Table 3-1]

[0086]
[Table 3-2]

[0087]
　As shown in Tables 3-1 and 3-2, in the examples according to the present invention, work hardening of more than 180 GPa is performed up to a region having a tensile strength of 1310 MPa or more and a true stress value of 600 MPa or more in the stress-strain curve. The rate was maintained. In particular, in the examples in which the Al content is more than 0.50%, 0.55% or more, 0.60% or more (for example, Example Nos. 9, 38, 42, etc.), these values ​​tend to be good. rice field. On the other hand, in the comparative example in which at least one of the requirements of the present invention was not satisfied, either characteristic was inferior. In particular, according to Examples 39 and 40, the heating rate in the temperature range of 830 ° C to the holding temperature T (840 ° C to 900 ° C) slightly exceeded 1.0 ° C / s (= 1.1 ° C / s). It turned out that good results could not be obtained by itself.
[0088]
　Further, even in a plated steel sheet obtained by hot-dip galvanizing or hot-dip galvanizing and alloying the above steel sheet, the physical properties of the present embodiment (having a tensile strength of 1310 MPa or more and having a stress-strain curve) A work hardening rate of more than 180 GPa is maintained up to a region where the true stress value is 600 MPa or more).
[0089]
　(LME resistance)
　Subsequently, slabs having the chemical compositions of steel grades A, C, D and X in Table 1 were cast, and the production conditions of Example No. 1 were applied to produce a steel sheet. A 50 mm × 80 mm test piece was collected from the manufactured steel sheet. Further, a slab having the chemical composition of A in Table 1 was cast, and after applying the production conditions of Example No. 1, it was immersed in a hot-dip galvanized bath to produce a hot-dip galvanized steel sheet. A 50 mm × 80 mm test piece was collected from the manufactured steel sheet.
　FIG. 1 shows a state of a test in which two steel plates are spot welded and the melt resistant metal embrittlement crack resistance is evaluated. A hot-dip galvanized steel sheet was used as the steel sheet 1d in FIG. 1, two steel sheets to be evaluated were used as the steel sheet 1e, and two sheets were stacked and spot-welded with a pair of electrodes 4a and 4b. Welding conditions are as follows.
　Using a servo motor pressure type single-phase AC spot welder (power frequency 50Hz), while pressurizing at a pressure of 450kgf (4413kgm / s 2 ), the current value is 6.5kA and the inclination angle of the electrode is 3 °. , No upslope, energization time 0.4 seconds, holding time after energization was 0.1 seconds, and the plated steel plate was welded. Then, the steel structure of the region in the center of the nugget of the steel sheet was observed using an optical microscope. The case where cracks did not occur was evaluated as A, the case where cracks with a length of less than 500 μm were observed was evaluated as B, and the cases where cracks with a length of 500 μm or more were observed were evaluated as C. A evaluation and B evaluation were passed.
　The steel sheet having the chemical composition of steel type A and C and the hot-dip galvanized steel sheet having the chemical composition of steel type A were evaluated as A and showed very good LME resistance. A steel sheet having a chemical composition of steel type D was evaluated as B.
　On the other hand, the steel sheet having the chemical composition of steel type X whose Si content deviates from this embodiment was evaluated as C, and sufficient LME resistance was not shown.
Industrial applicability
[0090]
　According to the present invention, it is possible to provide a steel sheet having a tensile strength of 1310 MPa or more and maintaining a work hardening rate of more than 180 GPa up to a region where the true stress value in the stress-strain curve is 600 MPa or more, and a method for manufacturing the same. can.
The scope of the claims
[Claim 1]
　The chemical composition is by mass%,
　C: 0.20 to 0.40%,
　Si: 0.10% to 1.0%,
　Al: 0.20% to 1.0%,
　Mn: 0.1 to 4 .0%,
　P: 0.0200% or less,
　S: 0.0200% or less,
　N: 0.0200% or less,
　O: 0.0200% or less,
　Ni: 0 to 1.00%,
　Mo: 0-1 .00%,
　Cr: 0 to 2.000%,
　Ti: 0 to 0.500%,
　B: 0 to 0.0100%,
　Nb: 0 to 0.500%,
　V: 0 to 0.500%,
　Cu : 0 to 0.500%,
　W: 0 to 0.10%,
　Ta: 0 to 0.10%,
　Sn: 0 to 0.050%,
　Co: 0 to 0.50%,
　Sb: 0 to 0. 050%,
　As: 0 to 0.050%,
　Mg: 0 to 0.050%,
　Ca: 0 to 0.040%,
　Y: 0 to 0.050%,
　It contains Zr: 0 to 0.050% and
　La: 0 to 0.050%
, the balance is composed of iron and impurities,
　Si + Al satisfies 0.30 to 1.4%, and the
　plate thickness is 1/4 part. The metallographic structure is
　　ferrite, bainite and pearlite: 0 to 10% in total, 　retained
　　austenite: 1 to 15%, and the
　　balance is martensite in terms of area ratio. A steel plate characterized in that
the proportion of retained austenite present is 70% or more .
[Claim 2]
　The chemical composition is, in mass%,
　Ni: 0.01 to 1.00%,
　Mo: 0.01 to 1.00%,
　Cr: 0.001 to 2.000%,
　Ti: 0.001 to 0. 500%,
　B: 0.0001 to 0.0100%,
　Nb: 0.001 to 0.500%,
　V: 0.001 to 0.500%,
　Cu: 0.001 to 0.500%,
　W: 0 .001 to 0.10%,
　Ta: 0.001 to 0.10%,
　Sn: 0.001 to 0.050%,
　Co: 0.001 to 0.50%,
　Sb: 0.001 to 0.050 %,
　As: 0.001 to 0.050%,
　Mg: 0.0001 to 0.050%,
　Ca: 0.001 to 0.040%,
　Y: 0.001 to 0.050%,
　Zr: 0. The steel sheet according to claim 1, wherein the steel sheet contains one or more selected from the group consisting of 001 to 0.050% and
　La: 0.001 to 0.050% .
[Claim 3]
　The steel sheet according to claim 1 or 2, wherein the surface thereof has a hot-dip galvanized layer.
[Claim 4]
　The steel sheet according to claim 1 or 2, wherein the surface thereof has an alloyed hot-dip galvanized layer.
[Claim 5]
　The steel sheet according to any one of claims 1 to 4, wherein the grain boundary thickness of the former austenite is 50 nm to 2 μm.
[Claim 6]
　A hot-rolling step in which a slab having the chemical composition according to claim 1 or 2 is hot-rolled to obtain a hot-rolled steel sheet, and a
　cold-rolled steel sheet after pickling the hot-rolled steel sheet and then cold-rolling to obtain a cold-rolled steel sheet. It has a cold rolling step and
　an annealing step of annealing the cold-rolled steel sheet. In the annealing step 　, the 　　cold-rolled steel sheet is subjected to T ° C., which is a temperature of 840 ° C. to 900 ° C., starting from 830 ° C. The temperature range as the end point is heated at a heating rate of 1.0 ° C./s or less, and held at the 　　T ° C. for {T / 13- (100 × Si) 0.8- (70 × Al) 0.5 } seconds or longer. A method for manufacturing a steel plate, which comprises 　　cooling at an average cooling rate of 20 ° C./s to 60 ° C./s to a cooling stop temperature of 300 ° C. or lower after the holding .

[Claim 7]
　Hot-dip galvanizing is performed by controlling the cold-rolled steel sheet after the annealing step to a temperature range of (zinc plating bath temperature -40) ° C to (zinc plating bath temperature +50) ° C and immersing it in a hot-dip galvanizing bath.
The method for manufacturing a steel plate according to claim 6, wherein the steel plate is formed .
[Claim 8]
　The method for manufacturing a steel sheet according to claim 7, wherein the hot-dip galvanizing is alloyed in a temperature range of 300 to 500 ° C.