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    • 专利摘要:
    COATED STEEL SHEET FOR USE IN HOT PRESSING AND METHOD OF HOT PRESSING THE COATED STEEL SHEET. The present invention relates to a coated steel sheet for use in hot pressing which is excellent in hot lubricating capacity, coating adhesion, spot welding ability, and corrosion resistance of the coated and a method for pressing the of the coated steel sheet. Present invention is a coated steel plate for use in hot pressing and a method of hot pressing the coated steel plate characterized by being a coated steel plate for use in hot pressing that contains a layer of Al coating which is formed on one surface or on both surfaces of said steel sheet, and a surface coating layer which is formed on said Al coating layer, said surface coating layer containing at least one Zn compound that is selected of a group comprised of Zn hydroxide, Zn phosphate, and organic Zn acid.
    公开号:BR112014019984B1
    申请号:R112014019984-1
    申请日:2013-02-08
    公开日:2021-03-09
    发明作者:Shintaro Yamanaka；Maki Jun；Masao Kurosaki；Kazuhisa Kusumi
    申请人:Nippon Steel Corporation；
    IPC主号:
    专利说明:

    Technical field
    [001] The present invention relates to a coated steel plate for use in hot pressing which is coated with an Al coating which is comprised mainly of Al and which is excellent in hot lubricating capacity, coating adhesion, spot welding capability, and corrosion resistance of the coated layer and a method of hot pressing such coated steel sheet. Background art
    [002] In recent years, to protect the environment and prevent global warming, the demand to keep fossil fuel consumption low has increased. This demand had an impact on several producing industries. For example, even for automobiles, which are essential means of transport for the activities of daily living, no exceptions. Improving fuel economy, etc. the decrease in chassis weight has been sought. However, in automobiles, just reducing the weight of the chassis is not allowed in terms of product performance. It is necessary to ensure adequate security.
    [003] Much of the structure of an automobile is formed by an iron-based material, in particular a steel plate. Reducing the weight of this steel sheet is important to lighten the weight of the chassis. However, as explained above, it is not allowed to just reduce the weight of the steel sheet. Ensuring the mechanical strength of the steel sheet is sought simultaneously. Similar demands are made on the steel plate in several other manufacturing industries in addition to the automobile production industry. Consequently, a steel sheet that has increased mechanical strength to allow the thickness to be reduced compared to the steel sheet conventionally used while maintaining or improving mechanical strength is being researched and developed.
    [004] In general, a material that has a high mechanical strength tends to freeze in shape after bending or other forming and it is difficult to form in a complicated shape. As a means to solve this problem with the forming capacity, the so-called "hot pressing method (also called hot stamping method, hot pressing method, or cooling method in the mold) can be mentioned". With this method of hot pressing, the material to be shaped is heated once to a high temperature to soften the steel sheet by heating, and then the steel sheet is shaped by pressing to conform it, and then it is cooled. According to this pressing method, the material is heated once to a high temperature to make it soft, so the material can be easily shaped by pressing. In addition, due to the hardening effect caused by cooling after pressing, the material may have increased its mechanical strength. Therefore, the hot pressing method allows a shaped product to be obtained that has both good shape freezing and high mechanical strength.
    [005] However, by applying this method of hot pressing to the steel plate, heating the steel plate to a high temperature of 800 ° C or more causes the surface of the steel plate to oxidize and scale (oxides) to form. Therefore, after executing the conformation by hot pressing, a step of removing this scale (peeling step) becomes necessary and the productivity drops. In addition, on members that require corrosion resistance, etc., the surfaces of the members have to be treated to make them rust-proof or covered with a metal after being worked. A surface cleaning step and a surface treatment step become necessary, so productivity also drops.
    [006] As a method to suppress such a drop in productivity, the method of providing the steel sheet with a coating can be mentioned. As a cover for the steel sheet, an organic material or an inorganic material or other various materials are generally used. Among these, a galvanized and annealed sheet, which has a sacrificial corrosion action against the steel sheet, is being widely used for steel sheet for automobiles, etc., from the point of view of anti-corrosion performance and production technology. of the steel sheet. However, the heating temperature (700 to 1000 ° C) in the hot pressing conformation is higher than the decomposition temperature of the organic material or the melting point and the boiling point of Zn or other metal. When hot pressing is used to heat, the surface coating and coating layer evaporate causing a noticeable deterioration in the surface properties.
    [007] Therefore, as the steel plate to which the hot pressing method that is accompanied by high temperature heating is applied, it is desirable to use a steel plate that is provided with an Al-based metallic covering, which has a boiling point higher than that of the cover of an organic material, or a steel plate coated with Al. Here, a “steel plate coated with Al” includes plates to which other elements other than Al have been added to improve the characteristics of the coating layer. The Al of the coating layer must be 50% or more, by weight%.
    [008] By providing the metallic cover based on Al, it is possible to prevent the scale from forming on the surface of the steel plate and, therefore, flaking and other steps become unnecessary, so the shaped product is improved in productivity. In addition, an Al-based metal coating also has a rust-proof effect, so corrosion resistance is also improved. The method of hot pressing the steel sheet which comprises a steel sheet which has a predetermined chemical composition and is provided with an Al-based metal cover is described in PLT 1.
    [009] However, when an Al-based metal coating is provided, depending on the preheating conditions before forming by hot pressing, the Al coating will melt, and then the Fe will diffuse from the steel plate and cause the formation of an Al-Fe alloy layer and, furthermore, growth of the Al-Fe alloy layer until the surface of the steel sheet becomes an Al-Fe alloy layer. This layer of Al-Fe alloy is extremely hard, so there was a problem that the contact with the mold at the moment of forming by pressing caused work marks on the shaped product.
    [0010] An Al-Fe alloy layer is less sliding on its surface and is poorer in lubrication capacity. In addition, this Al-Fe alloy layer is hard and breaks easily. The coating layer suffers from fractures and spraying, etc., so the forming capacity drops. In addition, any peeled Al-Fe alloy layer adheres to the mold or the surface of the Al-Fe alloy layer of the steel plate, is strongly rubbed against, and adheres to the mold or intermetallic compounds derived from the Al-Fe alloy layer to adhere to the mold and make the conformed product decline in quality. For this reason, it is necessary to periodically remove the Al-Fe intermetallic compounds that have adhered to the mold. This becomes a cause of a drop in the productivity of the conformed product or an increase in production costs.
    [0011] In addition, an Al-Fe alloy layer is low in reactivity with the usual phosphate treatment. Therefore, the surface of the Al-Fe alloy layer cannot be formed with a chemically converted coating (phosphate coating) as a pretreatment by electroplating paint. Even when a chemically converted coating is not formed, making the material good at adhesion to the coating then making the amount of Al deposition sufficient, the corrosion resistance of the coated sheet will also become excellent, but increasing the amount deposition of Al, the adhesion of intermetallic Al-Fe compounds to the mold will increase.
    [0012] Adhesion of Al-Fe intermetallic compounds includes the case where peeled parts of the Al-Fe alloy layer deposit, and the case where the surface of the Al-Fe alloy layer is strongly rubbed against and deposited. When a steel plate with a surface coating is formed by hot pressing, the lubrication capacity is improved, strong rubbing and adhesion by the surface of the Al-Fe alloy layer is facilitated. However, the improvement in lubrication capacity is not effective in relieving the deposition of peeled parts of the Al-Fe alloy layer in the mold. However, the improvement in lubrication capacity is not effective in relieving the deposition of the peeled parts in the Al-Fe alloy layer in the mold. To alleviate the deposition of the peeled parts of the Al-Fe alloy layer in the mold, it is more effective to reduce the amount of Al deposition in the Al coating.
    [0013] Therefore, the steel sheet that prevents the shaped product from being conformed to work marks is described in PLT 2. The steel sheet that is described in PLT2 is a steel sheet that has a predetermined chemical composition on the surface of the which an Al-based metal coating is provided and, furthermore, on the surface of that Al-based metal coating, an inorganic compound coating, an organic compound coating, or a compound coating, composed of the same containing at least an element between Si, Zr, Ti, or P is formed. In the steel sheet that is formed with such a surface coating as described in PLT 2, even at the moment of forming by pressing after heating, the surface coating will never peel and, therefore, it is possible to avoid the formation of work marks in the moment of forming by pressing. However, with the surface coating that is described in PLT 2, sufficient lubrication capacity cannot be obtained at the time of forming by pressing, so an improvement in the lubricant is sought.
    [0014] PLT 3 describes a method to solve the problem of deterioration of the surface of the galvanized steel sheet due to the evaporation of the galvanizing layer in the hot pressing of the galvanized steel sheet. That is, it causes the formation of a high melting zinc oxide (ZnO) layer as a barrier layer on the surface of the galvanizing layer to thereby prevent the evaporation of Zn in the Zn coating layer in the bottom layer. . However, the method that is described in PLT 3 is based on a steel sheet that has a galvanizing layer. The Al content in the galvanizing layer is allowed to be up to 0.4%. However, the Al content is desirably low. The method that is described in PLT 3 is to prevent evaporation of the Zn from the Zn coating layer. Al is included only incidentally. However, with the incidental inclusion of Al in the Zn coating layer, it is not possible to completely prevent the evaporation of Zn in the Zn coating layer. Therefore, the general practice is to use Al coated steel sheet that has a high boiling Al as the main component.
    [0015] PLT 4 describes a method of applying a compound of the wurtzite type to the surface of an Al coated steel plate. The method that is described in PLT 4, improves the hot lubrication capacity and the chemical conversion capacity and guarantees the adhesion of the coating to the surface before forming by hot pressing by adding a binder ingredient to the surface of the coating. However, the binder of the method that is described in PLT 4 ends up breaking due to the heat at the time of forming by hot pressing and, therefore, there was a problem that the wurtzite-type compound fell on the adhesion of the steel sheet lining. conformation moment.
    [0016] PLT 5 describes a galvanized and annealed steel sheet that is conformed to a surface coating layer that contains Zn hydroxide and Zn sulfate. However, the steel sheet, which is described in PLT 5, forms a coating layer on the surface of the galvanized and annealed steel sheet, so although it is excellent in corrosion resistance, there is the problem that the zinc is the galvanized and annealed layer ended up evaporating at the time of hot pressing. In addition, both surfaces of the steel sheet that is described in PLT 5 are formed with an oxide layer that has 3Zn (OH) 2-ZnSO4-nH2O (n = 0 to 5). ZnSO4 dissolves the Al coating layer, so an Al coated steel plate cannot be used.
    [0017] PLT 6 describes a steel plate that is comprised of an Al coated steel plate that is formed with a coating layer on the surface that contains a Zn compound that is selected from Zn sulfate, Zn nitrate, and Zn chloride. However, an aqueous solution of Zn sulfate, Zn nitrate, or Zn chloride is high in pH, so when the treatment solution is coated when the surface coating layer forms, it acts to dissolve the steel sheet Al-coated. As a result, there was a problem that the corrosion resistance of the coated was degraded. In addition, although the cause is not certain, there was a problem that the welding capacity was also degraded. This problem was particularly noticeable when Zn sulfate and Zn nitrate were included as the Zn compound.
    [0018] PLT 7 describes a steel plate that is comprised of an Al coated steel plate that is formed with a surface coating layer that contains a vanadium compound, a phosphoric acid compound, and at least one type of metallic compound that is selected from Al, Mg and Zn. However, the coating layer on the steel sheet surface that is described in PLT 7 contains a vanadium compound, so the valence of the vanadium compound causes several colors to be formed and, therefore, there was the problem of an uneven appearance. List of citations Patent Literature
    [0019] PLT 1: Japanese Patent Publication No. 2000-38640A
    [0020] PLT 2: Japanese Patent Publication No. 2004-211151A
    [0021] PLT 3: Japanese Patent Publication No. 2003-129209A
    [0022] PLT 4: WO2009 / 131233A
    [0023] PLT 5: Japanese Patent Publication n ° 2010-077498A
    [0024] PLT 6: Japanese Patent Publication No. 2007-302982A
    [0025] PLT 7: Japanese Patent Publication No. 2005-048200A Summary of the invention Technical problem
    [0026] Al has a high boiling point and a high melting point, so an Al coated steel sheet is considered promising as a steel sheet that is used for an element for which corrosion resistance is demanded, as like a steel sheet for automobiles. Therefore, several proposals were made regarding the application of Al coated steel plate for hot pressing. However, a layer of Al-Fe alloy cannot provide good lubricity in hot pressing and the pressing forming capacity is lower, etc., so when using hot pressing to obtain a complicated shape of a shaped product , an Al coated steel plate is not being used. In addition, in recent years, for use in automobiles, the steel sheet is mainly coated after being shaped. Al coated steel sheet has also been required to offer chemical conversion capacity (coating capacity) after hot pressing and corrosion resistance of the coated. In addition, the steel plate that is used for car chassis that has spot welding capability is also being required.
    [0027] The present invention has been made in consideration of the above situation. The purpose of the present invention is to provide an Al coated steel plate for use in hot pressing which is excellent in hot lubricating capacity, coating adhesion, spot welding ability, and corrosion resistance of the coating, and a method of hot pressing an Al coated steel sheet. Solution to the problem
    [0028] To solve the above problem, the inventors etc. have engaged in intense studies and as a result have discovered that a coating layer is formed on the surface that contains a compound containing Zn in the Al coating layer, the Al coating layer that is formed on one or both surfaces of the plate of steel, the lubrication capacity at the time of forming by hot pressing becomes better and the chemical conversion capacity is also greatly improved. In addition, they found that by not including a vanadium compound in the coated surface layer, it is possible to prevent the valence of the vanadium compound from causing various colors to be formed and making it possible to solve the problem of uneven appearance. In addition, they found that by not including a vanadium compound in the coated surface layer, it is possible to prevent the vanadium compound's valency from causing multiple colors and making it possible to solve the problem of the irregular appearance of the steel sheet. In addition, they found that including a predetermined amount of a Zn compound with a high solubility in water, such as Zn sulfate or Zn nitrate, the deposition ability at the time of application and the adhesion of the coating and the capacity spot welding becomes inferior. Based on these findings, the inventors completed the present invention. The essence of the present invention is as follows. (1) Coated steel plate for use in hot pressing characterized by being a coated steel plate for use in hot pressing that contains a steel plate, a layer of Al coating that is formed on one surface or both steel sheet surfaces, and a surface coating layer that is formed in the Al coating layer,
    [0029] The surface coating layer containing at least one Zn compound which is selected from a group comprised of Zn hydroxide, Zn phosphate and an organic Zn acid. (2) The coated steel sheet for use in hot pressing according to item (1) characterized by the fact that the amount of deposition of a Zn compound in the surface coating layer is 0.5 to 7 g / m2 per surface as Zn. (3) The coated steel sheet for use in hot pressing as it has (2) characterized by the fact that the surface coating contains, in addition to the Zn compound, at least one among a resin ingredient, a bonding agent silane, or silica in a combined ratio of 5 to 30% by weight relative to the total amount of the Zn compound. (4) The coated steel sheet for use in hot pressing according to any of the items (1) to (3) characterized by the fact that the Al coating layer contains Si: 3 to 15%. (5) The coated steel plate for use in hot pressing according to any of the items (1) to (3) characterized by allowing, as the content of the Zn compound, the inclusion of one or both between Zn sulfate and nitrate of Zn, in% by weight of 10% or less, respectively. (6) The coated steel sheet for use in hot pressing according to item (4) characterized by allowing, as the content of the Zn compound, the inclusion of one or both between Zn sulfate and Zn nitrate, in% by mass , respectively 10% or less. (7) A hot pressed coated steel plate method characterized by stamping a coated steel plate that contains a layer of Al coating that is formed on one surface of said steel plate or on both surfaces of said plate. steel and the aforementioned surface coating layer which is formed in the Al coating layer and which contains at least one Zn compound which is selected from the group comprising Zn hydroxide, Zn phosphate, and an organic Zn acid, and then heat and press the heated coated steel sheet. (8) The method of hot pressing a coated steel sheet according to item (7), characterized by the fact that when heating before pressing, the average rate of temperature rise is up to 300 ° C / s at the moment when the coated steel sheet is heated by ohmic heating or induction heating from 50 ° C to a temperature 10 ° C less than the maximum peak temperature. Advantageous effects of the invention
    [0030] According to the present invention, it is possible to provide a coated steel sheet for use in hot pressing which is excellent in lubricity, coating adhesion, spot welding ability, and corrosion resistance of the coated and a hot pressing method to improve productivity in the hot pressing stage. Brief description of the drawings.
    [0031] FIG. 1 is an explanatory view explaining an equipment for assessing the hot lubrication capacity of the steel sheet for use in the hot pressing of the present invention.
    [0032] FIG. 2 is an explanatory view explaining the hot lubricating capacity of the steel sheet for use in the hot pressing of the present invention. Description of modalities
    [0033] In the following the present invention will be explained in detail.
    [0034] Coated steel sheet for use in hot pressing
    [0035] Initially, the coated steel sheet for use in hot pressing of the present invention will be explained. The steel sheet for use in hot pressing of the present invention is comprised of a steel sheet on which on one or both of its surfaces a layer of Ale coating is formed on whose surface the Al coating layer is also formed. a surface coating layer that contains a Zn compound.
    [0036] Steel sheet before coating
    [0037] As steel sheet before coating, a steel sheet that has a high mechanical strength is desirably used (meaning tensile strength, elasticity limit, elongation, embossing capacity, hardness, impact value, fatigue strength, strength creep, and other properties related to mechanical deformation and fracture). An example of the pre-coating steel plate that is used for the steel plate for use in hot pressing is shown below.
    [0038] Initially, the chemical composition will be explained. Note that the “%” symbols mean% by mass, unless otherwise indicated. The chemical composition of the steel sheet before coating preferably contains, in weight%, C: 0.1 to 0.4%, Si: 0.01 to 0.6%, and Mn: 0.5 to 3%. In addition, it preferably contains at least one element between Cr: 0.05 to 3.0, V: 0.01 to 1.0%, Mo: 0.01 to 0.3%, Ti: 0.01 to 0 , 1%, and B: 0.0001 to 0.1%. In addition, the balance is comprised of Fe and the inevitable impurities.
    [0039] C is included to guarantee the desired mechanical strength. If the C content is less than 0.1%, sufficient mechanical strength cannot be achieved. On the other hand, if the C content exceeds 0.4%, the steel sheet can be hardened, but melting fracture easily occurs. Therefore, the C content is preferably 0.1 to 0.4%.
    [0040] Si is an element that improves the mechanical resistance. Like the C, it is included to ensure the desired mechanical strength. If Si is less than 0.01%, the strength-enhancing effect is difficult to guarantee and a sufficient improvement in mechanical strength cannot be achieved. On the other hand, Si is an easily oxidizable element. Consequently, if Si exceeds 0.6%, when Al coating is performed by hot dipping, the wetting capacity drops and uncoated parts are liable to be formed. Therefore, the Si content is preferably made from 0.01 to 0.6%.
    [0041] Mn is an element that improves the mechanical strength and is also an element that improves the hardening capacity. In addition, Mn is effective in preventing embrittlement due to the inevitable impurity S. If the Mn content is less than 0.5%, these effects cannot be achieved. On the other hand, if the Mn content exceeds 3%, the residual Y phases become very large and the resistance is liable to fall. Therefore, the Mn content is preferably 0.5 to 3%.
    [0042] Cr, V, and Mo are elements that improve the mechanical properties and are also elements that suppress the formation of perlite at the moment of cooling from the annealing temperature. These effects cannot be achieved if the Cr content is less than 0.05%, the V content is less than 0.01%, or the Mo content is less than 0.01%. On the other hand, if the levels exceed: Cr: 3.0%, V: 1.0%, or Mo: 0.3%, the surface area rate of the hard phases becomes excessive and the forming capacity deteriorates.
    [0043] Ti is an element that improves the mechanical strength and is an element that improves the heat resistance of the Al coating layer. When the Ti content is less than 0.01%, the effect of improving the mechanical strength and oxidation resistance cannot be obtained. On the other hand, if Ti is excessively included, carbides and nitrides are formed and the steel is liable to be softened. In particular, when Ti exceeds 0.1%, the desired mechanical strength cannot be achieved. Therefore, the Ti content is preferably made from 0.01 to 0.1%.
    [0044] B is an element that acts to improve the resistance at the moment of hardening. If the B content is less than 0.0001%, such an effect of improving strength cannot be achieved. On the other hand, if the B content exceeds 0.1%, inclusions are formed in the steel sheet causing the embrittlement and the fatigue resistance is likely to be reduced. Therefore, the B content is preferably made from 0.0001% to 0.1%.
    [0045] Note that the chemical composition of the steel plate mentioned above before coating is an example. Other chemical compositions are also possible. For example, as a deoxidizing element, 0.001 to 0.08% Al may also be contained. In addition, impurities that inevitably end up in the production process can also be included.
    [0046] The steel sheet before the coating that has such a chemical composition can be hardened by heating by the method of hot pressing, etc., even after the coating in order to give a tensile strength of approximately 1500 MPa or more. Even a steel sheet that has such a high tensile strength can be easily shaped by the hot pressing method in the state of softening by heating. In addition, the shaped product can have a high mechanical strength and, even when thinned to reduce weight, the mechanical strength can be maintained or improved.
    [0047] Al coating layer
    [0048] A coating layer of Al is formed on one or both surfaces of the steel plate before coating. The Al coating layer is, for example, formed on one or both surfaces of the steel sheet by the hot-dip method, but the invention is not limited to this.
    [0049] In addition, the chemical composition of the Al coating layer must contain Al: 50% or more. The elements other than Al are not particularly limited, but Si can be proactively included for the following reasons.
    [0050] If Si is included, a layer of Al-Fe-Si alloy is formed at the interface between the coating and the iron base and, therefore, it is possible to suppress the layer formation of the fragile Al-Fe alloy that is formed in the time of hot-dip coating. If the Si content is less than 3%, the Al-Fe alloy layer will thicken in the Al coating execution step, fracture in the coating layer will be aided at the time of work, and corrosion resistance can be adversely affected. . On the other hand, if the Si content exceeds 15%, the volume rate of the Si-containing layer will increase and the workability of the coating layer or the corrosion resistance is likely to fall. Therefore, the Si content in the coating layer is preferably made from 3 to 15%.
    [0051] The Al coating layer prevents corrosion of the steel sheet for use in the hot pressing of the present invention. In addition, when working steel sheet for use in hot pressing by the hot pressing method, even if heated to a high temperature, the surface will never oxidize and the scale (iron oxides) will never be formed. Using the Al coating layer to prevent scale formation, it is possible to eliminate the scale removal step, the surface cleaning step, the surface treatment step, etc., and it is possible to improve the productivity of the conformed product. In addition, the Al coating layer is greater at the boiling point and melting point than the covering coating comprised of an organic material or a covering coating comprised of another material based on a metal (e.g. based on Zn). Therefore, when using the hot pressing method to conform it, the coating will not evaporate, so forming at a high temperature becomes possible, forming capacity in hot pressing forming is also increased, and easy forming becomes possible.
    [0052] Heating at the time of hot dip coating and hot pressing can cause the Al coating layer to bond with Fe on the steel plate. Consequently, the Al coating layer is not necessarily formed into a single layer with a constant chemical composition and will include partially bonded layers (alloy layers).
    [0053] Surface coating layer
    [0054] The surface coating layer is formed on the surface of the Al coating layer. The surface coating layer includes one or more Zn compounds that are selected from the group comprised of Zn hydroxide, Zn phosphate, and acid organic Zn. As a compound of Zn, Zn hydroxide and Zn phosphate are particularly preferred. As organic Zn acid, Zn acetate, Zn citrate, Zn oxalate, Zn oleate, and others such as Zn salts of carboxylic acids and Zn salts of hydroxyl acids, Zn gluconate, etc., can be mentioned . These compounds have the effect of improving the lubrication capacity in hot pressing or the reactivity with the chemical conversion solution. Zn hydroxide and Zn phosphate have a small solubility in water, so they are used as suspensions, while Zn acetate, which has a high solubility in water, is preferably used as an aqueous solution. Note that these Zn compounds may contain one or both of Zn sulfate and Zn nitrate, but if they exceed 10% by mass, as explained above, the corrosion resistance of the coating and the weldability are degraded. Therefore, the allowable values for the contents of Zn sulfate and Zn nitrate are preferably 10% or less.
    [0055] Next, the case in which Zn hydroxide is contained in the surface coating layer will be used as an example for the explanation. Zn hydroxide breaks down on heating to form a smooth coating and results in better corrosion resistance of the coating than even the ZnO use case. Note that even when using a Zn compound other than Zn hydroxide, a surface coating layer is formed in the same way as in the case of Zn hydroxide and a similar effect can be obtained.
    [0056] The surface coating layer containing Zn hydroxide can be formed, for example, by applying a coating containing Zn hydroxide and baking and drying it to harden it after application so as to form so a coating film on the Al coating layer. As a method of applying Zn hydroxide, for example, the method of mixing a suspension containing Zn hydroxide and a predetermined organic binder and applying it to the surface of the layer can be mentioned. of Al coating and the spray coating method, etc. As a predetermined organic binder, for example, a polyurethane-based resin, a polyester-based resin, an acrylic-based resin, a silane, silica bonding agent, etc. can be mentioned. These organic binders are made soluble in water in order to allow mixing with the Zn hydroxide suspension. The treatment solution thus obtained is coated on the surface of the Al coated steel plate.
    [0057] Zn hydroxide is not particularly limited in particle size, but desirably has a size of 50 to 1000 nm. The particle size of the Zn hydroxide is made the particle size after heat treatment. That is, the particle size after keeping it in the oven at 900 ° C for 5 to 6 minutes, and then the rapid cooling in the mold is done as determined by observation with a scanning electron microscope (SEM) etc.
    [0058] The contents of the resin ingredient, silane bonding agent, silica, and other binder ingredients in the surface coating are preferably, by weight of the Zn hydroxide, together, 5 to 30%. If the content of the binder ingredients is less than 5%, the deposition effect is not sufficiently obtained and the coating peels off easily. In order to stably obtain the deposition effect, the binder ingredient is preferably made, by weight ratio, 10% or more. On the other hand, even if the content of the binding ingredient exceeds 30%, the deposition effect becomes saturated and the odor that is produced at the time of heating becomes noticeable, then this is not preferable. The upper limit of the content of the binder ingredient is most preferably made at 16%.
    [0059] The surface coating layer containing the Zn compound of the present invention is confirmed to have a higher lubricity compared to the inorganic compound coating, the organic coating compound, or the composite compound coating containing at least one element between Si, Zr, Ti, and P which are described in PLT 2. For this reason, the forming capacity is also improved.
    [0060] The amount of Zn hydroxide deposition on the surface coating layer that is formed on the Al coated steel sheet is preferably 0.5 to 7 g / m 2 per surface converted to the amount of Zn. If the amount of Zn hydroxide deposition is 0.5 g / m2 or more as Zn, as shown in FIG. 2, the lubrication capacity is improved. 1.5 g / m2 or more is more preferable. On the other hand, if the amount of Zn hydroxide deposition is above 7 g / m2 as Zn, the Al coating layer and the surface coating layer become very thick and the weldability and ink adhesion decrease. Therefore, Zn hydroxide is preferably deposited on the surface of the surface coating layer in an amount of 0.5 to 7 g / m2 as Zn per surface. In addition, considering also the weldability and paint adhesion, the amount of deposition of Zn hydroxide is particularly preferably 0.5 to 2 g / m2.
    [0061] Note that, as the method of measuring the amount of deposition of Zn hydroxide, for example, the fluorescent X-ray method can be used. The fluorescent X-ray method uses several types of standard samples with known amounts of Zn hydroxide deposition in order to prepare a calibration line and convert the Zn intensity of the sample being measured to the amount of Zn hydroxide deposition.
    [0062] As a method of cooking and drying after applying the treatment solution, for example, it is possible to use the method of using a hot air oven, an induction heating oven, an infrared oven, etc. In addition, a method that uses a combination of these is also possible. At this point, depending on the type of binder that is included in the treatment solution, instead of baking and drying after application, it is also possible, for example, to cure by ultraviolet rays, electric rays, etc. As an organic binder, polyurethane or polyester or even acrylic or a silane binding agent, etc. can be mentioned. However, the method for forming the Zn hydroxide surface coating layer is not limited to these examples. Several methods can be used to form the layer.
    [0063] Note that when a binder is not used, after the treatment solution is applied to the Al coating layer, the surface coating layer is somewhat low in adhesion before the curing treatment. If rubbed with vigorous force, it can partially peel off.
    [0064] If the surface coating layer is heated once at the moment of forming by pressing, it has an extremely strong adhesion. PLT 4 describes how to improve adhesion before hot pressing forming, but the present invention improves adhesion after hot pressing forming. Improvement of adhesion after hot pressing conformation cannot be achieved if a wurtzite-type compound which is described in PLT 4 is included in the surface coating and is an important feature of the present invention. Because the Zn hydroxide is heated, it is expected to be dehydrogenated and partially become Zn oxide, etc., and the crystal structure will change. At that time, it is believed that fine particles easily proceed to sinter. Likewise, Zn phosphate and organic Zn acid are also believed to break after being heated. A compound with low water solubility such as Zn hydroxide and Zn phosphate can be applied to an Al coated steel plate in a solution state. In addition, Zn hydroxide, Zn phosphate, and organic Zn acid are believed to precipitate as compounds in the cooking step after application or the heating step at the time of hot stamping, but compared to a solution dispersed in water , there is no secondary aggregation in the water and precipitation occurs in a finer form. Therefore, it is believed that the precipitated particles sinter and therefore the strength as a coating can be easily maintained.
    [0065] Surface coating layer improves lubrication capacity, so even with an Al coated steel plate that is lower in forming capacity, the forming capacity at the time of forming by hot pressing can be improved. In addition, it is possible to enjoy the excellent corrosion resistance of the Al coated steel sheet. In addition, the excellent lubricity of the surface coating layer suppresses the adhesion of the Al-Fe intermetallic compounds in the mold. Even if the Al coating layer sprays, the surface coating layer containing the Zn compound can prevent the powder (Al-Fe intermetallic compound powder) from adhering to the mold that is used for later pressing forming the hot. Consequently, a step of removing dust from the Al-Fe intermetallic compound that adheres to the mold, etc., becomes unnecessary, so the productivity of the shaped product can also be improved.
    [0066] In addition, the surface coating layer can play the role of a protective layer that protects from damage to the Al coating layer that may occur at the time of forming by hot pressing and can improve the forming capacity. In addition, the surface coating layer does not decrease spot welding capacity and coating adhesion or other aspects of performance. If the treatment solution when the surface coating layer is formed with high water solubility, the spot weldability and coating adhesion deteriorate. If the treatment solution has a high solubility in water, the applied treatment solution easily leaves the steel plate and the deposition capacity deteriorates.
    [0067] In addition, the surface coating layer can greatly improve the corrosion resistance of the coating and can reduce the amount of Al deposition of the Al coating layer compared to the past. As a result, even when hot pressing is carried out quickly, adhesion can be reduced and the productivity of the shaped product is also increased.
    [0068] Hot pressing method
    [0069] Next, the method of hot pressing the steel sheet for use in hot pressing of the present invention will be explained.
    [0070] In the hot pressing method of the present invention, the coated steel sheet for use in hot pressing is initially cut as required, and then heated to a high temperature to make the coated steel sheet for use in hot pressing. hot soften. In addition, the coated steel sheet softened for use in hot pressing is shaped by pressing to conform it, and is then cooled. By softening the coated steel plate for use in hot pressing once this way, it is possible to easily perform the subsequent pressings. In addition, the coated steel sheet for use in hot pressing of the present invention can be hardened by heating and cooling and obtain a high tensile strength of 1500 MPa or more.
    [0071] As a heating method, in addition to the usual electric oven, a radiant tube oven, an infrared oven, etc. can be employed.
    [0072] The Al coated steel sheet melts if heated to the melting point or more and simultaneously diffuses with Fe what changes the Al phase to an Al-Fe alloy phase and an Al-Fe-Si phase. The Al-Fe alloy phase and the Al-Fe-Si alloy phase have high melting points of 1150 ° C or similar. The Al-Fe phase and the Al-Fe-Si phase come in a plurality of types and if heated to a high temperature or heated for a long time, they change to an alloy phase with a higher concentration of Fe.
    [0073] The state of the surface that is desirable for the final shaped product is a state bound to the surface and a state where the concentration of Fe in the alloying phase is not so high. If the unbound Al remains, only that portion corrodes quickly, the corrosion resistance of the coating deteriorates, and bubbles occur extremely easily, so this is not desirable. On the other hand, if the concentration of Fe in the alloy phase becomes too high, the alloy phase itself decreases in corrosion resistance, the coated corrosion resistance deteriorates, and bubbles occur easily. That is, the corrosion resistance of the alloy phase depends on the concentration of Al in the alloy phase. Therefore, to improve the corrosion resistance of the coating, the state of the bond is controlled by the amount of Al deposition and the heating conditions.
    [0074] In the present invention, the average rate of temperature rise in the region of temperatures from 50 ° C to a temperature 10 ° C below the maximum peak temperature is preferably 10 to 300 ° C / s. The average rate of temperature rise manages productivity in the coated steel plate for use in hot pressing. If the average temperature rise rate is less than 10 ° C / s, softening the steel plate for use in hot pressing takes time. On the other hand, if above 300 ° C, softening is quick, but the bonding of the coating layer becomes noticeable and causes spraying. The general average rate of temperature rise is, in the case of heating in the atmosphere, about 5 ° C / s. The average rate of temperature rise of 100 ° C / s or more can be achieved by ohmic heating or high frequency induction heating.
    [0075] The coated steel sheet for use in hot pressing of the present invention can obtain a high average rate of temperature rise, so the productivity of the shaped product can be improved. In addition, the average rate of temperature rise has an effect on the chemical composition and thickness of the Al-Fe alloy phase, so it is one of the important factors in the quality control of coated steel sheet for use in hot pressing. In the case of the coated steel plate for use in hot pressing of the present invention, the rate of temperature rise can be increased to 300 ° C / s, so a wider range of quality control is possible.
    [0076] Regarding the maximum peak temperature, due to the principle of the hot pressing method, heating is necessary in the austenite region, so generally a temperature of 900 to 950 ° C or similar is employed. In the hot pressing method of the present invention, the maximum peak temperature is not particularly limited, but is less than 850 ° C, sufficient cooling hardness is not achieved, so this is not preferable. In addition, the Al coating layer has to be made with an Al-Fe alloy phase. From this point of view, it is not preferable to make the maximum peak temperature less than 850 ° C. On the other hand, if the maximum peak temperature exceeds 1000 ° C, bonding will continue for a long time, the concentration of Fe in the Al-Fe alloy phases will increase, and a drop in the corrosion resistance of the coating will be facilitated. The upper limit of the maximum peak temperature cannot be uniformly defined since it also depends on the rate of temperature rise and the amount of Al deposition, but even considering the economy, it is not preferable to make the maximum peak temperature be 1100 ° C or more.
    [0077] Advantageous effects of the coated steel sheet for use in hot pressing and hot pressing method of the present invention.
    [0078] The coated steel sheet for use in hot pressing of the present invention has a surface coating layer that contains a compound that contains Zn, in particular that contains Zn hydroxide, so a high lubricity capacity is obtained and the chemical conversion capacity is improved. In addition, the coated steel sheet for use in hot pressing of the present invention is resistant to peeling of the coating after forming. As a result, adhesion of Al-Fe intermetallic compounds to the mold is avoided, forming capacity and productivity at the time of hot pressing forming are improved, and the chemical conversion capacity after hot pressing forming is also improved. . In addition, the steel sheet for use in hot pressing of the present invention is excellent in adhesion of the Al coating layer and the surface coating layer after forming and also excellent in corrosion resistance of the shaped product, that is, the corrosion resistance of the coated. In addition, the steel sheet for use in hot pressing of the present invention is excellent in adhesion of the Al coating layer and the surface coating layer after forming and also excellent in corrosion resistance of the shaped product. the corrosion resistance of the coated.
    [0079] The reason why the chemically converted coating forms due to a Zn compound such as Zn hydroxide is not clear at this stage, but the chemical conversion reaction proceeds while triggering an acid etching reaction of the material. The surface of the intermetallic compound Al-Fe is extremely inert to the acid, so the reaction is thought to have difficulty proceeding. A Zn compound is an amphoteric compound and dissolves in an acid, so it is believed to react with a chemical conversion solution. EXAMPLES
    [0080] In the following, examples will be shown while also explaining the present invention. Note that the present invention is not limited to the examples that are shown below. Example 1
    [0081] The cold-rolled steel sheet of the chemical composition shown in Table 1 (sheet thickness: 1.4 mm) was used. This cold-rolled steel sheet was coated with Al by the Sendzimir process. The annealing temperature was made at about 800 ° C, the Al plating bath contained Si: 9%, and Fe which was eluted from the cold rolled steel sheet was contained. The amount of Al deposition after coating was adjusted by the gas drying method to 160 g / m2 on both surfaces. After cooling, an aqueous suspension or solution that was shown in Table 2 was coated with a coating cylinder and was cooked at about 80 ° C to produce a test material. Note that each solution that is shown in Table 2 was obtained by using reagents and mixing with distilled water to form a suspension or aqueous solution.
    [0082] The characteristics of the test material thus produced were evaluated by the following methods. Note that the average rate of temperature rise when heating up to 900 ° C was 5 ° C / s. (1) Hot lubrication capacity
    [0083] The equipment that is shown in FIG. 1 was used to assess the hot lubrication capacity. A 150 x 200 mm test material was heated to 900 ° C, so a steel ball was pushed against it from the top at 700 ° C to measure the push charge and the draw charge. The ratio (thrust load) / (loot load) was made by the dynamic friction coefficient. (2) Adhesion of the coating
    [0084] The test material was placed in an oven atmosphere, heated to 900 ° C for 6 minutes, removed, and then immediately fixed in a stainless steel mold and quickly cooled. The cooling rate at that time was 150 ° C / s. Then, the test material was cut to 50 x 50 mm and used for a packaging test. The method was to move the mesh to which 2.0 kgf (1 kgf is 9.8N) of load was applied on the back and forth basis 10 times over a length of 30 mm, measure the amount of Zn deposition before and after the test, and calculate the amount of percentage reduction. (3) Spot welding capability.
    [0085] The test material was placed in an oven atmosphere, heated to 900 ° C for 6 minutes, removed, and then immediately fixed in a stainless steel mold and cooled quickly. The cooling rate at that time was 150 ° C / s. Then, the test material was cut to 30 x 50 mm and the appropriate current range for spot welding was measured (difference between the upper current limit and the lower current limit). The measurement conditions were as follows: The lower current limit was the current value when the nugget size 4t1 / 2 (t: plate thickness) was 4.4 mm, while the upper current limit was made the current dust generator.
    [0086] Electrode: made of copper chrome, type DR (end size 6 mm, shape of radius 4R)
    [0087] Applied voltage: 400 kgf (1 kgf is 9.8N)
    [0088] Electrification time: 12 cycles (60 Hz) (4) Corrosion resistance of the coated
    [0089] The test material was inserted into the atmosphere of the oven, heated to 900 ° C for 6 minutes, removed, and then immediately fixed in a stainless steel mold and cooled quickly. The cooling rate at that time was 150 ° C / s. Next, the test material was cut to 70 x 150 mm and was converted chemically using a chemical conversion solution (PB-SX35) produced by Japan Parkerizing, and then an electrodeposition coating (Powernix 110) produced by Nippon Paint and was baked at 170 ° C to form a 20 μm coating.
    [0090] The corrosion resistance of the coating was assessed based on the JASO M609 of the Society of Automotive Engineers of Japan. The coating was previously cut by a cutter and the width of the cut bubbles after a corrosion test of 180 cycles (60 days) (maximum value on one side) was measured. The reference material was a common corrosion-proof steel sheet comprised of hot-dip galvanized steel sheet with a zinc deposit of 45 g / m2 per surface. If the coating's corrosion resistance is better than that of the reference material, use as a corrosion-proof steel sheet is possible. Note that the width of the bubbles of the reference material was 7 mm. Table 1
    Table 2

    [0091] * 1 - exclusion, in mass%, of 20% urethane resin in relation to Zn compounds in addition to Zn compounds.
    [0092] * 2 - Quantity when everything is Zn Table 3

    [0093] Note 1) - „A + D“ indicates inclusion of A and D in equal amounts. The amount of deposition of the surface coating was made 1 g / m2 for the total amount of Zn.
    [0094] Note 2) - „A + 5 to 15% G“ indicates inclusion of G in 5 to 15% by weight in relation to A. The amount of deposition of the surface coating was made 1 g / m2 for the total amount of Zn.
    [0095] Note 3) - „A + 5 to 15% H“ indicates inclusion of H in 5 to 15% by weight in relation to A. The amount of deposition of the surface coating was made 1 g / m2 for the total amount of Zn.
    [0096] The results of the evaluation are shown in Table 3. The hot lubrication capacity is shown by the measured dynamic friction coefficient, the adhesion coefficient is shown by the amount of Zn% reduction before and after heating, the ability to spot welding is shown by the appropriate current range, and the corrosion resistance of the coated is shown by the width of the bubbles. Note that No. 7 was a steel sheet coated with Al in the state without the formation of a surface coating layer.
    [0097] From Table 3 it was confirmed that by the formation of the surface coating layers that contain Zn compounds from A to E, it is possible to improve the hot lubrication capacity, the adhesion of the coating, and the corrosion resistance of the coated without cause deterioration of the spot welding ability.
    [0098] No. 6 is a comparative example where a treatment solution comprising a ZnO suspension and a mixed urethane binder is coated. Although the coating's hot lubrication capacity and corrosion resistance were excellent, the coating adhesion was 25% or notably lower compared to the examples of the invention.
    [0099] In addition, the comparative examples G and H where the surface coating layers containing Zn compounds are formed (nos 11 and 12) were inferior in coating adhesion and in spot welding capacity. This is because the treatment solutions that contain the compounds G and H have high solubility in water, come out easily when coated in Al-coated steel layers, and are inferior in deposition capacity. However, as shown in paragraphs 8 and 10, if the levels in the surface coating layers of G and H are, in% by mass, 10% or less, it was confirmed that the effect on the deterioration of the coating adhesion and the ability to spot welding was small.
    [00100] Next, it was determined the extent to which a surface coating containing a Zn compound should be formed by changing the amount of surface coating deposition and evaluating the hot lubrication capacity. The amount of deposition of the surface coating was evaluated by the amount of deposition of Zn in the surface coating. The treatment solution used was one that contained the Zn compound of A from Table 2. The results are shown in FIG. two.
    [00101] As is clear from FIG. 2, it has been confirmed that by an amount of Zn deposition of 0.5 g / m2 or more, more preferably 1 g / m2 or more, the hot lubrication capacity can be improved. The various values in FIG. 2 are shown in Table 4. As is clear from Table 4, it was confirmed that by an amount of Zn deposition of 2 g / m2, the value of the coefficient of hot friction became saturated. Table 4 - Hot friction coefficient
    Example 2
    [00102] A treatment solution was prepared by changing the addition ratio (%) of a urethane resin to a suspension containing the Zn compound of Table 2 in relation to Zn (OH) 2. This was applied to the Al coated steel sheet of Example 1 to form a surface coating layer and prepare a test material. The cooking conditions were the same as in Example 1. In addition, the adherence of this test material was assessed. The evaluation methods were the same as in Example 1, except for the evaluation that was performed before heating. That is, the test material was cut to 50 x 50 mm and subjected to a packaging test. The method was to move the mesh to which 1.5 kgf (1 kgf is 9.8 N) of load was applied at the base of the back and forth 10 times over a length of 30 mm, measured the amount of Zn deposition before and after the test, the percentage reduction amount is calculated. Table 5 - Adhesion of the coating before heating

    [00103] The results are shown in Table 5. It must be confirmed that the adhesion before heating has been improved by the addition of urethane resin. In addition, it must be confirmed that even if 16% or more urethane resin is added, the effect has become saturated. Example 3
    [00104] A steel plate was used for hot pressing of the present invention which was formed using a treatment solution containing the Zn compound of No. 1 in Example 1. An infrared oven was used to heat the steel sheet to an average heating rate of 30 ° C / s to assess the characteristics of the test material. The evaluation methods were similar to the methods that were shown in Example 1, except for the heating method. The results of the evaluation are shown in Table 6. As a result, the corrosion resistance of the coating was superior to the case of No. 1. It must be confirmed that the rapid heating method was effective. Table 6 - Results of the assessment at the time of application of rapid heating
    Example 4
    [00105] A cold-rolled steel sheet of the chemical composition that is shown in Table 1 (sheet thickness 1.4 mm) was used. This cold-rolled steel sheet was coated with Al by the Sendzimir process. The Al coating bath was changed in terms of Si concentration to 3, 6, 9, 13, 15, 18 and 21%. In addition, it contained Fe which was eluted from the cold rolled steel sheet. The amount of Al deposition after coating was adjusted by the gas drying method to 160 g / m2 on both surfaces. After cooling, a treatment solution that contained the compound Zn which was shown by A in Table 2 was coated with a coating cylinder and was baked at about 80 ° C to produce test materials. These test materials were evaluated for characteristics by methods similar to Example 1. Note that the amount of Zn deposition was, in each case, about 1 g / m2. The results of the evaluation are shown in Table 7. As is clear from Table 7, it should be considered that when the Si concentration is 3 to 15%, the corrosion resistance of the coating is particularly excellent. Table 7

    [00106] As explained above, although the preferred embodiments of the present invention have been explained in detail, the present invention is not limited to those embodiments. Any modalities that are within the scope described in the claims should be considered to be included in the present invention. Industrial applicability
    [00107] According to the present invention, when hot pressing the coated Al steel sheet, once the lubrication capacity is good and the working capacity is improved, a more complicated shape of the shaped product than those of the past can be shaped by pressing. In addition, there can be labor savings in the maintenance and inspection of the hot press mold and the productivity of the shaped product can be improved. The formed product after hot pressing is also good at chemical conversion capacity, so that the painting capacity and corrosion resistance of the final shaped product can also be improved. In this way, the present invention allows to hot-press an Al coated steel sheet to be expanded for the automotive industry, etc. Therefore, the present invention has a high application value in the industry.
    权利要求:
    Claims (6)
    [0001]
    1. Coated steel sheet for use in hot pressing, characterized by the fact that a steel sheet consists of an aluminum layer that is formed on one surface or on both surfaces of the said steel sheet, and a coating layer surface that is formed in said Al coating layer, wherein the chemical composition of said Al coating layer contains 50% by weight or more of Al, and said surface coating layer consists of one or more Zn compounds and a binder, in which at least one Zn compound is selected from the group consisting of Zn hydroxide, Zn acetate, Zn citrate, Zn oxalate, Zn oxalate, Zn oleate, Zn salts of hydroxylated acids and Zn gluconate; whereby the Zn compounds optionally additionally contain one or both of Zn sulfate and Zn nitrate, wherein, as the content of said Zn compounds, the one or both of the Zn sulfates and Zn nitrate are contained respectively in 10 % by mass or less; and the binder contains at least one of a resin ingredient, silane and silica coupling agent, and the content of the resin ingredient, silane coupling agent, silica and other binder ingredients in the surface coating are, for reason of mass with the total amount of Zn Compounds, together from 5% to 30%.
    [0002]
    2. Coated steel sheet for use in hot pressing according to claim 1, characterized by the fact that the amount of deposition of one or more Zn compounds in said surface coating layer is 0.5 to 7, 0 g / m2 per surface as Zn.
    [0003]
    3. Coated steel sheet for use in hot pressing, according to claim 2, characterized by the fact that said surface coating contains, in addition to the Zn compounds, at least one of a resin ingredient, coupling agent silane or silica, in a total amount of 5% to 30% by weight ratio in relation to the total amount of said Zn compounds.
    [0004]
    4. Coated steel sheet for use in hot pressing according to any one of claims 1 to 3, characterized in that said coating layer Al contains Si between 3% to 15% by weight.
    [0005]
    5. Method of hot pressing a coated steel sheet, characterized by stamping a galvanized steel sheet as defined in any of claims 1 to 4, then heating it, and pressing said hot-coated steel sheet.
    [0006]
    6. Hot pressing method of a coated steel plate, according to claim 5, characterized by the fact that, on heating before pressing, the average rate of temperature rise is 10 ° C / second at 300 ° C / second when the said galvanized steel sheet is heated by heating or ohmic induction heating from 50oC to a temperature 10oC below the maximum peak temperature of 850 ° C to 1100 ° C.
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    同族专利:
    公开号 | 公开日
    US10092938B2|2018-10-09|
    US20150020562A1|2015-01-22|
    CA2864392C|2018-01-02|
    ES2765101T3|2020-06-05|
    RU2014137101A|2016-04-10|
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    KR101974182B1|2019-04-30|
    TW201335425A|2013-09-01|
    JPWO2013122004A1|2015-05-11|
    MX365687B|2019-06-11|
    JP2015165049A|2015-09-17|
    JP6028761B2|2016-11-16|
    CA2864392A1|2013-08-22|
    KR20160078521A|2016-07-04|
    CN104093880A|2014-10-08|
    EP2816139B1|2019-10-09|
    JP2014139350A|2014-07-31|
    IN2014DN06844A|2015-05-22|
    RU2584105C2|2016-05-20|
    BR112014019984A2|2017-06-13|
    CN104093880B|2016-12-21|
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    PL2816139T3|2020-04-30|
    MX2014009731A|2014-11-10|
    WO2013122004A1|2013-08-22|
    EP2816139A1|2014-12-24|
    MX2019003385A|2019-07-08|
    EP2816139A4|2015-12-09|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2019-09-10| B25D| Requested change of name of applicant approved|Owner name: NIPPON STEEL CORPORATION (JP) |
    2020-09-08| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2021-01-05| B09A| Decision: intention to grant|
    2021-03-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-029396|2012-02-14|
    JP2012029396|2012-02-14|
    PCT/JP2013/053070|WO2013122004A1|2012-02-14|2013-02-08|Plated steel plate for hot pressing and hot pressing method of plated steel plate|
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