Technical field
[0001]The present invention, hot press at the workability (lubricity) and corrosion resistance (corrosion resistance after painting) can be well expressed, of the preferred Al-based plated steel sheet as a hot press.
BACKGROUND
[0002]Recently, for environmental protection and suppression of global warming, there is an increasing inhibit request the consumption of fossil fuels, the demand has affected to various manufacturing industries. No exception for the automotive industry to produce a moving means indispensable to everyday life such as to suppress the consumption of fuel, such as by reducing vehicle weight are demanded. Many automotive components are iron, which is formed in particular steel, to reduce the total weight of the steel sheet used, weight of the vehicle body, is important for eventual fuel consumption suppression.
[0003]However, since the motor vehicle is required to secure safety, simply it is not allowed to reduce the plate thickness of the steel sheet is required to have the maintenance of the mechanical strength of the steel sheet. Demand for such steel sheet, not only in the automotive industry, has increased as well in a variety of manufacturing industries. Therefore, by increasing the mechanical strength of the steel sheet, even thinner than the steel plate which has been conventionally used, for the steel sheet which can maintain or improve the mechanical strength, research and development have been conducted.
[0004]
　In general, a material having excellent mechanical strength, in a molding process of bending, etc., tend to formability, shape fixability is lowered, the case of processing into complex shapes, processing itself becomes difficult. As a means for solving the problems of the moldability, so-called "hot press method (hot stamping method, a hot press method, die quenching method, also called press hardening.)" Can be mentioned. In the hot pressing method, by heating to a material that is molded object once high temperature (austenite region), after shaping by performing press working with respect to the softened steel sheet by heating and cooling.
[0005]
　According to this hot pressing process, since the once softened by heating to a high temperature material, the material can be easily press working, further, by hardening effect due to cooling after molding, the mechanical strength of the material it is possible to increase. Thus, this hot pressing, it is possible to obtain a good shape fixability and high mechanical strength and both the molded article.
[0006]
　However, if the steel sheet to hot-pressing, for example, when heated to a high temperature of at least 800 ° C., the iron is oxidized scale (oxide) on the surface is generated. Therefore, after the hot pressing, the step of removing the scale (descaling process) is required, the productivity is lowered. Furthermore, in the case of a molded article corrosion resistance is required, subjected to rust-preventive treatment to the surface of the molded article after the hot pressing, or for forming a metal film, surface cleaning process or surface treatment step is required, even more productivity is reduced.
[0007]
　Examples of suppressing such a decrease in productivity, and a method of forming a film on the steel sheet. Generally, the coating on the steel sheet, various materials such as organic materials and inorganic materials are used. Of these zinc-plated steel sheet with a sacrificial corrosion protection action on the steel sheet, in view of the corrosion protection and the steel sheet production technology, widely used in the automotive steel sheets, etc. (Patent Document 1).
[0008]
　However, the heating temperature in the hot press (700 ° C. or higher, 1000 ° C. or less) is higher than such boiling point of the decomposition temperature and Zn (zinc) in the organic material. Therefore, when heating the steel sheet for hot press, since the plated layer of the steel sheet surface or evaporate or oxidize, the surface properties are significantly deteriorated, slidability also be exacerbated during hot pressing . To prevent this by containing aluminum in a predetermined range in the zinc plating layer, further measures such as forming a coating that melts at a press temperature is needed on the galvanized layer (Patent Document 2).
[0009]
　Therefore, with respect to the steel sheet is heated to a high temperature during hot pressing, for example, as compared with the metal coating of the organic material film or Zn-based form a high boiling point Al (aluminum) -based metal film, the so-called Al-based plated it is desirable that the steel plate. By forming the Al-based metal coating, it is possible to prevent the adhesion of scale to the steel sheet surface, thereby improving the productivity because the process is not necessary, such as descaling process. Further, since the metal film of Al-based also anticorrosive effect is also improved corrosion resistance after painting.
[0010]
　Such a method of using an Al-based plated steel sheet formed on the steel for hot pressing having a predetermined steel composition of metal coating Al systems have been proposed (e.g., see Patent Document 3). One of the challenges of hot pressing an aluminum-based plating material as disclosed in Patent Document 3, there is improvement in the workability during hot pressing. The workability during hot pressing, Dari wedged mold for Fe-Al-Si plating layer formed during the heating is rigid, or deposited in a mold for the friction coefficient is large, such as there is a concern. These concerns, scratched surface of the product, which may lower the appearance quality.
[0011]
　As a means for solving the above problems, a method of adhering a coating layer containing zinc oxide (ZnO) on the plating surface has been proposed (e.g., see Patent Document 4). The method disclosed in Patent Document 4, specifically, for the shedding inhibition of ZnO a resin component and a silane coupling agent or the like is deposited on the surface of the steel sheet a coating layer containing as a binder, 300 ° C. or higher during hot pressing, 500 ° C. to volatilize the organic solvent component of the binder in the following is a way to leave only ZnO. Such method, an organic solvent is burned, and the ZnO and gold metal by voids generated by evaporation becomes point contact, lubricity is to be improved.
[0012]
　In addition to lubricity in hot pressing, Atsushi Nobori characteristics and the time for heating by heating or infrared in the heating furnace, chemical conversion treatability after hot pressing, in order to improve the corrosion resistance after painting the method of coating the ZnO or the like has been proposed (e.g., see Patent documents 5 to 8).
CITATION
Patent Document
[0013]
Patent Document 1: JP 2010-242188 Patent Publication
Patent Document 2: JP 2011-32498 JP
Patent Document 3: JP 2000-38640 JP
Patent Document 4: WO 2009/131233 Patent
Patent Document 5: JP 2012-92365 JP
Patent Document 6: JP 2013-227620 Patent Publication
Patent Document 7: JP 2013-221202 JP
Patent Document 8: WO 2014/181653
Summary of the Invention
Problems that the Invention is to Solve
[0014]
　As disclosed in Patent Documents 5 to 8, by forming a surface coating layer containing ZnO on the Al-based plating, slidability during hot pressing is improved. However, the present inventors have studied, preheat the Al-based plated steel sheet before hot pressing and heated placed on a conveyor for conveying, for ZnO film superposition portion in contact with the conveyor is lost, preheat Doing hot press after, reduces the hot slidability of the site, it was found that it is not possible as a whole obtain sufficient workability (lubricity).
[0015]
　The present invention was made in view of the above circumstances, to suppress disappearance of ZnO at the contact portion between the conveyor during heating, hot pressing time of workability (lubricity) and corrosion resistance (corrosion resistance after painting) and to provide a suitable Al-based plated steel sheet as well is capable of expressing, for hot pressing and the like.
Means for Solving the Problems
[0016]
[1]
　and the base material, the Al-based plating layer formed on at least one surface of the base material,
　an intermediate coating layer formed on the surface of the Al-based plating layer,
　formed on the surface of the intermediate coating layer, the average particle size 0.10μm or more, and less ZnO particles 5.00, containing an organic resin, the amount of deposition of the ZnO particles of metal Zn converted at 0.5 g / m 2 or more, 10.0 g / m 2 or less and a surface coating layer,
　wherein the intermediate coating layer, Al-based plated steel sheet, characterized in that one of the conditions are satisfied in the following (a) from (C).
(A) a thickness of 10nm or more and 1000nm or less, and composed mainly of S, Al and O, the mass ratio of the S and Al [S] / [Al] is 0.0008 or more, 0.49 or less, and, S and O mass ratio of [S] / [O] is 0.001 or more, and 0.55 or less.
(B) borate, silicate, sulfonate, sulfinate, permanganate, comprises one or oxo acid salt of two or more phosphate deposition thickness of 10nm or more, 500 nm or less .
(C) aluminum, at least one of alkali metals and alkaline earth metals, a fluoride salt, the amount of fluorine contained is 20 mg / m 2 or more.
[2]
　The intermediate coating layer, satisfies the conditions specified in the (A),
　The intermediate thickness of the coating layer is 20nm or more, Al-based plated steel sheet according to [1], wherein the at 400nm or less.
[3]
　The intermediate coating layer, the meet conditions specified (A), the
　said weight ratio of S and Al contained in the intermediate coating layer [S] / [Al] is 0.005 or more, 0.1 or less and the weight ratio of S and O [S] / [O] is 0.005 or more, Al-based plated steel sheet according to, characterized in that it is less than 0.12 [1] or [2].
[4]
　The weight ratio of the S and Al contained in the intermediate coating layer [S] / [Al] is 0.008 or more, 0.05 or less, and the weight ratio of S and O [S] / [O] is 0.01 or more, Al-based plated steel sheet according to any one of [1] to [3], wherein the at 0.08.
[5]
　The intermediate coating layer, satisfies the conditions specified in the (B),
　wherein the oxo acid salt is sodium borate, sodium silicate, sodium phosphate, potassium phosphate, lithium phosphate, magnesium phosphate, to calcium phosphate, aluminum phosphate, zinc sulfonate, sodium sulfinate, potassium permanganate, zinc orthosilicate, lithium silicate, and characterized in that one or more members selected from any of the permanganate zinc Al-based plated steel sheet according to [1].
[6]
　The intermediate coating layer, satisfies the conditions specified in the (B),
　The oxo acid salt is a mixture of a permanganate and silicate, and 1 or more in a mixing ratio of Mn / Si mass ratio, to characterized in that 50 or less [1] or [5] Al-based plated steel sheet according.
[7]
　The intermediate coating layer, the meet conditions specified (C), the
　said amount of fluorine contained in the intermediate coating layer is 2000 mg / m 2 Al according to equal to or less than [1] system plated steel sheet.
[8]
　The intermediate coating layer, the meet conditions specified (C), the
　said fluoride salt is AlF 3 , Alof, LiF, NaF, KF, MgF two , CaF 2 at least one or two in characterized in that there, Al-based plated steel sheet according to [1] or [7].
[9]
　on both surfaces of the base material, the Al-based plating layer, the intermediate coating layer, and any one of the characterized in that the three layers of the surface coating layer was formed [1] to [8] Al-based plated steel sheet according to item.
[10]
　Al included in the Al-based plating layer, Al-based plated steel sheet according to any one of claims 1 to 9, characterized in that at least 70% by mass%.
[11]
　The base material is, in mass%,
　C: 0.01% or more, 0.5% or
　less, Si: 2.0% or
　less, Mn: 0.01% or more, 3.5% or
　less, P: 0.1% or
　less, S: 0.05%
　hereinafter, Al: 0.001% or more, 0.1% or
　less, N: 0.01% or less,
　any one of [1] to [10], wherein the balance being Fe and unavoidable impurities Al-based plated steel sheet according to.
[12]
　The base material further contains, by mass%,
　Ti: 0.005% or more, 0.1% or
　less, B: 0.0003% or more, 0.01% or
　less, Cr: 0.01% or more,
　1.0%, Ni: 0.01% or more, 5.0% or
　less, Mo: 0.005% or more, 2.0% or
　less, Cu: 0.005% or more, of 1.0% or less, Al-based plated steel sheet according to, characterized in that it contains one or two or more [11].
BRIEF DESCRIPTION OF THE DRAWINGS
[0017]
[Figure 1] Al-based plating layer on one side, the intermediate coating layer, and a cross-sectional conceptual view of Al-based plated steel sheet of the present invention provided with the surface coating layer.
[Figure 2] on both sides, Al-based plating layer, the intermediate coating layer, and a cross-sectional conceptual view of Al-based plated steel sheet of the present invention provided with the surface coating layer.
DESCRIPTION OF THE INVENTION
[0018]
　Hereinafter, suitable as a hot press, Al-based plated steel sheet according to the present invention (hereinafter, simply referred to as "steel plate") describing the embodiments in detail. The following embodiments are not intended to limit the present invention. The constituent elements of the above embodiments, those skilled person that can be easily replaced, or substantially the same. Moreover, various forms included in the embodiment, a person skilled in the art can arbitrarily combined within obvious limits.
　It shows an example of Al-based plated steel sheet of the present invention in FIG. Al-based plated steel sheet 100 of the present invention, the Al-based plating layer 103 is formed on the surface of the base 101, to form an intermediate coating layer 105 on the surface of the Al-based plating layer 103, the surface film on the surface of the intermediate film layer 105 by forming the layer 107, composed. The surface coating layer 107 is composed of ZnO particles 109 conjugated with the organic resin 111.
　The intermediate coating layer 105 is a layer of anti-reducing the hot antioxidant of Al of the Al-based plating layer 103 during pressing, and ZnO particles 109 in the surface film layer 107. More specifically, during hot pressing, ZnO particles 109 in the surface coating layer 107, the is reduced to Al in the Al-based plating layer 103 Zn next, Zn disappears by evaporation at elevated temperature in press the to prevent.
　In order to obtain such an effect, the intermediate coating layer 105 is required to have a certain degree of insulation and oxygen barrier properties. Furthermore, to withstand sliding during pressing, adhesion between the Al-based plating layer 103 is also required. The present inventors, as a satisfying such conditions the intermediate coating layer 105 was confirmed one of conditions must be met from the following (A) (E).
(A) a thickness of 10nm or more and 1000nm or less, and composed mainly of S, Al and O, the mass ratio of the S and Al [S] / [Al] is 0.0008 or more, 0.49 or less, and, S and O mass ratio of [S] / [O] is 0.001 or more, and 0.55 or less.
(B) borate, silicate, sulfonate, sulfinate, permanganate, comprises one or oxo acid salt of two or more phosphate deposition thickness of 10nm or more, 500 nm or less .
(C) aluminum, at least one of alkali metals and alkaline earth metals, a fluoride salt, the amount of fluorine contained is 20 mg / m 2 or more.
(D) Formula (1) Al-based layered double hydroxide represented by a metal M converted at 10 mg / m 2 or more, 1000 mg / m 2 comprising less.
[M 2+ 1-x Al 3+ x (OH) 2 ] [A n- x / n · mH 2 O] · · · (1)
　wherein, M 2+ is a divalent metal ion (Zn 2+An excluding), A n- is the n-valent anion, x is 1 less than a positive number, n represents the valence of the anion, m is a positive number. (E)
Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlN, TiN, Si 3 N 4 , TiC, ceramic deposited film composed of any one of SiC, or Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlN, TiN, Si 3 N 4 , TiC, consists composite ceramic deposited film composed of two or more of SiC, is 10nm or more thickness, 1000 nm or less. 　Hereinafter, the conditions (A) from (E), as the first to fifth embodiments will be described respectively.
[0019]
　First Embodiment:
　First, for each layer of the first embodiment will be described in detail below. First embodiment, the intermediate coating layer 105, satisfies the condition (A).
[0020]
　
　[preform 101]
　The (member for forming the Al-based plating layer 103) base material 101 used for the Al-based plated steel sheet 100 of the first embodiment, hot after plating layer formed even if the press, excellent mechanical strength (tensile strength, yield point, elongation, diaphragm, hardness, impact value, fatigue strength, which means the properties related to mechanical deformation and fracture of the creep strength, etc. ) using a member such as to have a. For example, using a member having enhanced hardenability by the addition of C (carbon) and alloying elements. Thus, Al-based plating layer 103 to be described later, the intermediate coating layer 105 and the Al-based plated steel sheet 100 obtained by forming a surface coating layer 107, in automotive parts obtained by applying the hot press is excellent mechanical strength expression.
[0021]
　That is, the first embodiment of the preform 101 of the Al-based plating steel sheet 100 can utilize a known long as it has excellent mechanical strength. For example, although those having the following ingredients can be used as the base material 101, components of the base material 101 is not limited to this.
[0022]
　Preform 101 of the first embodiment, for example, by mass%, C: 0.01% or more, 0.5% or less, Si: 2.0% or less, Mn: 0.01% or more, 3.5 % or less, P: 0.1% or less, S: 0.05% or less, Al: 0.001% or more, 0.1% or less, N: it contains 0.01% or less, Ti: 0.005% or 0.1% or less, B: 0.0003% or more, 0.01% or less, Cr: 0.01% or more, 1.0% or less, Ni: 0.01% or more, 5.0% or less, Mo: 0.005% or more, 2.0% or less, Cu: 0.005% or more, can contain one or more than 1.0% optionally, further W, V, nb, can contain elements such as Sb, the balance consists of Fe and unavoidable impurities. Hereinafter, each component added in the base material 101 will be described in detail. Units% of each component means all mass% in the following description.
[0023]
　(C: 0.01% or more, 0.5% or less)
　carbon (C) is inevitably contained in steel, also be contained in order to ensure the mechanical strength for the purpose of the base material 101. Thereby excessively reducing the content of C is to increase the smelting cost, it is preferable to contain 0.01% or more. Further, when the content of C is 0.1% or more, because a large amount is not necessary to add other alloying elements to improve the mechanical strength, a large effect of improving strength by the addition of C . On the other hand, when the content of C is 0.5 percent, but it is possible to further cure the preform 101, is easily melt cracking occurs. Therefore, C is 0.01% or more, preferably contained at 0.5% or less, from the viewpoint of melt-break preventing a strength increase of 0.1% or more, it added in a content of 0.4% or less it is more preferable to be. The content of C is 0.15% or more, still more preferably 0.35% or less.
[0024]
　(Si: 2.0% or less)
　of silicon (Si), such as is added as a deoxidizing agent, is an element inevitably contained in refining process of steel. However, since impairing the like surface properties as ductility lowered and the resulting hot-rolled process during excessive addition steel sheet production of Si, it is preferable that 2.0% or less.
　Further, Si is one of the strengthening element to improve the mechanical strength of the base material 101, similarly and C, and may be added in order to ensure the mechanical strength of interest. When the content of Si is less than 0.01%, hardly exhibits the strength improving effect, sufficient improvement in mechanical strength is difficult to obtain. Meanwhile, Si because it is also a oxidizable elements, the content of Si is 0.6 percent, when performing molten Al-based plating, decreased wettability, there is a possibility that the non-coating occurs . Therefore, Si is 0.01% or more, and more preferably added at a content of 0.6% or less. The content of Si is 0.05% or more, more preferably 0.5% or less.
[0025]
　(Mn: 0.01% or more, 3.5% or less)
　manganese (Mn), such as is added as a deoxidizing agent, is an element inevitably contained in refining process of steel. However, excessive addition of Mn impairs the quality of uniformity due to segregation of Mn during casting, the steel sheet is excessively hardened, hot, because it causes a decrease in ductility during cold working, 3.5% or less it is preferable that the. On the other hand, decreasing the content of Mn less than 0.01%, the process and the cost of removing the Mn is increased, the content of Mn is preferably 0.01% or more. Therefore, Mn is preferably 0.01% or more, 3.5% or less.
　In addition, Mn is one of the strengthening elements of the base material 101, is also one of the elements to improve the hardenability. Further, Mn is also is effective suppressing the hot embrittlement due, which is one of the inevitable impurities S (sulfur). Therefore, the content of Mn by 0.5% or more, can be obtained improving hardenability and the effect of hot shortness suppressed. On the other hand, when the content of Mn is 3 percent, there is a possibility that the residual γ phase becomes too much strength decreases. Therefore, Mn is 0.5% or more, and more preferably added in an amount of 3% or less. The content of Mn is 1% or more, still more preferably 2% or less.
[0026]
　(P: 0.1% or less)
　phosphorus (P) is also a solid solution strengthening element while an element which is inevitably contained, which is an element which relatively inexpensively increase the strength of the base material 101. However, it is preferable to 0.001% the lower limit of the content of economic refining limits. On the other hand, when the content of P is 0.1 percent, there is a possibility that the toughness of the base material 101 is lowered. Therefore, the P content is 0.001% or more and 0.1% or less. The content of P is 0.01% or more, still more preferably 0.08% or less.
[0027]
　(S: 0.05% or less)
　sulfur (S) is an element inevitably contained, become starting points of fracture becomes inclusions in the matrix 101 as MnS, to inhibit ductility and toughness machining It becomes a factor of sexual degradation. Therefore, the S content is preferably as low, it is preferable to 0.05% the upper limit of the content. Meanwhile, since the increase in manufacturing costs in order to reduce the content of S is expected, the lower limit of the content is preferably set to 0.001%. The content of S is 0.01% or more, still more preferably 0.02% or less.
[0028]
　(Al: 0.001% or more, 0.1% or less)
　aluminum (Al) is a component contained in the base material 101 as a deoxidizer, but also plating inhibition element. Therefore, the upper limit of the content of Al is preferably 0.1%. On the other hand, although not limit is particularly defined for the content of Al, from economical refining limit is preferably, for example, 0.001%. The content of Al is 0.01% or more, still more preferably 0.08% or less.
[0029]
　(N: 0.01% or less)
　nitrogen (N) is an element which is inevitably contained, from the viewpoint of stabilizing the various properties of the base material 101, it is preferable to fix the content Specifically, it is possible to fix on the basis of Ti, the content of elements such as Al. On the other hand, when the content of N is too large, Ti, becomes large content of such Al, an increase in the manufacturing cost of the base material 101 is expected, the upper limit of the content of N is set to 0.01% preferable.
[0030]
　(Ti: 0.005% or more, 0.1% or less, B: 0.0003% or more, 0.01% or less, Cr: 0.01% or more, 1.0% or less, Ni: 0.01% or more , 5.0% or less, Mo: 0.005% or more, 2.0% or less, Cu: 0.005% or more, one or more than
　1.0%) (Ti: 0.005% or more 0.1% or less)
　of titanium (Ti) is one of the strengthening elements of the base material 101, is also an element improving the heat resistance of the Al-based plating layer 103 formed on the base material 101 surface. When the content of Ti is less than 0.005%, it is impossible to obtain the strength improving effect and heat resistance and sufficient. Meanwhile, Ti is excessively added, for example by forming a carbide or nitride, the base material 101 is likely to be softened. In particular, when the content of Ti is 0.1 percent, is likely not to obtain the mechanical strength of interest. Therefore, Ti is 0.005% or more, it is preferably added at a content of 0.1% or less. The content of Ti is 0.03% or more, still more preferably 0.08% or less.
[0031]
　(B: 0.0003% or more, 0.01% or less)
　of boron (B) is an element which acts during quenching has the effect of improving the strength of the base material 101.
　When the content of B is less than 0.0003%, such effect of improving the strength is not sufficiently obtained. On the other hand, when the content of B is 0.01 percent, inclusions in the matrix 101 (e.g., BN, carbonitrides borides, etc.) is embrittled is formed, which may lower the fatigue strength. Therefore, B is 0.0003% or more, it is preferably added in a content of 0.01% or less. The content of B is 0.001% or more, still more preferably 0.008% or less.
[0032]
　(Cr: 0.01% or more, 1.0% or less)
　Chromium (Cr), the Al-based plating layer 103 when forming the Al-Fe alloy layer alloyed base material an Al-based plated layer 103 101 by generating the interface between, Al-based plating layer 103 has an effect of suppressing generation of AlN which causes peeling off. Further, Cr is one of the elements to improve the wear resistance, is also one of the elements to improve the hardenability. When the content of Cr is less than 0.01%, it is impossible to sufficiently obtain the aforementioned effect. On the other hand, when the content of Cr is 1.0 percent, also increases the manufacturing cost of the steel sheet not only the above effect is saturated. Therefore, Cr is 0.01% or more, it is preferably added at a content of 1.0% or less. The content of Cr is 0.5% or more, more preferably 1.0% or less.
[0033]
　(Ni: 0.01% or more, 5.0% or less)
　of nickel (Ni) has the effect of improving the hardenability during hot pressing. Further, the Ni also has the effect of increasing the corrosion resistance of the base material 101. However, when the content of Ni is less than 0.01%, it is impossible to sufficiently obtain the aforementioned effect. On the other hand, when the content of Ni is 5.0 percent, also increases the manufacturing cost of the steel sheet not only the above effect is saturated. Therefore, Ni is 0.01% or more, it is preferably added in a content of 5.0% or less.
[0034]
　(Mo: 0.005% or more, 2.0% or less)
　of molybdenum (Mo) has the effect of improving the hardenability during hot pressing. Further, the Mo has the effect of increasing the corrosion resistance of the base material 101. However, when the content of Mo is less than 0.005%, it is impossible to sufficiently obtain the aforementioned effect. On the other hand, if the content of Mo is 2.0 percent, also increases the manufacturing cost of the steel sheet not only the above effect is saturated. Therefore, Mo is 0.005% or more, it is preferably added in a content of 2.0% or less.
[0035]
　(Cu: 0.005% or more, 1.0% or less)
　of copper (Cu) has the effect of improving the hardenability during hot pressing. Further, the Cu also has the effect of increasing the corrosion resistance of the base material 101. When the content of Cu is less than 0.005%, it is impossible to sufficiently obtain the aforementioned effect. On the other hand, when the content of Cu is 1.0 percent, also increases the manufacturing cost of the steel sheet not only the above effect is saturated. Therefore, Cu is 0.005% or more, it is preferably added at a content of 1.0% or less.
[0036]
　(W, V, Nb, Sb )
　Incidentally, the base material 101 of the first embodiment, in addition to the plurality of elements as described above, tungsten (W), vanadium (V), niobium (Nb), antimony (Sb) elements may be selectively added and the like. The addition amount of these elements, if known range may be employed for any of the added amount.
[0037]
　(Balance)
　the remainder of the base material 101 is iron (Fe) and only unavoidable impurities. The inevitable impurities, a component to be mixed in the course of the components, or the production is contained in the raw material, refers to intentionally not were contained Ingredient in the base material 101.
[0038]
　Such preform 101 formed by component, by hardening by heating due to hot pressing, it is possible to have a mechanical strength of at least about 1500 MPa. There is a steel sheet having such excellent mechanical strength but, if processed by hot pressing, it is possible to perform the press in a state softened by heating, can be easily molded. Further, after pressing, the base material 101 which is cooled from the high temperature, high mechanical strength can realize, may also be maintained or improved mechanical strength as the thin to the thus lighter.
[0039]
　[Al-based plating layer
　103] Al-based plating layer 103 is formed on at least one surface of the base material 101. Al-based plating layer 103 is, for example, can be formed by hot dipping method, not the forming method is not limited to this. Al-based plating layer 103 only needs to contain Al as a main component. Herein, the term "main component" refers to containing Al 50 mass% or more. Preferred major amount is, Al is not less than 70 mass%, Al-based plating layer 103 preferably contains an Al 70 mass% or more. Components other than Al is not particularly limited, the Si may be added any amount.
[0040]
　Al-based plating layer 103 prevents corrosion of the base material 101. Also, Al-based plating layer 103, when the hot press prior to the heating to prevent the scale (iron oxide) is formed on the surface of the steel sheet. Therefore, by Al-based plating layer 103 on at least one surface of the base material 101 is present, the scale removal step can be omitted and surface cleaning step and surface treatment step, and thus improve the productivity of automobile parts it can be. Furthermore, Al-based plating layer 103, and coating by an organic material, other metal-based material (e.g., Zn-based materials) because of its high melting point than the coating by, during hot pressing, and can be processed at high temperatures Become.
[0041]
　A part or all of Al included in the Al-based plating layer 103, and when hot-dip plating, during hot pressing, may be Fe alloyed with the base material 101. Therefore, Al-based plating layer 103 is not necessarily limited to component is formed of a single layer is constant, partially alloyed layer (alloy layer), or changes from a concentration gradient surface steel - it may become encompasses aluminum gradient alloy layer.
[0042]
　Intermediate coating layer 105 '
　intermediate coating layer 105 is formed on the surface of the Al-based plating layer 103, it acts on the anti-reducing of ZnO antioxidant and surface film layer 107 of Al in the plating layer. Intermediate coating layer 105 has a thickness of 10nm or more and 1000nm or less, as a primary component, the S and Al and O. The term "a main component", S, Al, a total mass of O, refers to accounts for at least 85 mass% in the intermediate coating layer 105. Typically, S, Al, component elements other than O raw material, an element to be mixed inevitably derived from the production process.
　When the Al-based plating layer 103 on both surfaces of the base material 101 is formed, it is possible to form the intermediate coating layer 105 on at least one side of the Al-based plating layer 103. Of course, if the Al-based plating layer 103 on only one surface of the base material 101 is formed, directly formed thereon (see FIG. 1). Furthermore, if the Al-based plating layer 103 is formed on both surfaces of the base material 101, formed directly adjacent on each of the both surfaces of the Al-based plating layer 103, Al-based plating layer 103, an intermediate film layer 105, to form a three-layer of the surface coating layer 107 (see FIG. 2).
　Intermediate coating layer 105, the electrolyte solution containing S ions Al-based plating layer 103 as the anode, for example, can be formed by energizing a solution including sulfuric acid, subjected to anodic oxidation. Further, aluminum sulfate (Al 2 (SO 4 ) 3 ) and / or by heating by coating and hydrates thereof, it is possible to form an intermediate coating layer 105.
[0043]
　The intermediate coating layer 105 of the first embodiment, Al, in addition to of O, the largest comprising a S. S is, Al oxide containing S that constitutes the intermediate coating layer 105 in the form of (alumina) but typically considered, of a mixture of Al oxide and other sulphate salts containing the S morphology may be contained in the intermediate coating layer 105. For example, in the form of a mixture with aluminum sulfate, or aluminum sulfate and other sulfates, S is may be contained in the intermediate coating layer 105. Incidentally, the sulfate, magnesium sulfate, may be a copper sulfate. It will be described later content allowance than S, Al and O. The intermediate coating layer 105 may be formed of aluminum sulfate itself.
[0044]
　If the intermediate film layer 105 does not contain S, for example, be formed Al oxide by air oxidation, Al does not contain S 2 O 3 only is formed, oxidation of Al in the plating layer and it is impossible to obtain the effect of reducing the prevention of ZnO in the surface film layer 107. Further, even when forming an Al-based oxide by anodic oxidation in a solution without S, Al of the porous structure 2 O 3 for dense structure are layers formed is not formed, the anodic oxide film, the effect of anti-reducing the Al antioxidant and ZnO of can not be obtained. The reason is not necessarily clear, if it contains S, estimates that do not because denseness of the intermediate coating layer 105 is increased. For example, when subjected to anodic oxidation in an electrolytic solution containing S ions Al-based plating layer 103 as an anode, a dense layer containing the S is formed on the Al-based plating layer 103. Therefore, by the S it is taken into the intermediate coating layer 105 as aluminum sulfate, the intermediate coating layer 105 is presumed to have been densified.
[0045]
　And since as described above, it is necessary to define the S content in the intermediate coating layer 105. In the first embodiment, the S content in the intermediate coating layer 105, the weight ratio of S and Al [S] / [Al] (S / Al ratio) is 0.0008 or more, 0.49 or less, and, S and O mass ratio of [S] / [O] (S / O ratio) is 0.001 or more, were defined by 0.55 or less. The mass ratio of S and Al [S] / [Al] is less than 0.0008, or, if the mass ratio of the S and O [S] / [O] is less than 0.001, S in the intermediate coating layer 105 the amount is too small, it is not possible to prevent the reduction of ZnO. On the other hand, the mass ratio of the S and Al [S] / [Al] is 0.49, or greater than, the mass ratio of the S and O [S] / [O] is 0.55, greater than in the intermediate coating layer 105 of too amount S large amount, O, since the compound forming the Al tends to disappear by decomposition, can not prevent the reduction of ZnO.
[0046]
　Furthermore, to increase the effect of reducing the prevention of ZnO in antioxidant and a surface coating layer 107 of Al in the plating layer, S / Al ratio in the intermediate coating layer 105, and controls the lower limit of the S / O ratio it is preferable to. S / Al ratio, the lower limit of the S / O ratio is correlated with the density of the intermediate coating layer 105 and is estimated, S / Al ratio is preferably 0.005 or more, more preferably 0.008 above, S / O ratio is preferably 0.005 or more, more preferably 0.01 or more. Meanwhile, in order to maintain the effect of lubricity enhancing the by surface coating layer 107, S / Al ratio, it is preferable to control the upper limit of the S / O ratio. S / Al ratio, the upper limit of the S / O ratio is estimated in the form of a surface coating layer 107 and the correlation, S / Al ratio, a number of the surface film layer 107 when the S / O ratio is too high holes are formed, corrosion resistance and adhesion after coating may decrease. Therefore, the upper limit of S / Al ratio is preferably 0.1 or less, more preferably 0.05 or less, the upper limit of the S / O ratio is preferably 0.12 or less, more preferably 0.08 or less.
[0047]
　The mass ratio of S and Al contained in the intermediate coating layer 105 [S] / [Al], the weight ratio of S and O [S] / [O] is an Auger electron spectroscopy (Auger Electron Spectroscopy, AES), X-ray photoelectron spectroscopy (electron spectroscopy for Chemical analysis, ESCA), high-frequency glow discharge optical emission spectrometry (glow discharge spectroscopy, GDS) by, it was determined by measuring the depth direction from the surface of the Al-based plated steel sheet 100, Al, O and it can be calculated from the S concentration conversion profile. In the case of forming the intermediate coating layer 105 by anodic oxidation, S / O ratio, the conditions of the anodic electrolysis, in particular, can be controlled by the concentration of S ions contained in the electrolyte.
[0048]
　The intermediate coating layer 105 of the first embodiment, other S, Al and O, and other components may include the remaining less than 15 weight percent if necessary. The intermediate coating layer 105 of the first embodiment is preferably composed of S and alumina, the internal and the intermediate coating layer 105, it may contain impurities of the processing liquid residues and the like in the interface between the surface coating layer 107 is there. As the impurity, Al 2 O 3 , Alof, AlH 3 O 3 , AlO (OH), Al 2 O 3 trihydrate, Al 2 O 3 may be contained monohydrate and the like. Capacity of the impurities is preferably 10 mass% or less.
[0049]
　The thickness of the intermediate coating layer 105, is less than 10 nm, it does not function well as a barrier for preventing the diffusion of oxygen, to obtain the effect of reducing the prevention of ZnO in antioxidant and a surface coating layer 107 of Al in the plating layer can not. Furthermore, can not be sufficiently secured corrosion resistance after painting to can not be secured paint adhesion for zinc phosphate coating weight upon conversion treatment with Zn remaining amount is small (zinc phosphate treatment) becomes insufficient. Therefore, the lower limit of the thickness of the intermediate coating layer 105 and above 10 nm, preferably not less than 20 nm. On the other hand, if the thickness of the intermediate coating layer 105 is greater than 1000 nm, weldability is inhibited. Therefore, the upper limit of the thickness of the intermediate coating layer 105 and 1000nm or less, preferably 400nm or less. The thickness of the intermediate coating layer 105 is formed on the surface of the Al-based plated steel sheet 100, Al-based plating layer 103, cross-sectional scanning electron microscope of the intermediate coating layer 105 and the surface coating layer 107 (Scanning Electron Microscope, SEM) or transmission electron microscope (transmission electron microscope, TEM) can be observed by measures. An intermediate coating layer 105, Al-based plating layer 103, the difference in contrast, the electron microscopic photograph, since the interface between (boundary) can be clearly observed from the intermediate coating layer 105, for measuring a distance to the boundary it is thus possible to determine the thickness of the intermediate coating layer 105. In the case of forming the intermediate coating layer 105 by anodic oxidation, thickness, condition of the anodic electrolysis, in particular, it can be controlled by the current density and the quantity of electricity.
[0050]
　[Surface film layer 107 '
　surface film layer 107 has an average particle diameter of 0.10μm or more, and less ZnO particles 109 5.00, while containing an organic resin 111, the amount of deposition of the ZnO particles 109 of metal Zn terms 0.5 g / m 2 or more, 10.0 g / m 2 is required to be less. In the case where the Al-based plated layer 103 on both surfaces of the base material 101 is formed, on at least one side of the intermediate coating layer 105 on the Al-based plating layer 103, to form a surface film layer 107 it can.
[0051]
　Surface film layer 107, for example, can be formed using a solution prepared by mixing the components in the various solvents mentioned above such as water or an organic solvent.
[0052]
　(ZnO particles 109)
　in order to obtain good workability and corrosion resistance in hot pressing, on the intermediate coating layer 105, an average particle diameter of 0.10μm or more, the following ZnO particles 109 5.00 is a metal Zn terms 0 .5G / m 2 or more, 10.0 g / m 2 is required to be formed at a coverage of less. ZnO particles 109 contacts the mold and the point to improve the workability by lowering the dynamic friction coefficient. However, the average particle size is less than 0.10μm of ZnO particles 109, since the contact point between the ZnO grains 109 and the mold is too large at the time of press working, can not be sufficiently improved processability.
[0053]
　On the other hand, the average particle size of the ZnO particles 109 is more than 5.00, weldability is deteriorated. ZnO is an insulating, when the particle size is small, it is possible to sufficiently ensure the current point to collapse during welding 圧加. However, ZnO particles 109 is less likely to collapse during the welding 圧加 average particle diameter of the ZnO grains 109 grow to larger than 5 [mu] m. As a result, it is impossible to ensure a sufficient current supply point, weldability since dust is likely out worse.
[0054]
　The measurement method of the average particle size of the ZnO particles 109 is not particularly limited. For example, scanning electron microscopy (SEM, Scanning Electron Microscope) such as by, by observing any 10 or more ZnO particles 109 at 2000 times to measure the maximum particle diameter of each particle, be determined by calculating the average value good. Alternatively, using a particle size distribution measuring device may determine the average particle size of the ZnO particles 109.
[0055]
　Further, 0.5 g / m at a coverage of all of the ZnO particles 109 of the surface coating layer 107 is metal Zn terms 2 by weight, it is impossible to obtain sufficient workability during hot pressing. Further, as the amount of deposition of the ZnO particles 109 increases, although the workability and the corrosion resistance of the steel sheet is increased, since the film resistance of the surface coating layer 107 is increased, the steel sheet resistance weldability (for example, spot weldability) There is reduced. In other words, the adhesion amount of all of the ZnO particles 109 of the surface coating layer 107 is 10.0 g / m of a metal Zn terms 2 exceeds, it is difficult to obtain a sufficient resistance weldability of the steel sheet.
　Herein, the term coating weight and, at the time of hot press, a deposition amount before heating placed on a conveyor.
[0056]
　(Organic resin 111)
　in the Al-based plated steel sheet 100 of the first embodiment, the organic resin 111 which is a component of the surface coating layer 107, as long as it functions as a binder to hold the ZnO particles 109 in the coating It is not particularly limited. The organic resin 111 is lost by burning during hot pressing prior to the heating, it does not affect the press working, welding, or the like is a subsequent process. The organic resin 111 when the drug water-based, it is preferable to use a ZnO as well as stable cation resin in weakly alkaline, for example, can be used cationic urethane resin and a cationic acrylic resin. In the first embodiment, for the concentration (g / kg) ratio of the organic resin in the drug, not specified. The resin that can be used as the organic resin 111 of the first embodiment, cationic urethane resin (Dai-ichi Kogyo Seiyaku Co., product name SUPERFLEX 650), and the like.
[0057]
　In order to sufficiently express the function as a binder in the organic resin 111, the content of the organic resin 111 on the entire surface coating layer 107, by mass%, 10% or more, it is preferable that 60% or less. When the content is less than 10%, acts as a binder is not sufficiently expressed, the coating film before the heating is likely to peel. In order to get a stable an action as the binder, the content of the organic resin 111, more preferably 15% or more. On the other hand, when the content of the organic resin 111 is 60 percent, the occurrence of unpleasant odor upon heating becomes remarkable.
[0058]
　Incidentally, adhesion of ZnO particles 109 to Al-based plating layer 103 above can be measured by a calibration curve method using a XRF (fluorescent X-ray, X-ray Fluorescence).
[0059]
　The method of forming the intermediate coating layer 105 and the surface film layer 107 on the Al-based plating layer 103 above is not particularly limited. Intermediate coating layer 105 may be formed by anodic oxidation in a solution containing S ions. Further, by applying a solution containing S ions may be subjected to heat treatment. When forming the intermediate coating layer 105 by anodic oxidation, the conditions of anodic electrolysis, in particular, it is possible to control the thickness by the quantity of electricity. If the heat treatment, it is possible to control the thickness of the intermediate coating layer 105 by the heating temperature and holding time. S / O ratio of the intermediate coating layer 105 can be controlled by the concentration of S ions contained in the solution. The surface coating layer 107 is an aqueous solution or a solvent prepared by dissolving the main component of the, on the Al-based plating layer 103 was applied by a known method such as a roll coater or a spray, followed by drying, can be formed .
　The concentration of the electrolytic solution, when using a sulfuric acid solution, in the case of anodic oxidation, 1 vol% or more with respect to the solvent, an aqueous sulfuric acid solution of 10 vol% or less, can be used. It is also formed by baking the aqueous aluminum sulfate solution. The concentration of aluminum sulfate aqueous solution in that case, 20 vol% or more with respect to the solvent, preferably at most 35 vol%, the amount of coating is 0.5 ml / m 2 or more, 5 ml / m 2 or less. Current density, when using an acid solution, in the case of anodic oxidation, 10 mA / cm 2 or more, 500mA / cm 2 or less and it can be, the quantity of electricity, than 15C, be less 1500C (Coulomb) it can.
　Further, in forming the surface coating layer 107 is not particularly limited for the drying method after coating, hot air, the IH (induction heating, Induction Heating), NIR (near infrared, Near InfraRed), such as electric heating it can be used each method. Furthermore, the heating temperature in drying, taking into account the glass transition temperature of the organic resin 111 is a binder (Tg), is preferably set as appropriate.
[0060]
　As described above, according to the first embodiment of the Al-based plated steel sheet 100 (steel), the surface film layer 107 and the intermediate coating layer 105, hot without ZnO film is lost at the contact portion between the conveyor to express the excellent lubricity of the press, it is possible to achieve excellent corrosion resistance after excellent workability and hot pressing during hot pressing or the like. Further, according to the Al-based plated steel sheet 100 of the first embodiment, the presence of surface film layer 107 having excellent lubricating properties, it is possible to suppress the adhesion to the mold. Even if the Al-based plating layer 103 was powdering by heating, the presence of the surface coating layer 107 having excellent lubricity, the molds used in the subsequent press powder (Al-Fe powder, etc.) that adhesion is suppressed. Therefore, in the case of hot pressing the Al-based plated steel sheet 100 of the first embodiment, such step of removing the Al-Fe powder and adhesion to the mold is not required, to achieve excellent productivity can.
[0061]
　Second Embodiment:
　Next, each layer of the second embodiment will be described in detail below. Second embodiment, the intermediate coating layer 105, satisfies the condition (B).
[0062]
[Preform 101]
　base material 101 used for the Al-based plated steel sheet 100 of the second embodiment, even when the hot press after plating layer formed, excellent mechanical strength (tensile strength, yield point, elongation, diaphragm, hardness, impact value, fatigue strength, which means the properties related to mechanical deformation and fracture of the creep strength, etc.) using a member having a. For example, using a member having enhanced hardenability by the addition of C (carbon) and alloying elements. Thus, with respect to the steel sheet obtained by forming the Al-based plating layer 103 and the surface film layer 107, in the automotive parts obtained by performing hot pressing, it is excellent mechanical strength expression.
[0063]
　Preform 101 of the second embodiment may utilize a known long as it has excellent mechanical strength. For example, although those having the same composition as the first embodiment can be utilized as the base material 101, components of the base material 101 is not limited to this.
[0064]
[Al-based plating layer
　103] Al-based plating layer 103 is formed on at least one surface of the base material 101. Al-based plating layer 103 is, for example, the same method may include the composition as the first embodiment.
[0065]
Intermediate coating layer 105 '
　intermediate coating layer 105 is formed on the surface of the Al-based plating layer 103, which acts as an oxidizing agent. Intermediate coating layer 105 borates, silicates, sulfonate, sulfinate, permanganate, comprises one or oxo acid salt of two or more phosphate deposition thickness of 10nm or more, it is necessary that the 500nm or less. When the Al-based plating layer 103 on both surfaces of the base material 101 is formed, it is possible to form the intermediate coating layer 105 on the surface of at least one side of the Al-based plating layer 103. Intermediate coating layer 105 is, for example, in various solvents such as water or an organic solvent, coating the solution prepared by mixing the components described above, and dried, can be formed. Intermediate coating layer 105 preferably contains the oxo acid salt as a main component (50 mass percent). More preferably, the intermediate coating layer 105, with the exception of unavoidable impurities, consisting of oxo acid salt.
[0066]
　It is less than adhesion thickness 10nm of the intermediate coating layer 105, since the ZnO particles 109 of Al-based plating layer 103 and the surface film layer 107, portions of contact would exist, suppress the loss of ZnO on heating of the hot press Can not do it. In addition, corrosion resistance worse. On the other hand, when the deposition thickness of the intermediate coating layer 105 exceeds 500 nm, since the greater the volume contraction amount during the film formation, the mechanical strength of the intermediate film layer 105 is lowered, the paint adhesion is deteriorated. Measurement of adhesion thickness of the intermediate coating layer 105 (film thickness), observing the cross section by a scanning electron microscope, the thickness of the intermediate coating layer 105 may be the average value and the film thickness was measured 10 points arbitrarily .
[0067]
(Oxo acid salts)
　borate, silicate, sulfonate, sulfinate, permanganate, intermediate coating layer 105 comprises one or oxo acid salt of two or more phosphate, formed It becomes sometimes uniform film, to prevent the Al-based plating layer 103, the contact between the ZnO contained in the surface coating layer 107 (ZnO particles 109). Furthermore, oxo acid salt contained in the intermediate coating layer 105, upon heating of the hot press acts as an oxidizing agent for promoting the oxidation of Al, suppress loss caused by the reduction of ZnO.
[0068]
　Oxo acid salt, in order to more remarkably the inhibitory effect of ZnO disappears, borates, silicates, sulfonate, sulfinate, permanganate, one phosphate or at two or more there is a need. Furthermore, these, although the effect of the permanganate oxidizing agent is very large, weak adhesion to the base material, whereas, silicates, the effect as the oxidizing agent, the permanganate reach although no high adhesion to the base material. Therefore, by a mixture obtained by mixing a permanganate and silicate in proper ratio, it is possible to achieve both adhesion with the matrix of ZnO loss suppressed and the film to high. Result of studies by the present inventors, one or more of a mixing ratio of permanganate and silicates with Mn / Si mass ratio, the balance of by 50 or less, the adhesion and the effect of suppressing the ZnO loss There was found to be in very good. Various oxo acid salt be identified by X-ray diffractometry (XRD), Mn / Si ratio is calculated from the measurement result of the calibration curve method using a fluorescent X-ray analyzer (XRF).
[0069]
　Examples of oxo acid salt, sodium borate, sodium silicate, sodium phosphate, potassium phosphate, magnesium phosphate lithium phosphate, calcium phosphate, aluminum phosphate, zinc sulfonate, sodium sulfinate, potassium permanganate, zinc orthosilicate, lithium silicate, including but permanganate zinc, and the like.
[0070]
[Surface film layer 107 '
　surface film layer 107 has an average particle diameter of 0.10μm or more, and less ZnO particles 109 5.00, while containing an organic resin 111, 0 deposition amount of ZnO particles 109 of metal Zn terms .5G / m 2 or more, 10.0 g / m 2 is required to be less. In the case where the Al-based plated layer 103 on both surfaces of the base material 101 is formed, at least, on the surface of the intermediate coating layer 105 on one side of the Al-based plating layer 103, to form a surface film layer 107 it can.
[0071]
　Surface film layer 107 is, for example, in various solvents such as water or an organic solvent, can be formed using a solution prepared by mixing the components described above.
[0072]
(ZnO particles 109)
　in order to obtain good workability and corrosion resistance hot pressing, the surface of the Al-based plating layer 103, an average particle diameter of 0.10μm or more and less ZnO particles 109 5.00, Zn metal converted at 0.5 g / m 2 or more, 10.0 g / m 2 is required to be formed at a coverage of less. ZnO particles 109 contacts the mold and the point to improve the workability by lowering the sliding friction coefficient. However, the average particle size is less than 0.10μm of ZnO particles 109, since the contact point between the ZnO grains 109 and the mold is too large at the time of press working, can not be sufficiently improved processability.
[0073]
　Meanwhile, ZnO is an insulator, the average particle size of the ZnO particles 109 is more than 5.00, less likely to collapse during welding 圧加, it can not be sufficiently ensured conductive point, making it easier out dust weldability is deteriorated.
[0074]
　The method of measuring the average particle size of the ZnO particles 109 is not particularly limited. For example, by scanning electron microscope (SEM) to measure the particle size by observing any 10 or more ZnO particles 109 at 2000 times may be obtained by calculating the average value. Alternatively, using a particle size distribution measuring device may determine the average particle size of the ZnO particles 109.
[0075]
　Further, the amount of deposition of all of the ZnO particles 109 of the surface coating layer 107, 0.5 g / m of a metal Zn terms 2 by weight, it is impossible to obtain sufficient workability during hot pressing. As the amount of deposition of the ZnO particles 109 increases, although the workability and the corrosion resistance of the steel sheet is increased, since the film resistance of the surface coating layer 107 is increased, the resistance weldability of the steel sheet (for example, spot weldability) decreases . In other words, the adhesion amount of all of the ZnO particles 109 of the surface coating layer 107, 10.0 g / m of a metal Zn terms 2 exceeds, it is difficult to obtain a sufficient resistance weldability of the steel sheet.
[0076]
　Deposition of ZnO particles 109 to Al-based plating layer 103 above can be measured by a calibration curve method using a XRF (fluorescent X-ray, X-ray Fluorescence).
[0077]
(Organic resin 111)
　in the steel plate of the second embodiment, the organic resin 111 which is a component of the surface coating layer 107, as long as it functions as a binder to hold the ZnO grains 109 in the surface coating layer 107, in particular but it is not limited. The organic resin 111 is lost by burning during hot pressing prior to the heating, it does not affect the press working, welding, or the like is a subsequent process. The organic resin 111 when the drug water-based, it is preferable to use a ZnO as well as stable cation resin in weakly alkaline, for example, can be used cationic urethane resin and a cationic acrylic resin. In the second embodiment, for the concentration (g / kg) ratio of the organic resin 111 in the drug, not specified.
[0078]
　In order to sufficiently express the function as a binder in the organic resin 111, the content of the organic resin 111 on the entire surface coating layer 107, by mass%, 10% or more, it is preferable that 60% or less. When the content is less than 10%, acts as a binder is not sufficiently expressed, the coating film before the heating is likely to peel. In order to get a stable an action as the binder, the content of the organic resin 111, more preferably 15% or more. On the other hand, when the content of the organic resin 111 is 60 percent, odor generation during heating becomes remarkable.
[0079]
　Next, the method of forming the intermediate coating layer 105 and the surface film layer 107 on the Al-based plating layer 103 above, respectively, but are not limited to, an aqueous solution or solvent to dissolve the respective main component of the, Al-based plating layer on the surface of, and coated according to a known method such as a roll coater or a spray can be formed by drying. Although there is no particular limitation on the drying method after coating, hot air, the IH (induction heating), NIR (near infrared), such as electric heating, can be used each method. Furthermore, the heating temperature in drying, taking into account the glass transition temperature of the organic resin 111 is a binder (Tg), is preferably set as appropriate.
[0080]
　As described above, according to the Al-based plated steel sheet 100 of the second embodiment, the surface coating layer 107 and the intermediate coating layer 105, without ZnO disappears at the contact portion with the conveyor, in hot press to express the excellent lubricity, it is possible to achieve excellent corrosion resistance after excellent workability and hot pressing during hot pressing or the like. Further, according to the steel plate of the second embodiment, the presence of surface film layer 107 having excellent lubricating properties, it is possible to suppress the adhesion to the mold. Even if the Al-based plating layer 103 was powdering by heating, the presence of the surface coating layer 107 having excellent lubricity, the molds used in the subsequent press powder (Al-Fe powder, etc.) that adhesion is suppressed. Therefore, when the steel plate of the second embodiment to hot press, including the step of removing the Al-Fe powder and adhesion to the mold is not required, it is possible to realize excellent productivity.
[0081]
　Third Embodiment:
　Next, for each layer of the third embodiment will be described in detail below. The third embodiment, the intermediate coating layer, satisfies the condition (C).
[0082]
[Preform 101]
　as the base material 101 used for the third embodiment of the Al-based plated steel sheet 100, even if the hot press after plating layer formed, excellent mechanical strength (tensile strength, yield point, elongation , diaphragm, hardness, impact value, fatigue strength, which means the properties related to mechanical deformation and fracture of the creep strength, etc.) using a member having a. For example, using a member having enhanced hardenability by the addition of C (carbon) and alloying elements. Thus, with respect to the steel sheet obtained by forming the Al-based plating layer 103 and the surface film layer 107, in the automotive parts obtained by performing hot pressing, it is excellent mechanical strength expression.
[0083]
　A third embodiment of the preform 101 of the steel plate can be used a known long as it has excellent mechanical strength. For example, although those having the same composition as the first embodiment can be utilized as the base material 101, components of the base material 101 is not limited to this.
[0084]
[Al-based plating layer
　103] Al-based plating layer 103 is formed on at least one surface of the base material 101. Al-based plating layer 103 is, for example, the same method may include the composition as the first embodiment.
[0085]
Intermediate coating layer 105 '
　on the surface of the Al-based Intermediate coating layer 105, for example, the various solvents of water and organic solvents, can be formed using a solution prepared by mixing the ingredients.
　Specific fluoride salt, AlF 3 , Alof, LiF, NaF, KF, MgF two , CaF 2 of one kind or two or more kinds can be cited, but the invention is not limited thereto.
[0086]
　By constituting the intermediate coating layer 105 of aluminum, an alkali metal and alkaline earth metal fluoride salt, the intermediate coating layer 105 becomes uniform film during its formation, the Al-based plating layer 103, ZnO surface coating layer 107 there can be the site of contact ceases to exist, to suppress disappearance of ZnO on heating of the hot press.
　Incidentally, when the intermediate coating layer 105 of aluminum, are formed with alkali metals and alkaline earth metals other than fluoride salts, when heated hot stamping, since the intermediate coating layer 105 reacts with the Al-based plating layer 103, the film uniformity is lost, there is a site of contact between the Al-based plating layer 103 and ZnO, it may not be prevented the loss of ZnO.
[0087]
　Fluoride salts contained in the intermediate coating layer 105 contributes to uniformity of the intermediate coating layer 105. The amount of fluorine contained in the intermediate coating layer 105 (F) (also referred to as coating weight) 20 mg / m 2 by the above, it is possible to obtain sufficient lubricity and corrosion resistance.
[0088]
　On the other hand, lubricity and corrosion resistance as the fluoride salt increases although increased, decreased spot weldability because the electrical resistance of the film increases. The amount of fluorine (F) contained in the intermediate coating layer 105 is 2000 mg / m 2 as long or less, it is possible to obtain a sufficient spot weldability.
[0089]
　The amount of fluorine (F), depending calibration curve method using an electron beam microanalyzer, can be measured.
[0090]
　Note that the fluoride salt contained in the intermediate coating layer 105, fluorine (F) an amount of 100 mg / m 2 or more, 1000 mg / m 2 by mass or less, because the effect is that achieved at higher than the respective level, more preferable.
[0091]
[Surface film layer 107 '
　surface film layer 107 has an average particle diameter of 0.10μm or more, and less ZnO particles 109 5.00, while containing an organic resin 111, the amount of deposition of the ZnO particles 109 of metal Zn terms 0.5 g / m 2 or more, 10.0 g / m 2 is required to be less. In the case where the Al-based plated layer 103 on both surfaces of the base material 101 is formed on the surface of at least one side of the intermediate coating layer 105 on the Al-based plating layer 103, to form a surface film layer 107 it can.
[0092]
　Surface film layer 107 is, for example, in various solvents such as water or an organic solvent, can be formed using a solution prepared by mixing the components described above.
[0093]
(ZnO particles
　109) ZnO particles 109 contacts the mold and the point to improve the workability by lowering the dynamic friction coefficient. However, the average particle size is less than 0.10μm of ZnO particles 109, since the contact point between the ZnO grains 109 and the mold is too large at the time of press working, can not be sufficiently improved processability.
[0094]
　Meanwhile, ZnO is an insulator, the average particle size of the ZnO particles 109 is more than 5.00, it becomes difficult to collapse at the time of welding圧加, can not be sufficiently ensured conductive point, making it easier out dust weldability is deteriorated.
　Therefore, the average particle size of the ZnO particles 109 0.10μm or more, preferably not more than 5.00.
[0095]
　The method of measuring the average particle size of the ZnO particles 109 is not particularly limited. For example, scanning electron microscopy (SEM, Scanning Electron Microscope) using a like, by measuring the particle diameter by observing any 10 or more ZnO particles 109 at 2000 times may be obtained by calculating the average value. Alternatively, using a particle size distribution measuring device may determine the average particle size of the ZnO particles 109.
[0096]
　Also, increasing the workability during hot pressing, it is necessary to secure the amount of some ZnO particles 109, Zn amount (also referred to as coating weight) 0.5 g / m 2 to be equal to or greater than favored
arbitrariness. On the other hand, as the amount of ZnO particles 109 increases, although lubricating property and corrosion resistance is increased, the electric resistance of the film is increased. Therefore, in order to ensure the spot weldability, 10.0 g / m with Zn amount upper limit of the amount of ZnO particles 109 2 is preferably set to.
Incidentally, the amount of ZnO particles 109, 1.0 g / m with Zn amount 2 or more, 7.0 g / m 2 when A, since the effect is exhibited at a higher level, more preferably.
　Note that the amount of ZnO particles 109 here, during hot pressing, which is the amount deposited before the heat put into the conveyor.
[0097]
　Deposition of ZnO particles 109 can be measured by a calibration curve method using a XRF (fluorescent X-ray, X-ray Fluorescence).
[0098]
　(Organic resin 111)
　surface coating layer 107, may be contained an organic resin 111 as described above, the organic resin 111 holds the ZnO in the surface coating layer 107, it is sufficient to function as a binder, in particular It is not intended to be limiting. This organic resin 111 during hot before pressing the heating is lost by burning, it does not affect the machining and welding a subsequent process. When using the agent of water-based instead of the organic resin 111, it is desirable to use a ZnO as well as stable cation resin in weakly alkaline, for example, cationic urethane resin and a cationic acrylic resin. In the third embodiment, for the concentration (g / kg) ratio of the organic resin 111 in the drug, not specified.
[0099]
　In order to sufficiently express the function as a binder in the organic resin 111, the content of the organic resin 111 on the entire surface coating layer 107, by mass%, 10% or more, it is preferable that 60% or less.
[0100]
　If the content is less than 10%, the binder effect is not obtained sufficiently, coating before heating is liable to peel. In other words, when the content of the resin 111 in a weight ratio of 10% or more, it is possible to stably obtain the binder effect. On the other hand, if the content of the resin 111 is greater than 60% by mass ratio is not preferable because the smell at the time of heating becomes remarkable.
[0101]
　Method of forming a surface coating layer 107 is not particularly limited, a solution prepared by mixing the components described above in various solvents such as water or an organic solvent, in a known manner of a roll coater or a spray or the like on the surface of the intermediate coating layer coated, it can be formed by drying. There is no particular limitation on the drying method after coating, hot air, the IH (induction heating), NIR (near infrared), can be used electrical heating system or the like. However, Atsushi Nobori during drying, taking into account the glass transition temperature of the resin 111 (Tg) is a binder, it is preferable to appropriately set.
[0102]
　As described above, according to the third embodiment of the Al-based plated steel sheet 100, the surface coating layer 107 of the outermost layer, without ZnO disappears at the contact portion with the conveyor, excellent in hot press to express the lubricity, it is possible to achieve excellent corrosion resistance after excellent workability and hot pressing during hot pressing or the like. Further, according to the steel plate of the third embodiment, the presence of surface film layer 107 having excellent lubricating properties, it is possible to suppress the adhesion to the mold. Even if the Al-based plating layer 103 was powdering by heating, the presence of the surface coating layer 107 having excellent lubricity, the molds used in the subsequent press powder (Al-Fe powder, etc.) that adhesion is suppressed. Therefore, when the steel plate of the third embodiment will be hot press, including the step of removing the Al-Fe powder and adhesion to the mold is not required, it is possible to realize excellent productivity.
[0103]
　Fourth Embodiment:
　Next, each layer of the fourth embodiment will be described in detail below. The fourth embodiment, the intermediate coating layer, satisfies the condition (D).
[0104]
[Preform 101]
　as the base material 101 used in the fourth embodiment of the Al-based plated steel sheet 100, even if the hot press after plating layer formed, excellent mechanical strength (tensile strength, yield point, elongation , diaphragm, hardness, impact value, fatigue strength, using a member such as to have a means properties regarding mechanical deformation and destruction of such creep strength). For example, using a member having enhanced hardenability by the addition of C (carbon) and alloying elements. Thus, Al-based plating layer 103, with respect to the steel sheet obtained by forming an intermediate coating layer 105 and the surface film layer 107, in automotive parts obtained by applying the hot press, superior mechanical strength is expressed It is.
[0105]
　Preform 101 of steel plate of the fourth embodiment can utilize a known long as it has excellent mechanical strength. For example, it is possible to use a material having the same composition as the first embodiment, components of the base material 101 is not limited to this.
[0106]
[Al-based plating layer
　103] Al-based plating layer 103 is formed on at least one surface of the base material 101. Al-based plating layer 103 is, for example, the same method may include the composition as the first embodiment.
[0107]
Intermediate coating layer 105 '
　intermediate coating layer 105 is formed on the surface of the Al-based plating layer 103, the prevention of oxidation of Al in the Al-based plating layer 103, and acts on the anti-reducing of ZnO in the surface film layer 107. Intermediate coating layer 105, an Al-based layered double hydroxide represented by the following formula (1), the metal M converted at 10 mg / m 2 or more, 1000 mg / m 2 is required to contain less.
[M 2+ 1-x Al 3+ x (OH) 2 ] [A n- x / n · mH 2 O] · · · (1)
　where, M in the chemical formula (1) 2+ is a divalent metal an ion, a n- is the n-valent anion.
　A is not limited to one type of element may comprise a multi-element. Also, when containing a plurality of types of A, it need not be the same valence. In this case, n represents the chemical formula (1), and 1 or more, 3 or less.
[0108]
　In general, the layered double hydroxide is a double hydroxide trivalent metal ions dissolved in the divalent metal hydroxide is a compound of layered structure sandwiching an anion between layers of the hydroxide . Al-based layered double hydroxides, trivalent metal ions are Al, any divalent metal ion M 2+ comprises a.
[0109]
　When the Al-based plating layer 103 on both surfaces of the base material 101 is formed, it is possible to form the intermediate coating layer 105 on the surface of at least one side of the plated layer. Intermediate coating layer 105 is, for example, each of the above components in various solvents such as water or an organic solvent (Al 3+ , M 2+ , A n- ) a solution containing, by applying the Al-based plating layer 103 or dried, M 2+ ions and a n- alkaline solution containing ions, after or immersing the Al-based plated steel sheet 100 can be formed by washed with water and dried.
　Further, the x in the chemical formula 1 is a positive number less than 1, for example, is 1/3, 1/5 or more, and more preferably at 1/3 or less.
　Furthermore, m in Formula 1 is a positive number, for example a 2/3, 2/3 or more, more preferably 2 or less.
[0110]
　The intermediate coating layer 105 of the fourth embodiment, other Al-based layered double hydroxide may contain other components, if necessary. The fourth embodiment the intermediate coating layer 105 is preferably made of Al-based layered double hydroxide, inner or intermediate film layer 105, the impurity of the processing liquid residues and the like in the interface between the surface coating layer 107 there is a case that contains.
[0111]
　Al-based layered double hydroxides contained in the intermediate coating layer 105, 10 mg / m of a metal M terms 2 by weight, and Al-based plating layer 103, the site where the ZnO particles 109 of the surface coating layer 107 is in contact because would exist, it is impossible to suppress the loss of ZnO on heating of the hot press. On the other hand, Al-based layered double hydroxides contained in the intermediate coating layer 105, 1000 mg / m of a metal M terms 2 exceeds, the contact resistance increases, the spot weldability is deteriorated.
[0112]
　Hereinafter, the amount of a metal M in terms of the Al-based layered double hydroxides contained in the intermediate coating layer 105 may be referred to adhesion amount of the metal M in terms of the intermediate coating layer 105. Measurement of adhesion amount of the metal M in terms of the intermediate coating layer 105 can be measured by a calibration curve method of fluorescent X-ray analysis. Whether the intermediate coating layer 105 is in the Al-based layered double hydroxide can be confirmed by a wide-angle XRD (X-Ray Diffraction) analysis.
[0113]
　Metal ion M of the Al-based layered double hydroxide 2+ as, an alkaline earth metal ion, Fe 2+ , Ni 2+ , Co 2+ , Cu 2+ can be exemplified such as, 2 from group 11 metals ions or alkaline earth metal ion. Also, A n- represents a hydroxyl group (OH - ) and OH - may contain an anion other than, but chloride ions, it is desirable to include one or two or more any of the sulfate ion, carbonate ion . M 2+ is an alkaline earth metal ion, A n- is chloride ion, denseness is increased by including more than one kind or two kinds of sulfate ions, carbonate ions, Al contained in the Al-based plating layer 103 it can be further suppressed oxidation. Incidentally, M 2+ is Zn 2+ case, Al-based layered double hydroxides easily ZnO and ZnAl by heating 2 O 4 for would be decomposed into, it can not be maintained the structure of the layered double hydroxide Zn 2 +It is excluded.
[0114]
　Furthermore, Al-based layered double hydroxide metal ions M 2+ calcium ions, anions composition comprising a chloride ion (Ca 2 Al (OH) 6 Cl · 2H 2 For O), the intermediate film layer 105 since denseness is most improved, it is possible to suppress the oxidation of the reduced and Al in ZnO, preferred.
[0115]
[Surface film layer 107 '
　surface film layer 107 has an average particle diameter of 0.10μm or more, and less ZnO particles 109 5.00, while containing an organic resin 111, the amount of deposition of the ZnO particles 109 of metal Zn terms 0.5 g / m 2 or more, 10.0 g / m 2 is required to be less. In the case where the Al-based plated layer 103 on both surfaces of the base material 101 is formed on the surface of at least one side of the intermediate coating layer 105 on the Al-based plating layer 103, to form a surface film layer 107 it can.
[0116]
　Surface film layer 107 is, for example, in various solvents such as water or an organic solvent, can be formed using a solution prepared by mixing the components described above.
[0117]
(ZnO particles 109)
　in order to obtain good workability and corrosion resistance hot pressing, the surface of the Al-based plating layer 103, an average particle diameter of 0.10μm or more, with ZnO particles 109 metal Zn Conversion 5.00μm 0.5 g / m 2 or more, 10.0 g / m 2 is required to be formed at a coverage of less. ZnO particles 109 contacts the mold and the point to improve the workability by lowering the dynamic friction coefficient. However, the average particle size is less than 0.10μm of ZnO particles 109, since the contact point between the ZnO grains 109 and the mold is too large at the time of press working, can not be sufficiently improved processability.
[0118]
　Meanwhile, ZnO is an insulator, the average particle size of the ZnO particles 109 is more than 5.00, it becomes difficult to collapse at the time of welding 圧加, can not be sufficiently ensured conductive point, making it easier out dust weldability is deteriorated.
[0119]
　The method of measuring the average particle size of the ZnO particles 109 is not particularly limited. For example, scanning electron microscopy (SEM, Scanning Electron Microscope) using a like, by measuring the particle diameter by observing any 10 or more ZnO particles 109 at 2000 times may be obtained by calculating the average value. Alternatively, using a particle size distribution measuring device may determine the average particle size of the ZnO particles 109.
[0120]
　Further, the amount of deposition of all of the ZnO particles 109 of the surface coating layer 107, 0.5 g / m of a metal Zn terms 2 by weight, it is impossible to obtain sufficient workability during hot pressing. Further, as the amount of deposition of the ZnO particles 109 increases, although the workability and the corrosion resistance of the steel sheet is increased, since the electric resistance of the film of the surface coating layer 107 is increased, the steel sheet resistance weldability (for example, spot weldability ) is reduced. In other words, the adhesion amount of all of the ZnO particles 109 of the surface coating layer 107, 10.0 g / m of a metal Zn terms 2 exceeds, it is difficult to obtain a sufficient resistance weldability of the steel sheet.
　Herein, the term coating weight and, at the time of hot press, a deposition amount before heating placed on a conveyor.
[0121]
　Deposition of ZnO particles 109 to Al-based plating layer 103 above can be measured by a calibration curve method using a XRF (fluorescent X-ray, X-ray Fluorescence).
[0122]
　(Organic resin 111)
　in the steel sheet of the fourth embodiment, the organic resin 111 which is a component of the surface coating layer 107, as long as it functions as a binder to hold the ZnO particles 109 in the film is not particularly limited . The organic resin 111 is lost by burning during hot pressing prior to the heating, it does not affect the press working, welding, or the like is a subsequent process. The organic resin 111 when the drug water-based, it is preferable to use a ZnO as well as stable cation resin in weakly alkaline, for example, can be used cationic urethane resin and a cationic acrylic resin. In the fourth embodiment, the concentration (g / kg) ratio of the organic resin 111 in the drug, not specified.
[0123]
　In order to sufficiently express the function as a binder in the organic resin 111, the content of the organic resin 111 on the entire surface coating layer 107, by mass%, 10% or more, it is preferable that 60% or less. When the content is less than 10%, acts as a binder is not sufficiently expressed, the coating film before the heating is likely to peel. In order to get a stable an action as the binder, the content of the organic resin 111, more preferably 15% or more. On the other hand, when the content of the organic resin 111 is 60 percent, the occurrence of unpleasant odor upon heating becomes remarkable.
[0124]
　Next, the method of forming the intermediate coating layer 105 and the surface film layer 107 on the Al-based plating layer 103 above, respectively, but are not limited to, an aqueous solution or solvent to dissolve the respective main component of the, Al-based plating layer on the surface of, and coated according to a known method such as a roll coater or a spray can be formed by drying. Although there is no particular limitation on the drying method after coating, hot air, the IH (induction heating, Induction Heating), NIR (near infrared, Near InfraRed), such as electric heating, can be used each method. Furthermore, the heating temperature in drying, taking into account the glass transition temperature of the organic resin 111 is a binder (Tg), is preferably set as appropriate.
[0125]
　As described above, according to the fourth embodiment of the Al-based plated steel sheet 100 (steel), by providing a surface coating layer 107 and the intermediate coating layer 105, without ZnO disappears at the contact portion between the conveyor , for expressing excellent lubricity in hot pressing, it is possible to achieve excellent corrosion resistance after excellent workability and hot pressing during hot pressing or the like. Further, according to the steel sheet of the fourth embodiment, the presence of surface film layer 107 having excellent lubricating properties, it is possible to suppress the adhesion to the mold. Even if the Al-based plating layer 103 was powdering by heating, the presence of the surface coating layer 107 having excellent lubricity, the molds used in the subsequent press powder (Al-Fe powder, etc.) that adhesion is suppressed. Therefore, when the steel sheet of the fourth embodiment will be hot press, including the step of removing the Al-Fe powder and adhesion to the mold is not required, it is possible to realize excellent productivity.
[0126]
　Fifth Embodiment:
　Next, each layer of the fifth embodiment will be described in detail below. The fifth embodiment, the intermediate coating layer, satisfies the condition (E).
[0127]
　[Preform 101]
　The (member for forming the Al-based plating layer 103) base material 101 used for the Al-based plated steel sheet 100 of the fifth embodiment, even when the hot press after plating layer formation, excellent mechanical strength member so as to have a (tensile strength, yield point, elongation, diaphragm, hardness, impact value, fatigue strength, which means the properties related to mechanical deformation and fracture of the creep strength, etc.) use. For example, using a member having enhanced hardenability by the addition of C (carbon) and alloying elements. Thus, Al-based plating layer 103 to be described later, the intermediate coating layer 105 and the Al-based plated steel sheet 100 obtained by forming a surface coating layer 107, in automotive parts obtained by applying the hot press is excellent mechanical strength expression.
[0128]
　That is, the fifth base member 101 for Al-based plated steel sheet 100 of an embodiment of can utilize a known long as it has excellent mechanical strength. For example, it is possible to use a material having the same composition as the first embodiment, components of the base material 101 is not limited to this.
[0129]
　[Al-based plating layer
　103] Al-based plating layer 103 is formed on at least one surface of the base material 101. Al-based plating layer 103 is, for example, the same method may include the composition as the first embodiment.
[0130]
　Intermediate coating layer 105 '
　when the Al-based plating layer 103 on both surfaces of the base material 101 is formed, it is possible to form the intermediate coating layer 105 on at least one side of the Al-based plating layer 103. Of course, if the Al-based plating layer 103 on only one surface of the base material 101 is formed, directly formed thereon (see FIG. 1). Furthermore, Al-based plating layer 103 when formed on both surfaces of the base material 101 is formed directly adjacent on each of the both surfaces of the Al-based plating layer 103 (see FIG. 2).
[0131]
　Intermediate coating layer 105 is formed on the surface of the Al-based plating layer 103, it acts on the anti-reducing of ZnO in antioxidant and a surface coating layer 107 of Al in the Al-based plating layer 103. Intermediate coating layer 105 is Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlN, TiN, Si 3 N 4 , TiC, ceramic deposited film composed of any one of SiC, or Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlN, TiN, Si 3 N 4 , TiC, consists composite ceramic deposited film composed of two or more of SiC, is 10nm or more thickness is 1000nm or less.
[0132]
　When the Al-based plating layer 103 on both surfaces of the base material 101 is formed, it is possible to form the intermediate coating layer 105 on at least one side of the plated layer. Intermediate coating layer 105, for example, can be formed by chemical vapor deposition or physical vapor deposition.
[0133]
　The thickness of the intermediate coating layer 105, is less than 10 nm, it does not function well as a barrier for preventing the diffusion of oxygen, to obtain the effect of reducing the prevention of ZnO in antioxidant and a surface coating layer 107 of Al in the plating layer can not. Furthermore, can not be sufficiently secured corrosion resistance after painting to can not be secured paint adhesion for zinc phosphate coating weight upon conversion treatment with Zn remaining amount is small (zinc phosphate treatment) becomes insufficient. Therefore, the lower limit of the thickness of the intermediate coating layer 105 and above 10 nm, preferably not less than 20 nm. On the other hand, if the thickness of the intermediate coating layer 105 is greater than 1000 nm, weldability is inhibited. Therefore, the upper limit of the thickness of the intermediate coating layer 105 and 1000nm or less, preferably 400nm or less. The thickness of the intermediate coating layer 105 is formed on the surface of the Al-based plated steel sheet 100, Al-based plating layer 103, cross-sectional scanning electron microscope of the intermediate coating layer 105 and the surface coating layer 107 (Scanning Electron Microscope, SEM) or transmission electron microscope (transmission electron microscope, TEM) can be observed by measures. An intermediate coating layer 105, Al-based plating layer 103, the difference in contrast, the electron microscopic photograph, since the interface between (boundary) can be clearly observed from the intermediate coating layer 105, for measuring a distance to the boundary it is thus possible to determine the thickness of the intermediate coating layer 105.
[0134]
　The intermediate coating layer 105, Al can withstand heat temperature 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlN, TiN, Si 3 N 4 , TiC, ceramic deposited film made of any one of SiC or, al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlN, TiN, Si 3 N 4 and, TiC, composite ceramic deposited film of two or more SiC. However, or caused by hypofunction reduced by Al during heating, it passes through the oxygen, from the viewpoint of preventing the or advance the reduction of ZnO, of the above, it is particularly oxides.
　Also, of the oxides, for heating during cracking reduction, it is intended thermal expansion coefficient is low.
[0135]
　When the intermediate coating layer 105 is not deposited film, e.g., Al by atmospheric oxidation 2 O 3 be formed layers, such an effect that reduction preventing ZnO in antioxidant and a surface coating layer 107 of Al in the plating layer it can not be. Further, Al by anodic oxidation in a solution 2 O 3 be formed layers, Al in the porous structure 2 O 3 for dense structure are layers formed is not formed, the anodic oxide film, Al oxide of the effect of prevention and ZnO of anti-reducing can not be obtained. For example, by forming a deposited film by CVD (chemical vapor deposition), the intermediate coating layer 105 is presumed to have been densified.
[0136]
　[Surface film layer 107 '
　surface film layer 107 has an average particle diameter of 0.10μm or more, and less ZnO particles 109 5.00, while containing an organic resin 111, the amount of deposition of the ZnO particles 109 of metal Zn terms 0.5 g / m 2 or more, 10.0 g / m 2 is required to be less. In the case where the Al-based plated layer 103 on both surfaces of the base material 101 is formed, on at least one side of the intermediate coating layer 105 on the Al-based plating layer 103, to form a surface film layer 107 it can.
[0137]
　Surface film layer 107, for example, can be formed using a solution prepared by mixing the components in the various solvents mentioned above such as water or an organic solvent.
[0138]
　(ZnO particles 109)
　in order to obtain good workability and corrosion resistance in hot pressing, on the intermediate coating layer 105, an average particle diameter of 0.10μm or more, the following ZnO particles 109 5.00 is a metal Zn terms 0 .5G / m 2 or more, 10.0 g / m 2 is required to be formed at a coverage of less. ZnO particles 109 contacts the mold and the point to improve the workability by lowering the dynamic friction coefficient. However, the average particle size is less than 0.10μm of ZnO particles 109, since the contact point between the ZnO grains 109 and the mold is too large at the time of press working, can not be sufficiently improved processability.
[0139]
　On the other hand, the average particle size of the ZnO particles 109 is more than 5.00, weldability is deteriorated. ZnO is an insulating, when the particle size is small, it is possible to sufficiently ensure the current point to collapse during welding 圧加. However, ZnO particles 109 is less likely to collapse during the welding 圧加 average particle diameter of the ZnO grains 109 grow to larger than 5 [mu] m. As a result, it is impossible to ensure a sufficient current supply point, weldability since dust is likely out worse.
[0140]
　The method of measuring the average particle size of the ZnO particles 109 is not particularly limited. For example, scanning electron microscopy (SEM, Scanning Electron Microscope) to observe any 10 or more of ZnO particles 109 at 2000 times to measure the maximum particle diameter of each particle by like, may be obtained by calculating the average value . Alternatively, using a particle size distribution measuring device may determine the average particle size of the ZnO particles 109.
[0141]
　Further, 0.5 g / m at a coverage of all of the ZnO particles 109 of the surface coating layer 107 is metal Zn terms 2 by weight, it is impossible to obtain sufficient workability during hot pressing. Further, as the amount of deposition of the ZnO particles 109 increases, although the workability and the corrosion resistance of the steel sheet is increased, since the film resistance of the surface coating layer 107 is increased, the steel sheet resistance weldability (for example, spot weldability) There is reduced. In other words, the adhesion amount of all of the ZnO particles 109 of the surface coating layer 107 is 10.0 g / m of a metal Zn terms 2 exceeds, it is difficult to obtain a sufficient resistance weldability of the steel sheet.
　Herein, the term coating weight and, at the time of hot press, a deposition amount before heating placed on a conveyor.
[0142]
　(Organic resin 111)
　in the Al-based plated steel sheet 100 of the fifth embodiment, the organic resin 111 which is a component of the surface coating layer 107, as long as it functions as a binder to hold the ZnO particles 109 in the coating It is not particularly limited. The organic resin 111 is lost by burning during hot pressing prior to the heating, it does not affect the press working, welding, or the like is a subsequent process. The organic resin 111 when the drug water-based, it is preferable to use a ZnO as well as stable cation resin in weakly alkaline, for example, can be used cationic urethane resin and a cationic acrylic resin. In the fifth embodiment, the concentration (g / kg) ratio of the organic resin in the drug, not specified. The resin that can be used as the organic resin 111 of the fifth embodiment, the cationic urethane resin (Dai-ichi Kogyo Seiyaku Co., product name SUPERFLEX 650), and the like.
[0143]
　In order to sufficiently express the function as a binder in the organic resin 111, the content of the organic resin 111 on the entire surface coating layer 107, by mass%, 10% or more, it is preferable that 60% or less. When the content is less than 10%, acts as a binder is not sufficiently expressed, the coating film before the heating is likely to peel. In order to get a stable an action as the binder, the content of the organic resin 111, more preferably 15% or more. On the other hand, when the content of the organic resin 111 is 60 percent, the occurrence of unpleasant odor upon heating becomes remarkable.
[0144]
　Incidentally, adhesion of ZnO particles 109 to Al-based plating layer 103 above can be measured by a calibration curve method using a XRF (fluorescent X-ray, X-ray Fluorescence).
[0145]
　Next, the method of forming the intermediate coating layer 105 to the Al-based plating layer 103 above is not particularly limited as long form a deposition film. Can be applied relatively deposited film can be easily formed chemical vapor deposition and physical vapor deposition.
[0146]
　On the other hand, the method of forming the surface coating layer 107 is not particularly limited. The surface coating layer 107 is an aqueous solution or a solvent prepared by dissolving the main component of the, on the Al-based plating layer 103 was applied by a known method such as a roll coater or a spray, followed by drying, can be formed .
　Further, in forming the surface coating layer 107 is not particularly limited for the drying method after coating, hot air, the IH (induction heating, Induction Heating), NIR (near infrared, Near InfraRed), such as electric heating it can be used each method. Furthermore, the heating temperature in drying, taking into account the glass transition temperature of the organic resin 111 is a binder (Tg), is preferably set as appropriate.
[0147]
　As described above, in the hot pressing without According to the fifth embodiment of the Al-based plated steel sheet 100 (steel), the ZnO by surface coating layer 107 and the intermediate coating layer 105 at the contact portion between the conveyor disappear excellent for expressing the lubricity, it is possible to achieve excellent corrosion resistance after excellent workability and hot pressing during hot pressing or the like. Further, according to the Al-based plated steel sheet 100 of the fifth embodiment, the presence of surface film layer 107 having excellent lubricating properties, it is possible to suppress the adhesion to the mold. Even if the Al-based plating layer 103 was powdering by heating, the presence of the surface coating layer 107 having excellent lubricity, the molds used in the subsequent press powder (Al-Fe powder, etc.) that adhesion is suppressed. Therefore, when the Al-based plated steel sheet 100 of the fifth embodiment to hot press, such as the step of removing the Al-Fe powder and adhesion to the mold is not required, to achieve excellent productivity can.
Example
[0148]
　It will be specifically described by the inventors example the effect of the present invention. The present invention is not limited to the conditions used in the following invention examples.
[0149]
Example A:
　chemical compositions shown in Table 1 (the balance Fe and inevitable impurities) was used cold rolled steel sheet (thickness 1.4 mm) of, in Sendzimir method on both sides, using a conventional Al coating bath Al thereby forming a system plating layer 103.
　Incidentally, the adhesion amount of Al-based plating layer 103 with respect to the base material 101 is a gas wiping method, one side 160 g / m 2 was adjusted to.
[0150]
[Table 1]

[0151]
　Then, after cooling the preform 101 Al-based plating layer 103 is formed, Table 2, the formation conditions shown in Table 3, to form an intermediate coating layer 105 and the surface film layer 107, including each element. Sample No. A1 to A5, A7 to A15, Sample No. A17 through A23, A27 intermediate coating layer 105 of, Table 2, it was formed by performing the anodic oxidation under the conditions shown in Table 3. The sample No. A1 to A5, A8, A12 to A15, in the case of A18 to A23, A27, used is an aqueous solution of sulfuric acid, in the case of Sample No. A17, an aqueous solution of hydrochloric acid is used, if the sample No. A7, A9 or 11, mixing an aqueous solution of hydrochloric acid and sulfuric acid are used. Sample No. A6 and Sample No. A24, the table 2, a heat treatment was applied an aqueous solution under the conditions shown in Table 3, were prepared by subsequently performing baking. Sample No. A16 was the Al-based plating layer 103 was prepared by subjecting the atmospheric oxidation under the conditions shown in Table 3. Sample No. A25, A26 is one that does not perform any processing on the Al-based plating layer 103. Note that blank portions of Table 3 shows that the corresponding coating layer of the intermediate film layer 105 and the surface film layer 107 is not formed.
[0152]
　Thereafter, the dispersant of ZnO particles 109 (manufactured by Sakai Chemical Industry Co., Ltd., product name DIF-3ST4S) and cationic urethane resin (Dai-ichi Kogyo Seiyaku Co., Super product name Flex 650) as the organic resin 111 was prepared by mixing the solution was applied on the Al-based plating layer 103 to form an intermediate coating layer 105 by a roll coater, dried at peak metal temperature of 80 ° C., to form a surface coating layer 107. The organic resin 111 of the surface coating layer 107 was 30 wt% (70 wt% of ZnO). As for Sample No. A24, A25, without using an organic resin 111, and dried at 80 ° C. After applying the cyclopentasiloxane containing dispersed ZnO particles.
　There was thus obtained the Al-based plated steel sheet 100 of each test example. The above solution for forming a surface coating layer 107 shown in Table 2, Table 3, were adjusted by using commercially available reagents, it is mixed with distilled water. Incidentally, Table 2, the "Zn adhered amount" in Table 3, the total deposition amount of the value (unit obtained in terms of the mass of metal Zn in ZnO particles 109 per square meter of the intermediate coating layer 105, "G / M 2 is").
[Measurement conditions]
　The composition of the intermediate coating layer 105, the particle size of the ZnO particles 109, ZnO coating weight were identified in the following manner.
1. Composition of the intermediate coating layer 105:
　intermediate coating layer 105 was composed substantially Al, O, in S. S / Al ratio, S / O ratio, Al, O, for each of S, HORIBA Ltd. RF glow discharge optical emission surface analyzer (product name: GD-Profiler2) used, 600 Pa, output 35W, argon gas use conditions in measuring the 2μm depth, and outputs the most S in high surface of S concentration, Al, and O mass%. Five were measured, taking the average value.
2. The particle size of the ZnO particles 109
　manufactured by JEOL Ltd. scanning electron microscope (product name: JSM-7800F) with the ZnO particles 109 was observed at 2000-fold magnification, measuring the maximum particle size of 20 ZnO particles 109, and the particle size of the ZnO particles 109 calculates an average value.
3. ZnO deposition amount
　manufactured by Rigaku Corporation X-ray fluorescence analyzer (product name: ZSX Primus) was measured using a ZnO deposition amount under the following conditions. For the measurement, in advance, preparing a calibration curve showing the relationship between fluorescent X-ray intensity of metal Zn amount conversion, based on the calibration curve to determine the deposition amount.
　Measurement diameter: 30mm
　Measurement Atmosphere: Vacuum
　Spectrum: Zn-K [alpha
　with peak number counting Zn-K [alpha X-ray fluorescence analysis was measured under the above conditions.
[0153]
　Next, the way various properties of the steel sheet of each test example was prepared like was evaluated by the following method.
[0154]
　(1) Hot lubricity (lubricating property)
　against steel of each test example, by performing the mold pull-out tests in hot, to evaluate hot lubricity. More specifically, by inserting the steel sheet of each test example of 30 mm × 350 mm into the furnace, sandwiched between 2 sheets of width 60 mm × length 200 mm × thickness 30 mm SiC plate made of, and heated for 6 minutes at 900 ° C., the furnace after removal, the pressing SKD11 steel Tairakin type (width 50 mm × length 40 mm) from both sides of the steel sheet at about 700 ° C., was drawn. By sandwiching the both sides of the steel sheet by the SiC plate, the supply of oxygen from the surface sufficiently prevented, they simulate a situation in which ZnO film superposition portion in contact with the conveyor disappears at more severe conditions. Pressing and measuring the load and pulling loads, the value obtained in / pull-out load (2 × pressing load) was hot friction coefficient. The value of the dynamic friction coefficient means that the better hot lubricity is small, in the evaluation shown in Table 4, was passed less than 0.52.
[0155]
　(2) corrosion resistance after painting
　by inserting steel sheet of each test example of 120 mm × 200 mm into the furnace, placed in a direction contacting the evaluation surface on the SiC furnace pedestal, 50 mm × 50 mm × heated to 900 ° C. while carrying the SUS304 block of 70 mm, heated standing furnace 6 minutes at 900 ° C., after removal from the oven and immediately quenched sandwich in a stainless steel mold. The cooling rate at this time was about 0.99 ° C. / sec. Then sheared to 70 mm × 150 mm from the center of each steel sheet after cooling, Nippon Parkerizing Co., Ltd. chemical treatment solution after (PB-SX35) in the chemical conversion treatment, Nippon Paint Co., Ltd. electrodeposition coating ( the POWERNICS 110) thickness was applied to a 20 [mu] m, baked at 170 ° C.. Incidentally, inserting each steel sheet 70 mm × 150 mm with a welded thermocouple in the atmosphere furnace set at 900 ° C., where a temperature of until 900 ° C. was measured to calculate the average heating rate, 5 ° C. / sec Met.
[0156]
　Corrosion resistance after painting evaluation was carried out by the method specified in the Society of Automotive Engineers enactment of JASO M609. That is, crosscut in advance cutter in the coating film, the width of blistering the coating from the cross-cut after the corrosion test 180 cycles (60 days) the (one-sided maximum value) was measured. The value of the width of blistering the coating means the superiority of the smaller corrosion resistance, in the evaluation shown in Table 4, were evaluated as acceptable 5mm or less.
[0157]
　(3) Spot weldability
　spot weldability was evaluated as follows.
　Put steel of each test example was produced in the heating furnace, and heated standing furnace 6 minutes at 900 ° C., and quenched by sandwiching immediately mold stainless after removal. The cooling rate at this time was about 0.99 ° C. / sec. Then, sheared each steel sheet after cooling to 30 × 50 mm, the optimal spot welding current range - were measured (upper current limit current). Measurement conditions are as shown below. The lower limit current, the nugget diameter 3 × (t) 0.5 a current value when a, the upper limit current was scattered generated current.
　Current: DC
　electrode: chromium copper, DR (tip 6mmφ is 40R)
　pressure: 400 kgf (1 kgf is 9.8 N.)
　Energizing time: 240 ms
　above values that as spot weldability is excellent large means, in the evaluation shown in Table 4, was passed over 1.0KA.
[0158]
　(4) ZnO loss test
　punched steel plates of each test example 30 mm?, Superimposed on a SiC furnace pedestal 70 mm × 70 mm, while carrying the SUS304 block of 50 mm × 50 mm × 70 mm heated to 900 ° C., 900 heating standing furnace 6 minutes at ° C., after removal, was immediately quenched sandwich in a stainless steel mold. The Zn deposition amount before and after heating was measured by XRF to measure the Zn deposition amount of Zn in terms were calculated ZnO residual ratio of Zn terms.
　The evaluation shown in Table 4, in Zn residual ratio of 75% or more, 0.40 g / m of Zn remaining amount 2 was passed over.
[0159]
　As is clear from Table 4, which is formed directly on the Al-based plating layer 103, the intermediate film layer 105 is intended to include the S and Al oxide, its thickness is 10nm or more and 1000nm or less, intermediate surface film layer 107 formed directly on the film layer 105 is an average particle diameter of 0.10μm or more, it contained the following ZnO particles 109 and the organic resin 111 5.00, the adhesion amount of the ZnO particles 109 of metal Zn terms 0.5 g / m 2 or more, 10.0 g / m 2 for the Al-based plated steel sheet 100 within the scope of the present invention that are below (each inventive example), both the four evaluation of the (various characteristics and ZnO loss for all tests), it can be seen that good results are obtained.
[0160]
[Table 2]

[0161]
[table 3]

[0162]
[Table 4]

[0163]
　In contrast, Sample Nos. A16 to A27, either the intermediate coating layer 105 or the organic resin 111 is not present, the intermediate coating layer 105 is inappropriate thickness of or the intermediate coating layer 105 does not contain S, or ZnO particles 109 average particle size, one of the deposition amount of the ZnO particles 109 is out of the predetermined range of the present invention. About Al-based plated steel sheets outside the scope of the present invention (each sample No. A16 through A27) are both at least one of the four evaluation of the (various characteristics and ZnO loss test), we obtained good results is it can be seen that does not. Sample No. A16 and A17 are those containing no S other than Al oxide, respectively, formed by anodic oxidation in a solution containing no air oxidation and S. In particular, Sample No. A16 and A17 intermediate coating layer 105 does not contain S, and Sample No. A25 intermediate coating layer 105 is not, A26, Sample No. A18 less than the thickness of the intermediate coating layer 105, A27 weldability of Although evaluation is good, poor evaluation of ZnO loss tests, have poor corrosion resistance, workability and corrosion resistance degradation at the site ZnO has disappeared is concerned.
[0164]
Example B:
　The cold-rolled steel sheet having a composition shown in Table 5 (the balance Fe and inevitable impurities) (thickness 1.4 mm) was used as a base material 101, a conventional Al coating bath Sendzimir method on both surfaces to form an Al-based plating layer 103 using. Al-based annealing temperature of the plating layer 103 formed was about 800 ° C.. The adhesion amount of the Al-based plating layer 103 with respect to the base material 101, in the gas wiping method, one side 160 g / m 2 was adjusted to.
[0165]
[table 5]

[0166]
　Then, after cooling the preform 101 Al-based plating layer 103 is formed, to form an intermediate coating layer 105 and the surface film layer 107 shown in Table 6. Intermediate coating layer 105, when forming the surface film layer 107 are both the components shown in Table 6 A solution was prepared by mixing in a solvent, successively applied to the surface of the Al-based plating layer 103 by a roll coater, approximately It was baked at 80 ℃. However, Sample No. B26, B27 did not form an intermediate coating layer 105.
　The composition of the concrete solutions are as follows, using commercially available reagents were adjusted to the following composition by mixing with distilled water.
Sample No.
　B1: 2.0% Na 2 B 4 O 7 solution, pH 10
Sample No.
　B2: 10% aqueous sodium silicate solution, pH 12
Sample No.
　B3: 10% Na 3 PO 4 · 12H 2 O aqueous solution, pH 12
Sample No.
　B4: 2 % AlPO 4 solution + HNO 3 , pH 3
sample No. B5:
　2% bis (4-hydroxybenzene sulfonic acid) aqueous solution of zinc + HNO 3 , pH 3
Sample No.
　B6: 2% P- toluenesulfonic acid sodium aqueous solution + HNO 3 , pH 3
Sample No.
　B7: 5% KMnO 4 aqueous solution, pH 6
Sample No. B8, B10 ,
　B11: 2.5% KMnO 4 + 2.5% sodium silicate aqueous solution, pH 12
sample No. B9, B12 from
　B25: 2.5% KMnO 4 + 2.5% Zn 2 SiO 4 solution + CH 3 COOH, pH 4
[0167]
　Thereafter, the dispersant of ZnO particles 109 (manufactured by Sakai Chemical Industry Co., Ltd., product name DIF-3ST4S) and as the organic resin 111, a cationic urethane resin (Dai-ichi Kogyo Seiyaku Co., product name SUPERFLEX 650; liquid) were mixed the solution adjusted Te, is applied to the surface of the Al-based plating layer 103 to form an intermediate coating layer 105 by a roll coater, dried similarly reached plate temperature 80 ° C. and the formation of the intermediate coating layer 105, an organic resin 111 was to form a surface coating layer 107 was 30 wt% (70 wt% of ZnO). As for Sample No. B27, and dried at 80 ° C. after applying only dispersant ZnO particles 109.
[0168]
　[Measurement conditions]
　The composition of the intermediate coating layer 105, the thickness, the particle size of the ZnO particles 109, ZnO coating weight were identified in the following manner.
[0169]
　1. Composition of the intermediate coating layer 105:
　Rigaku Corporation X-ray diffraction apparatus (product name: SmartLab 3) used, using Cu-K [alpha line, by setting the incident angle to 90 degrees, ICDD data peaks obtained by the thin film method compared to, and identify the composition of the layered double hydroxide.
[0170]
　2. Thickness of the intermediate coating layer 105:
　cross-section was observed by a scanning electron microscope and a thickness of the average value of the thickness of the intermediate coating layer 105 was measured 10 points arbitrarily.
　3. Mn / Si mass ratio
　Rigaku Corporation X-ray fluorescence analyzer (product name: ZSX Primus) used to measure the deposition amount of Mn and Si in the following conditions to obtain the mass ratio from the deposition amount. For the measurement, in advance, Mn, preparing a calibration curve showing the relationship between the Si content and the fluorescent X-ray intensity, based on the calibration curve to determine the deposition amount.
Measurement diameter: 30 mm
, measurement atmosphere: vacuum
Spectrum: Mn-Kα (Si-Kα )
　with peak number counting Mn-K [alpha X-ray fluorescence analysis was measured by the above conditions (Si-Kα).
[0171]
　4. The particle size of the ZnO particles 109:
　manufactured by JEOL Ltd. scanning electron microscope (product name: JSM-7800F) with the ZnO particles 109 was observed at 2000-fold magnification, measuring the maximum diameter of the 20 ZnO particles 109, and the particle size of the ZnO particles 109 calculates an average value.
[0172]
　5. ZnO deposition amount
　manufactured by Rigaku Corporation X-ray fluorescence analyzer (product name: ZSX Primus) was measured using a ZnO deposition amount under the following conditions. For the measurement, in advance, preparing a calibration curve showing the relationship between the Zn content and the fluorescent X-ray intensity, based on the calibration curve to determine the deposition amount.
Measurement diameter: 30 mm
, measurement atmosphere: vacuum
Spectrum: Zn-K [alpha
　with peak number counting Zn-K [alpha X-ray fluorescence analysis was measured under the above conditions.
[0173]
　[Evaluation of Sample]
　Next, the way various properties of the steel sheet of each test example was prepared like was evaluated by the following method.
[0174]
(1) Hot lubricity:
　By performing the mold pull-out test in hot the sample was evaluated hot lubricity.
Insert each test example of 30 mm × 350 mm into the furnace, sandwiched between 2 sheets of width 60 mm × length 200 mm × thickness 30 mm SiC plate made of, and heated for 6 minutes at 900 ° C., after removal from the furnace, about 700 ° C. in SKD11 steel Tairakin-type (50mm width × 40 mm length) pressing from both sides of the steel sheet was drawn. Pressing and measuring the load and pulling loads, the value obtained in / pull-out load (2 × pressed load) was hot friction coefficient. Hot friction coefficient was evaluated as acceptable than 0.52.
[0175]
(2) corrosion resistance after
　painting: Insert the sample of each test example of 120 mm × 200 mm into the furnace, placed in a direction contacting the evaluation surface on the SiC furnace pedestal and heated to 900 ° C., 50 mm × while carrying the SUS304 block of 50 mm × 70 mm, heated standing furnace 6 minutes at 900 ° C., after removal from the oven and immediately quenched sandwich in a stainless steel mold. The cooling rate at this time was about 0.99 ° C. / sec. Then sheared to 70 mm × 150 mm from the center of each steel sheet after cooling, Nippon Parkerizing Co., Ltd. chemical treatment solution after (PB-SX35) in the chemical conversion treatment, Nippon Paint Co., Ltd. electrodeposition coating ( the POWERNICS 110) thickness was applied to a 20 [mu] m, baked at 170 ° C.. Incidentally, in the atmosphere furnace set at 900 ° C., where to insert each sample 70 mm × 150 mm with a welded thermocouple, the temperature of until 900 ° C. was measured to calculate the average heating rate, 5 ° C. / It was second.
　Corrosion resistance after painting evaluation was carried out by the method specified in the Society of Automotive Engineers enactment of JASO M609. That is, crosscut in advance cutter in the coating film, the width of blistering the coating from the cross-cut after the corrosion test 180 cycles (60 days) the (one-sided maximum value) was measured. The less than or equal to the width 5mm was passed.
[0176]
(3) Spot weldability:
　Spot weldability was evaluated as follows.
The sample was placed in each test example was produced in the heating furnace, and heated standing furnace 6 minutes at 900 ° C., and quenched by sandwiching immediately stainless steel mold after removal. The cooling rate at this time was about 0.99 ° C. / sec. Then, sheared each steel sheet after cooling to 30 mm × 50 mm, the optimal spot welding current range - were measured (upper current limit current). Measurement conditions are as shown below. The lower limit current nugget diameter 3 × (t) 0.5 a current value when a, the upper limit current was scattered generated current. Current range was passed more than 1.0A.
- current: DC
electrode: chromium copper, DR (tip 6mmφ is 40R)
- pressure: 400 kgf (1 kgf is 9.8 N.)
- energizing time: 240 ms
[0177]
(4) ZnO loss test (ZnO residual ratio, the residual amount):
　punched sample to 30mmφ of each test example, of 70 mm × 70 mm superimposed on the SiC furnace base, 50 mm × 50 mm × 70 mm of which was heated to 900 ° C. , while carrying the SUS304 block, heated standing furnace 6 minutes at 900 ° C., after removal, it was immediately quenched sandwich in a stainless steel mold. The Zn deposition amount before and after heating was measured by XRF, was calculated ZnO residual ratio with ZnO deposition amount. Residual amount 0.4 g / m 2 was passed over.
　The results are shown in Table 6.
[0178]
[Table 6]

[0179]
　Table 6 As is apparent, include an intermediate coating layer 105 salt oxo acid formed on the surface of the Al-based plating layer 103, deposited with a film thickness of 10nm or more and 500nm or less, the surface of the intermediate film layer 105 surface film layer 107 formed has an average particle diameter of 0.10μm or more, it contained the following ZnO particles 109 and the organic resin 111 5.00, the adhesion amount of ZnO particles 109 0.5 g / m 2 or more, 10. 0 g / m 2 of the following, for the Al-based plated steel sheet 100 in the range of the present application (B19 from sample No. B1), both, for all four evaluation described above, it is found that good results have been obtained .
[0180]
　In contrast, when or intermediate film layer 105 is not an average particle size, one of the deposition amount of the ZnO particles 109 is out of the present application a predetermined range, the present range of the Al-based of ZnO particles 109 the plated steel sheet 100 (B27 from sample No. B20), both, for at least one of the four evaluation of the (various characteristics and ZnO loss test), it can be seen that no good results.
[0181]
　Specifically, Sample No. B20 is ZnO residual amount the film thickness of the intermediate coating layer 105 is too thin, hot lubricity, corrosion resistance after coating was inferior.
　Sample No. B21, the film thickness of the intermediate coating layer 105 was inferior in corrosion resistance after painting too thick.
　Sample No. B22 has an average particle diameter is too small hot lubricity of ZnO particles 109 was inferior.
　Sample No. B23 has an average particle size of the ZnO particles 109 is too large was inferior spot weldability.
　Sample No. B24 is too small adhesion amount of ZnO particles 109, after coating a hot lubricity corrosion resistance was inferior.
　Sample No. B25 is too much amount of deposition of the ZnO particles 109 were inferior spot weldability.
　Sample No. B26, since not provided intermediate coating layer 105, ZnO remaining amount, hot lubricity, corrosion resistance after coating was inferior.
　Sample No. B27, since not provided intermediate coating layer 105 and the organic resin 111, ZnO remaining amount, hot lubricity, corrosion resistance after coating was inferior.
[0182]
　Example C:
　cold-rolled steel sheet having a composition shown in Table 7 (the balance Fe and unavoidable impurities, thickness 1.4 mm) was prepared as a base material 101, typically of Al plating Sendzimir method on both surfaces of the cold rolled steel sheet to form an Al-based plating layer 103 using the bath. Al-based annealing temperature of the plating layer 103 formed was about 800 ° C..
　The amount of Al-based plating layer 103 adhering to the base material 101, in the gas wiping method, one side 160 g / m 2 was adjusted to.
[0183]
[Table 7]

[0184]
　Then, after cooling the preform 101 Al-based plating layer 103 is formed, to form an intermediate coating layer 105 and the surface film layer 107 shown in Table 8. Intermediate coating layer 105, when forming the surface film layer 107 are both the components shown in Table 8 A solution was prepared by mixing in a solvent, successively applied to the surface of the Al-based plating layer 103 by a roll coater, approximately It was baked at 80 ℃. However, Sample No. C22, C23 did not form an intermediate coating layer 105.
　The composition of the concrete solutions are as follows, using commercially available reagents were adjusted to the following composition by mixing with distilled water.
Sample No. C1, C7 from C14, C18 from
　C21: 0.5% AlF 3 solution
Sample No.
　C2: 0.2% LiF solution
Sample No.
　C3: 3% NaF solution
Sample No.
　C4: 5% KF aqueous solution
sample No.
　C5: 0 .1% MgF + HNO 3 aqueous solution, pH 2
sample No.
　C6: 0.1% CaF + HNO 3 aqueous solution, pH 2
sample No.
　C15: 0.5% FeF 2 solution
Sample No.
　C16: 1% ZnF 2 · 4H 2 O aqueous solution
sample No.
　C17: 0.5% NiF 2 solution
[0185]
　Thereafter, the dispersant of ZnO particles 109 (manufactured by Sakai Chemical Industry Co., Ltd., product name DIF-3ST4S) and as the organic resin 111, a cationic urethane resin (Dai-ichi Kogyo Seiyaku Co., product name SUPERFLEX 650; liquid) were mixed the solution adjusted Te, is applied to the surface of the Al-based plating layer 103 to form an intermediate coating layer 105 by a roll coater, dried similarly reached plate temperature 80 ° C. and the formation of the intermediate coating layer 105, an organic resin 111 was to form a surface coating layer 107 was 30 wt% (70 wt% of ZnO). As for Sample No. C23 was dried at 80 ° C. after applying only dispersant ZnO particles 109.
[0186]
　[Measurement conditions]
　The composition of the intermediate coating layer 105, F adhesion amount, the particle size of the ZnO particles 109, ZnO coating weight were identified in the following manner.
[0187]
　1. Composition of the intermediate coating layer 105:
　Rigaku Corporation X-ray diffraction apparatus (product name: SmartLab 3) used, using Cu-K [alpha line, by setting the incident angle to 90 degrees, ICDD data peaks obtained by the thin film method compared to, and identify the composition of the layered double hydroxide.
[0188]
　2. F adhesion amount:
　Rigaku Corporation scanning X-ray fluorescence spectrometer (product name: ZSX Primes) was used to measure the F deposited per unit area by a calibration curve method. For the measurement, in advance, preparing a calibration curve showing the relationship between the F deposition amount and the characteristic X-ray intensity, based on the calibration curve to determine the deposition amount.
[0189]
　3. The particle size of the ZnO particles 109:
　manufactured by JEOL Ltd. scanning electron microscope (product name: JSM-7800F) with the ZnO particles 109 was observed at 2000-fold magnification, measuring the maximum diameter of the 20 ZnO particles 109, and the particle size of the ZnO particles 109 calculates an average value.
[0190]
　4. ZnO deposition amount
　manufactured by Rigaku Corporation X-ray fluorescence analyzer (product name: ZSX Primus) was measured using a ZnO deposition amount under the following conditions. For the measurement, in advance, preparing a calibration curve showing the relationship between the Zn content and the fluorescent X-ray intensity, based on the calibration curve to determine the deposition amount.
Measurement diameter: 30 mm
, measurement atmosphere: vacuum
Spectrum: Zn-K [alpha
　with peak number counting Zn-K [alpha X-ray fluorescence analysis was measured under the above conditions.
[0191]
　[Evaluation of Sample]
　Next, the way various properties of a sample of each test example was prepared like was evaluated by the following method.
[0192]
(1) Hot lubricity
　by making the mold pull-out test in hot the sample was evaluated hot lubricity.
Insert the steel sheet of each test example of 30 mm × 350 mm into the furnace, sandwiched between 2 sheets of width 60 mm × length 200 mm × thickness 30 mm SiC plate made of, and heated for 6 minutes at 900 ° C., after removal from the furnace, about pressing SKD11 steel Tairakin-type (50mm width × 40 mm length) from both sides of the steel sheet at 700 ° C., it was drawn. Pressing and measuring the load and pulling loads, the value obtained in / pull-out load (2 × pressed load) was hot friction coefficient. Hot friction coefficient was evaluated as acceptable than 0.52.
[0193]
(2) corrosion resistance after painting
　by inserting each sample 120 mm × 200 mm into the furnace, placed in a direction contacting the evaluation surface on the SiC furnace pedestal and heated to 900 ° C., of 50 mm × 50 mm × 70 mm while carrying the SUS304 block, heated standing furnace 6 minutes at 900 ° C., after removal from the oven and immediately quenched sandwich in a stainless steel mold. The cooling rate at this time was about 0.99 ° C. / sec. Then sheared to 70 mm × 150 mm from the center of each steel sheet after cooling, Nippon Parkerizing Co., Ltd. chemical treatment solution after (PB-SX35) in the chemical conversion treatment, Nippon Paint Co., Ltd. electrodeposition coating ( the POWERNICS 110) thickness was applied to a 20 [mu] m, baked at 170 ° C.. Incidentally, in the atmosphere furnace set at 900 ° C., where to insert each sample 70 mm × 150 mm with a welded thermocouple, the temperature of until 900 ° C. was measured to calculate the average heating rate, 5 ° C. / It was second.
　Corrosion resistance after painting evaluation was carried out by the method specified in the Society of Automotive Engineers enactment of JASO M609. That is, crosscut in advance cutter in the coating film, the width of blistering the coating from the cross-cut after the corrosion test 180 cycles (60 days) the (one-sided maximum value) was measured. The width 5.0mm or less was acceptable.
[0194]
(3) Spot weldability
　spot weldability was evaluated as follows.
　Put prepared samples in a heating furnace, and heated standing furnace 6 minutes at 900 ° C., and quenched by sandwiching immediately stainless steel mold after removal. The cooling rate at this time was about 0.99 ° C. / sec. Then, sheared each steel sheet after cooling to 30 mm × 50 mm, the optimal spot welding current range - were measured (upper current limit current). Measurement conditions are as shown below. The lower limit current nugget diameter 3 × (t) 0.5 a current value when a, the upper limit current was set to geographic generated current. Current range was passed more than 1.0A.
- current: DC
electrode: chromium copper, DR (tip 6mmφ is 40R)
- pressure: 400 kgf (1 kgf is 9.8 N.)
- energizing time: 240 ms
[0195]
(4) ZnO loss test (ZnO residual ratio, the residual amount)
　punched sample to 30mmφ of each test example, superimposed on the SiC furnace pedestal 70 mm × 70 mm, heated to 900 ° C., of 50 mm × 50 mm × 70 mm while carrying the SUS304 block, heated standing furnace 6 minutes at 900 ° C., after removal, it was immediately quenched sandwich in a stainless steel mold. ZnO deposition amount of Zn deposition amount before and after heating was measured by XRF and (remaining amount) was calculated ZnO residual ratio. Residual amount 0.4 g / m 2 was passed over.
　The results are shown in Table 8.
[0196]
[Table 8]

[0197]
　Table 8 As is evident, the surface of the Al-based plating layer 103, aluminum, at least one of an alkali metal and alkaline earth metal, an intermediate coating layer 105 is a fluoride salt, containing at least ZnO surface and the film layer 107 are sequentially formed, for Al-based plated steel sheet within the scope of the present application (C13 from sample No. C1), both the four evaluation described above for (various characteristics and ZnO loss test), good results were obtained.
[0198]
　In contrast, for the range of the Al-based plated steel sheet of the present (Sample No. C14 from C23), both, for the four evaluation described above, it was found that no good results.
　Specifically, sample No. C14 is too small F adhesion amount, hot lubricity, corrosion resistance after coating was inferior.
　Sample No. C15, C16, C17, as the intermediate coating layer 105, aluminum, and an alkali metal and fluoride salts other than alkaline earth metals, ZnO residual amount, hot lubricity, corrosion resistance after coating was poor .
　Sample No. C18 is too small amount ZnO deposited ZnO residual amount, hot lubricity, corrosion resistance after coating was inferior.
　Sample No. C19 was inferior spot weldability amount ZnO deposition is too much.
　Sample No. C20 is ZnO average particle size is too small, hot lubricity was poor.
　Sample No. C21 is, ZnO average particle size is too large, was inferior spot weldability.
　For Sample No. C22 is no intermediate film layer 105, ZnO remaining amount, hot lubricity, corrosion resistance after coating was inferior.
　Sample No. C23 because there is no intermediate film layer 105 and the resin 111, ZnO remaining amount, hot lubricity, corrosion resistance after coating was inferior.
[0199]
　The amount of fluorine 20 mg / m 2 or more, 2000 mg / m 2 is less than or equal to (C12 from Sample No. C1), or the amount of ZnO in the surface film layer 107, in Zn content, 0.5 g / m 2 or more , 10.0 g / m 2 in the case is less than or equal to (from sample No. C1 C14), it can be seen that the obtained superior results.
[0200]
　Example D:
　First, a sample was prepared which was subjected to sample numbers D1 ~ D26 under the following conditions.
[0201]
　Shown in Table 9 Chemical composition (the balance being Fe and inevitable impurities) was used cold rolled steel sheet of the (thickness 1.4 mm) as a base material 101, Al system using the conventional Al coating bath Sendzimir method on both surfaces the plating layer 103 was 60μm formed. Al-based annealing temperature of the plating layer 103 formed was about 800 ° C..
　Incidentally, the adhesion amount of Al-based plating layer 103 with respect to the base material 101 is a gas wiping method, one side 160 g / m 2 was adjusted to.
[0202]
[Table 9]

[0203]
　Then, after cooling the preform 101 Al-based plating layer 103 is formed, to form an intermediate coating layer 105 on the surface of the Al-based plating layer 103. In forming the intermediate coating layer 105, A shown in Table 10 n- ions and M 2+ containing ions, or immersed for 2 to 30 seconds to pH8 more aqueous solutions (Sample Nos. D1 ~ D14, D18 ~ D24) , or, by applying the aqueous solution by a bar coater, in a furnace at 200 ° C., or dried so as to reach plate temperature 80 ° C. (sample No. D15 ~ D17), was formed in any manner. However, Sample No. D25, D26 did not form an intermediate coating layer 105.
[0204]
　The composition of the concrete solutions are as follows, using commercially available reagents were adjusted to the following composition by mixing with distilled water.
Sample No. D1 ~ D3, D18 ~ D24:
　calcium saturated hydroxide and aqueous 5% NaCl solution, pH 12.5
Sample No. D4:
　magnesium saturation hydroxide, 5% diluted aqueous ammonia (30% content of 20% or higher) and 5% NaCl aqueous solution, pH 11
sample No. D5:
　barium saturated hydroxide and aqueous 5% NaCl solution, pH 13
sample No. D6:
　iron chloride 10 -6 aqueous solution was adjusted mol / L aqueous ammonia to pH8.5
sample No. D7:
　saturated hydroxide nickel, 5% aqueous ammonia (30% or less of 20% or higher content) and aqueous 5% NaCl solution, pH 11
sample No. D8:
　copper saturated hydroxide, (30% or less content of more than 20%) 5% aqueous ammonia, 5% NaCl aqueous solution, pH 11
sample No. D9:
　calcium saturation hydroxide, 5% Na2 SO4 solution, pH 12.5
sample No. D10:
　saturated Calcium carbonate, 5% aqueous solution of ammonium hydrogen carbonate, pH 10.5
Sample No. D11 ~ D14:
　Saturated aqueous solution of calcium hydroxide, pH 12.5
Sample No. D15:
　Concentration 10 g / L CaCO of 3 aqueous solution
sample No. D16:
　Concentration 10 g / L CaSO of 4 aqueous solution
sample No. D17:
　saturated MgCO 3 solution
[0205]
　Thereafter, the dispersant of ZnO particles 109 (manufactured by Sakai Chemical Industry Co., Ltd., product name DIF-3ST4S) and as the organic resin 111, a cationic urethane resin (Dai-ichi Kogyo Seiyaku Co., product name SUPERFLEX 650; liquid) were mixed the solution adjusted Te, is applied to the surface of the Al-based plating layer 103 to form an intermediate coating layer 105 by a roll coater, dried similarly reached plate temperature 80 ° C. and the formation of the intermediate coating layer 105, an organic resin 111 was to form a surface coating layer 107 was 30 wt% (70 wt% of ZnO). As for the sample No. D22, D26, and dried at 80 ° C. after applying only dispersant ZnO particles 109.
　There was thus obtained the Al-based plated steel sheet 100 of each test example.
[0206]
[Table 10]

[0207]
　Here, the "ZnO deposition amount" in Table 10, the total deposition amount of the value (unit obtained in terms of the mass of metal Zn in ZnO particles 109 per square meter of the intermediate coating layer 105 is "g / M 2 is a ").
[0208]
　[Measurement conditions]
　The composition of the intermediate coating layer 105, M deposition amount, the particle size of the ZnO particles 109, ZnO coating weight were identified in the following manner.
[0209]
　1. Composition of the intermediate coating layer 105:
　Rigaku Corporation X-ray diffraction apparatus (product name: SmartLab 3) used, using Cu-K [alpha line, by setting the incident angle to 90 degrees, ICDD data peaks obtained by the thin film method compared to, and identify the composition of the layered double hydroxide.
[0210]
　2. M deposition amount:
　Rigaku Corporation X-ray fluorescence analyzer (product name: ZSX Primus) was measured using a M adhesion amount under the following conditions. For the measurement, in advance, preparing a calibration curve showing the relationship between the M amount and fluorescent X-ray intensity, based on the calibration curve to determine the deposition amount.
Measurement diameter: 30 mm ,
measurement atmosphere: vacuum
Spectrum: M-K [alpha
　with peak number counting M-K [alpha X-ray fluorescence analysis was measured under the above conditions.
[0211]
　3. The particle size of the ZnO particles 109:
　manufactured by JEOL Ltd. scanning electron microscope (product name: JSM-7800F) with the ZnO particles 109 was observed at 2000-fold magnification, measuring the maximum diameter of the 20 ZnO particles 109, and the particle size of the ZnO particles 109 calculates an average value.
[0212]
　4. ZnO deposition amount
　manufactured by Rigaku Corporation X-ray fluorescence analyzer (product name: ZSX Primus) was measured using a ZnO deposition amount under the following conditions. For the measurement, in advance, preparing a calibration curve showing the relationship between the Zn content and the fluorescent X-ray intensity, based on the calibration curve to determine the deposition amount.
Measurement diameter: 30 mm
, measurement atmosphere: vacuum
Spectrum: Zn-K [alpha
　with peak number counting Zn-K [alpha X-ray fluorescence analysis was measured under the above conditions.
[0213]
　[Evaluation of Sample]
　Next, the way various properties of a sample of each test example was prepared like was evaluated by the following method.
[0214]
　(1) Hot lubricity
　by making the mold pull-out test in hot the sample was evaluated hot lubricity.
Insert the sample in each test example of 30 mm × 350 mm into the furnace, sandwiched between 2 sheets of width 60 mm × length 200 mm × thickness 30 mm SiC plate made of, and heated for 6 minutes at 900 ° C., after removal from the furnace, about pressing SKD11 steel Tairakin-type (50mm width × 40 mm length) from both sides of the steel sheet at 700 ° C., it was drawn. Pressing and measuring the load and pulling loads, the value obtained in / pull-out load (2 × pressed load) was hot friction coefficient. Hot friction coefficient was evaluated as acceptable than 0.52.
[0215]
　(2) corrosion resistance after painting
　samples of each test example of 120 mm × 200 mm was inserted into the furnace, placed in a direction contacting the evaluation surface on the SiC furnace pedestal and heated to 900 ° C., 50 mm × 50 mm while carrying the SUS304 blocks × 70 mm, heated standing furnace 6 minutes at 900 ° C., after removal from the oven and immediately quenched sandwich in a stainless steel mold. The cooling rate at this time was about 0.99 ° C. / sec. Then sheared to 70 mm × 150 mm from the center of each steel sheet after cooling, Nippon Parkerizing Co., Ltd. chemical treatment solution after (PB-SX35) in the chemical conversion treatment, Nippon Paint Co., Ltd. electrodeposition coating ( the POWERNICS 110) thickness was applied to a 20 [mu] m, baked at 170 ° C.. Incidentally, in the atmosphere furnace set at 900 ° C., where to insert each sample 70 mm × 150 mm with a welded thermocouple, the temperature of until 900 ° C. was measured to calculate the average heating rate, 5 ° C. / It was second.
　Corrosion resistance after painting evaluation was carried out by the method specified in the Society of Automotive Engineers enactment of JASO M609. That is, crosscut in advance cutter in the coating film, the width of blistering the coating from the cross-cut after the corrosion test 180 cycles (60 days) the (one-sided maximum value) was measured. The width 5.0mm or less was acceptable.
[0216]
(3) Spot weldability
　put prepared samples in a heating furnace, and heated standing furnace 6 minutes at 900 ° C., and quenched by sandwiching immediately mold stainless after removal. The cooling rate at this time was about 0.99 ° C. / sec. Then shearing the sample after cooling to 30 × 50 mm, the optimal spot welding current range - were measured (upper current limit current). Measurement conditions are as shown below. The lower limit current, the nugget diameter 3 × (t) 0.5 a current value when a, the upper limit current was scattered generated current. Current range was passed more than 1.0A.
- current: DC
　electrode: chromium copper, DR (tip 6mmφ is 40R)
　- pressure: 400 kgf (1 kgf is a is 9.8 N)
　· energization time: 240 ms
(4) ZnO loss test (ZnO residual ratio, residual amount):
　punched sample to 30mmφ of each test example, superimposed on the SiC furnace pedestal 70 mm × 70 mm, heated to 900 ° C., in a state carrying the SUS304 block of 50mm × 50mm × 70mm, 900 ℃ in heated stationary furnace 6 minutes, after removal, it was immediately quenched sandwich in a stainless steel mold. The Zn deposition amount before and after heating was measured by XRF was calculated residual ratio with Zn deposition amount. Residual amount 0.4 g / m 2 was passed over.
　Table 11 shows the above results.
[0217]
[Table 11]

[0218]
　Table 11 As is evident, formed on the surface of the Al-based plating layer 103, Al-based layered double hydroxide ([M 2+ 1-x Al 3+ x (OH) 2 ] [A n- x / n · mH 2 adhesion amount of O]) intermediate coating layer 105 made of the metal M converted at 10 mg / m 2 or more, 1000 mg / m 2 or less, the surface film formed on the surface of the intermediate film layer 105 layer 107 There average particle size 0.10μm or more, contained the following ZnO particles 109 and the organic resin 111 5.00, the adhesion amount of the ZnO particles 109 of metal Zn converted at 0.5 g / m 2 or more, 10.0 g / m 2 the Al-based plated steel sheet 100 in the range of the present application is less (sample Nos. D1 ~ D14), both, for all four evaluation described above, it is found that good results are obtained.
[0219]
　In contrast, and if the intermediate film layer 105 is not (sample No. D25, D26), the average particle size of ZnO particles 109, any of the deposition amount of the ZnO particles 109 is out of the present application a predetermined range, the Al-based plated steel sheet 100 outside the scope of this application (sample No. D18 ~ D24), both, for at least one of the four evaluation described above, it was found that no good results.
　Specifically, sample No. D15, D16, D17, instead of Al-based layered double hydroxide, calcium carbonate, calcium sulfate, magnesium carbonate, which has formed on the surface of the Al-based plating layer 103, heat during lubrication, corrosion resistance after coating was inferior in ZnO residual amount.
　Sample No. D18 is too small ZnO average particle size was inferior hot lubricity.
　Sample No. D19 is, ZnO average particle size is too large, was inferior spot weldability.
　Sample No. D20 is too small amount ZnO deposited ZnO residual amount, hot lubricity was poor.
　Sample No. D21 was inferior spot weldability amount ZnO deposition is too much.
　Sample No. D22 because there is no resin 111, ZnO remaining amount, hot lubricity was poor.
　Sample No. D23 is too small M adhesion amount ZnO remaining amount, hot lubricity was poor.
　Sample No. D24 was inferior spot weldability M adhesion amount is too much.
　For Sample No. D25 is that not an intermediate coating layer 105, ZnO residual amount, corrosion resistance after painting, hot lubricity was poor.
　Sample No. D26 has no resin 111, because it was not provided even intermediate coating layer 105, ZnO residual amount, corrosion resistance after painting, hot lubricity was poor.
[0220]
　Example E:
　chemical compositions shown in Table 12 (the remainder being Fe and unavoidable impurities) using cold rolled steel sheet (thickness 1.4 mm) of, using the conventional Al coating bath Sendzimir method to that cold-rolled steel sheet both sides to form an Al-based plated layer 103 Te. Al-based annealing temperature of the plating layer 103 formed was about 800 ° C..
[0221]
　Incidentally, the amount of Al-based plating layer 103 adhering to the base material 101, in the gas wiping method, one side 160 g / m 2 was adjusted to.
[0222]
[Table 12]

[0223]
　Then, to form after cooling a preform 101 which Al-based plating layer 103 is formed, an intermediate coating layer 105 shown in Table 13 on the surface. Formation of the intermediate coating layer 105 to the Al-based plating layer 103 surface of the sample No. E1 to E23 is performed by chemical vapor deposition, forming conditions were carried out under the conditions shown in Table 13. Coating thickness was controlled by the deposition time. Sample No. E24, E25 was not carried out the formation of the intermediate coating layer 105. Sample No. E26 as means for forming the intermediate coating layer 105 other than the deposition, 300 ° C., Al by oxidation in air for 24 hours 2 O 3 to form a film.
[0224]
　Thereafter, the sample numbers E1 to E23, E26, dispersants ZnO particles 109 (manufactured by Sakai Chemical Industry Co., Ltd., product name DIF-3ST4S) and cationic urethane resin (Dai-ichi Kogyo Seiyaku Co., Ltd. as the organic resin 111, product name Super the solution prepared by mixing flex 650) was applied on the intermediate coating layer 105 is formed on the Al-based plating layer 103 by a roll coater, dried at peak metal temperature of 80 ° C., to form a surface coating layer 107 . The organic resin 111 of the surface coating layer 107 was 30 wt% (70 wt% of ZnO). Further, Sample No. E24, for E25, not on the intermediate coating layer 105 was formed in the same manner as the surface coating layer 107 directly on the Al-based plating layer 103.
　There was thus obtained the Al-based plated steel sheet 100 of each test example. The above solution for forming a surface coating layer 107 shown in Table 13 were adjusted by using commercially available reagents, it is mixed with distilled water. Here, the "Zn adhered amount" in Table 13, the value (unit obtained a total coating weight in terms of the mass of metal Zn in ZnO particles 109 per square meter of the intermediate coating layer 105 is "g / m 2 is a ").
　Note that blank portion of the table 13 show that the intermediate coating layer 105 is not formed.
[0225]
[Measurement
　Conditions] The particle size of the ZnO particles 109, ZnO coating weight were identified in the following manner.
1. The particle size of the ZnO particles 109
　manufactured by JEOL Ltd. scanning electron microscope (product name: JSM-7800F) with the ZnO particles 109 was observed at 2000-fold magnification, measuring the maximum particle size of 20 ZnO particles 109, and the particle size of the ZnO particles 109 calculates an average value.
2. ZnO deposition amount
　manufactured by Rigaku Corporation X-ray fluorescence analyzer (product name: ZSX Primus) was measured using a ZnO deposition amount under the following conditions. For the measurement, in advance, preparing a calibration curve showing the relationship between fluorescent X-ray intensity of metal Zn amount conversion, based on the calibration curve to determine the deposition amount.
　Measurement diameter: 30mm
　Measurement Atmosphere: Vacuum
　Spectrum: Zn-K [alpha
　with peak number counting Zn-K [alpha X-ray fluorescence analysis was measured under the above conditions.
[0226]
[Table 13]

[0227]
　Coating structure is the presence of base material / plating layer / intermediate coating layer / surface coating layer by SEM cross-sectional observation was confirmed components by SEM-EDS.
　Next, the way various properties of the steel sheet of each test example was prepared like was evaluated by the following method.
[0228]
　(1) Hot lubricity (lubricating property)
　against steel of each test example, by performing the mold pull-out tests in hot, to evaluate hot lubricity. Insert the steel sheet of each test example of 30 mm × 350 mm into the furnace, sandwiched between 2 sheets of width 60 mm × length 200 mm × thickness 30 mm SiC plate made of, and heated for 6 minutes at 900 ° C., after removal from the furnace, about pressing SKD11 steel Tairakin type (width 50 mm × length 40 mm) from both sides of the steel sheet at 700 ° C., it was drawn. By sandwiching the both sides of the steel sheet by the SiC plate, the supply of oxygen from the surface sufficiently prevented, they simulate a situation in which ZnO film superposition portion in contact with the conveyor disappears at more severe conditions. Pressing and measuring the load and pulling loads, the value obtained in / pull-out load (2 × pressing load) was hot friction coefficient. The value of the dynamic friction coefficient means that the better hot lubricity is small, in the evaluation shown in Table 14, was passed less than 0.52.
[0229]
　(2) corrosion resistance after painting
　by inserting steel sheet of each test example of 120 mm × 200 mm into the furnace, placed in a direction contacting the evaluation surface on the SiC furnace pedestal, 50 mm × 50 mm × heated to 900 ° C. while carrying the SUS304 block of 70 mm, heated standing furnace 6 minutes at 900 ° C., after removal from the oven and immediately quenched sandwich in a stainless steel mold. The cooling rate at this time was about 0.99 ° C. / sec. Then sheared to 70 mm × 150 mm from the center of each steel sheet after cooling, Nippon Parkerizing Co., Ltd. chemical treatment solution after (PB-SX35) in the chemical conversion treatment, Nippon Paint Co., Ltd. electrodeposition coating ( the POWERNICS 110) thickness was applied to a 20 [mu] m, baked at 170 ° C.. Incidentally, inserting each steel sheet 70 mm × 150 mm with a welded thermocouple in the atmosphere furnace set at 900 ° C., where a temperature of until 900 ° C. was measured to calculate the average heating rate, 5 ° C. / sec Met.
[0230]
　Corrosion resistance after painting evaluation was carried out by the method specified in the Society of Automotive Engineers enactment of JASO M609. That is, crosscut in advance cutter in the coating film, the width of blistering the coating from the cross-cut after the corrosion test 180 cycles (60 days) the (one-sided maximum value) was measured. The value of the width of blistering the coating means the superiority of the smaller corrosion resistance, in the evaluation shown in Table 14, was evaluated as acceptable 5mm or less.
[0231]
　(3) Spot weldability
　spot weldability was evaluated as follows.
　Put steel of each test example was produced in the heating furnace, and heated standing furnace 6 minutes at 900 ° C., and quenched by sandwiching immediately mold stainless after removal. The cooling rate at this time was about 0.99 ° C. / sec. Then, sheared each steel sheet after cooling to 30 × 50 mm, the optimal spot welding current range - were measured (upper current limit current). Measurement conditions are as shown below. The lower limit current, the nugget diameter 3 × (t) 0.5 a current value when a, the upper limit current was scattered generated current.
　Current: DC
　electrode: chromium copper, DR (tip 6mmφ is 40R)
　pressure: 400 kgf (1 kgf is 9.8 N.)
　Energizing time: 240 ms
　in the evaluation shown in Table 14, and passed over 1.0kA did.
[0232]
　(4) ZnO loss test
　punched steel plates of each test example 30 mm?, Superimposed on a SiC furnace pedestal 70 mm × 70 mm, while carrying the SUS304 block of 50 mm × 50 mm × 70 mm heated to 900 ° C., 900 heating standing furnace 6 minutes at ° C., after removal, was immediately quenched sandwich in a stainless steel mold. The Zn deposition amount before and after heating was measured by XRF to measure the Zn deposition amount of Zn in terms were calculated ZnO residual ratio of Zn terms.
　The evaluation shown in Table 14, in Zn residual ratio of 75% or more, 0.40 g / m of Zn remaining amount 2 was passed over.
[0233]
　Table 14 As is evident, formed on the surface of the Al-based plating layer 103, the intermediate film layer 105 is Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlN, TiN, Si 3 N 4 , TiC, a ceramic deposition film formed of any one of SiC, the thickness of 10nm or more and 1000nm or less, the surface coating layer 107 formed on the surface of the intermediate film layer 105 is an average particle diameter of 0.10μm or more, 5. contained the following ZnO particles 109 and the organic resin 111 00μm, the amount of deposition of ZnO particles 109 metal Zn converted at 0.5 g / m 2 or more, 10.0 g / m 2 Al system within the scope of the invention that are less the plated steel sheet 100 (the invention examples), both, for all four evaluation of the (various characteristics and ZnO loss test), that good results have been obtained determine .
[0234]
[Table 14]

[0235]
　In contrast, sample numbers E1, E7, E18, E19, E22 to E26 are either intermediate coating layer 105 is not, or intermediate film layer 105 is not deposited film, the thickness of the intermediate coating layer 105 is inappropriate, or the average particle size of ZnO particles 109, any of the deposition amount of the ZnO particles 109 is out of the predetermined range of the present invention. Range of Al-based plated steel sheet of the present invention (the sample numbers E1, E7, E18, E19, E22 to E26) for both, at least one of the four evaluation of the (various characteristics and ZnO loss test) One for, it can be seen that no good results.
DESCRIPTION OF SYMBOLS
[0236]
　　　100 ... Al-based plated steel sheet
　　　101 ... base material
　　　103 ... Al-based plating layer
　　　105 ... intermediate coating layer
　　　107 ... surface film layer
　　　109 ... ZnO particles
　　　111 ... organic resin

The scope of the claims
[Requested item 1]
　And the base material, the Al-based plating layer formed on at least one surface of the base material,
　an intermediate coating layer formed on the surface of the Al-based plating layer,
　formed on the surface of the intermediate coating layer, the average particle diameter 0 .10μm above, contains the following ZnO particles 5.00, and an organic resin, the amount of deposition of the ZnO particles of metal Zn converted at 0.5 g / m 2 or more, 10.0 g / m 2 surface film is not more than a layer,
　wherein the intermediate coating layer, Al-based plated steel sheet, characterized in that one of the conditions are satisfied in the following (a) from (C).
(A) a thickness of 10nm or more and 1000nm or less, and composed mainly of S, Al and O, the mass ratio of the S and Al [S] / [Al] is 0.0008 or more, 0.49 or less, and, S and O mass ratio of [S] / [O] is 0.001 or more, and 0.55 or less.
(B) borate, silicate, sulfonate, sulfinate, permanganate, comprises one or oxo acid salt of two or more phosphate deposition thickness of 10nm or more, 500 nm or less .
(C) aluminum, at least one of alkali metals and alkaline earth metals, a fluoride salt, the amount of fluorine contained is 20 mg / m 2 or more.
[Requested item 2]
　The intermediate coating layer, the meet conditions specified (A), the
　said intermediate thickness of the coating layer is 20nm or more, Al-based plated steel sheet according to claim 1, characterized in that at 400nm or less.
[Requested item 3]
　The intermediate coating layer, the meet conditions specified (A), the
　said weight ratio of S and Al contained in the intermediate coating layer [S] / [Al] is 0.005 or more, 0.1 or less, the weight ratio of S and O [S] / [O] is 0.005 or more, Al-based plated steel sheet according to claim 1 or 2, characterized in that it is 0.12 or less.
[Requested item 4]
　The mass ratio of the S and Al contained in the intermediate coating layer [S] / [Al] is 0.008 or more, 0.05 or less, and the weight ratio of S and O [S] / [O] of 0.01 above, Al-based plated steel sheet according to any one of claims 1 to 3, characterized in that 0.08 or less.
[Requested item 5]
　The intermediate coating layer, satisfies the conditions specified in the (B),
　wherein the oxo acid salt is sodium borate, sodium silicate, sodium phosphate, potassium phosphate, lithium phosphate, magnesium phosphate, calcium phosphate, phosphorous aluminum, zinc sulfonate, sodium sulfinate, potassium permanganate, claim, wherein the zinc orthosilicate is lithium silicate, one or more selected from any of the permanganate zinc 1 Al-based plated steel sheet according to.
[Requested item 6]
　The intermediate coating layer, satisfies the conditions specified in the (B),
　wherein the oxo acid salt is a mixture of a permanganate and silicates, and mixing ratio of 1 or more Mn / Si mass ratio, Al-based plated steel sheet according to claim 1 or claim 5, characterized in that it is 50 or less.
[Requested item 7]
　The intermediate coating layer, the meet conditions specified (C), the
　amount of fluorine contained in the intermediate coating layer is 2000 mg / m 2 Al-based plated steel sheet according to claim 1, characterized in that not more than .
[Requested item 8]
　The intermediate coating layer, satisfies the conditions specified in the (C),
　wherein the fluoride salt is AlF 3 , Alof, LiF, NaF, KF, MgF two , CaF 2 is at least one or two wherein, Al-based plated steel sheet according to claim 1 or claim 7.
[Requested item 9]
　On both surfaces of the base material, the Al-based plating layer, the intermediate coating layer, and Al according to any one of claims 1 to 8, characterized in that three layers are formed of the surface coating layer system plated steel sheet.
[Requested item 10]
　The Al included in the Al-based plating layer, Al-based plated steel sheet according to any one of claims 1 to 9, characterized in that at least 70% by mass%.
[Requested item 11]
　The base material is a
　mass%, C: 0.01% or more, 0.5% or
　less, Si: 2.0% or
　less, Mn: 0.01% or more, 3.5% or
　less, P: 0.1 % or
　less, S: 0.05% or
　less, Al: 0.001% or more, 0.1% or
　less, N: 0.01% or less,
　claim the balance being Fe and unavoidable impurities 1 or Al-based plated steel sheet according to any one of 10.
[Requested item 12]
　The base material is further, by
　mass%, Ti: 0.005% or more, 0.1% or
　less, B: 0.0003% or more, 0.01% or
　less, Cr: 0.01% or more, 1.0 % or
　less, Ni: 0.01% or more, 5.0% or
　less, Mo: 0.005% or more, 2.0% or
　less, Cu: 0.005% or more, of 1.0%, one or Al-based plated steel sheet according to claim 11, characterized in that it contains two or more.