Specification
Title of invention: Sn-based plated steel sheet
Technical field
[0001]
The present invention relates to Sn-based plated steel sheets.
Background technology
[0002]
Tin (sn)-based plated steel sheets are well known as "tinplate" and are widely used for beverage and food cans. This is because sn is safe for the human body and is a beautiful metal. This type of plating type plated steel sheet is produced mainly by the electroplating method. This is because the electroplating method is more advantageous than the hot-dip plating method in controlling the amount of relatively expensive metal sn to the necessary minimum amount. By chromate treatment (electrolytic treatment, immersion treatment) using a hexavalent chromium chromium chromium chromium chromium chromium solution after being imparted with a metallic luster by plating or a subsequent heat treatment treatment, sn Coating is often applied on the base plating layer. The effect of this chromate is to suppress the surface of the tin - based plating layer , prevent yellowing of the appearance by suppressing the surface , and improve adhesion due to aggregation of stannous oxidation when used after being painted . Prevention of degradation of properties Black discoloration Improvement of black discoloration, etc. etc.
[0003]
On the other hand, in recent years, due to the growing concern for the environment and safety, there is a demand not only for products not to contain hexavalent chromium, but also for the chromate treatment itself not to be performed. However, sn sn sn sn sn sn sn sn without chromate, as described above, develops tin oxide, resulting in poor appearance, reduced adhesion, and reduced resistance to sulfurization and black discoloration.
[0004]
For this reason, there are proposals for Sn-based plated steel sheets with a film treatment that replaces the chromate film.
[0005]
For example , Patent Document 1 below proposes a plated steel sheet or steel sheet in which a synthetic film containing p and si is formed by treating a liquid containing phosphate ions and a silane coupling agent . Sassa Sairu.
[0006]
In the following patent document 2 , tin plating having a chemical conversion film containing alpp and at least one selected from , co and cu and a reactant layer of silane , silane coupling agent . Tin Plating Tin Plating Tin plating has been proposed.
[0007]
The following patent document 3 proposes a method of manufacturing a sn-plated steel sheet by applying a zinc multi-layer plating on a tin-plated surface and then heating until the zinc has substantially disappeared.
[0008]
In Patent Document 4 below , a steel plate for use with a zr film provided on a surface treatment layer containing sn and in Patent Document 5 below , a steel plate for containers and a steel plate having a zr compound layer are proposed respectively . te te te te
[0009]
The following Patent Document 6 proposes a container , a steel plate , and a steel plate having a lower nini layer , an island - shaped tin - plated layer , a chemical conversion containing tin phosphate , and a zr coating layer . there is there
[0010]
The following patent document 7 proposes a container steel sheet having a tin oxide and a film containing , ti and p on the surface of a tin-plated layer. Patent Document 7 also proposes that alternating electrolysis, in which cathodic electrolysis and anodic electrolysis are alternately performed, may be carried out to remove the film. been
prior art documents
patent literature
[0011]
Patent Document 1: Japanese Patent Application Laid-Open No. 2004-060052
Patent Document 2: Japanese Patent Application Laid-Open No. 2011-174172 Patent
Document Document 3: JP-A-63-290292 Patent
Literature Literature 4: Japanese Unexamined Patent Publication Japanese Unexamined Patent Publication
Literature 5: Japanese Patent Application Publication No. 2010-013728
Patent Document 6: Japanese Patent Application Laid-Open No. 2009-249691
Patent Document 7: International Publication No. 2015/001598 No. No. No. No. No. No. No. No. No. No. No. No.
Non-patent literature
[0012]
Non-Patent Document 1: The Surface Science Society of Japan, "Surface Analysis, Chemistry Selection, Line Photoelectron Electron Spectroscopy, Marumaru Publishing Co., Ltd., July 2008, p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p. 83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83 p.83
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0013]
However , the proposed sn and its production in Patent Document 1 and Patent Document 7 cannot sufficiently suppress the growth of stannic acid over time , resulting in yellowing resistance, Coating film Coating film Coating film Coating film There is room for improvement in the coating film and resistance to sulfuration black discoloration.
[0014]
Accordingly , the present invention has been made in view of the above problems , and the object of the present invention is to improve yellowing resistance , paint film adhesion and blackening without conventional chromate treatment . An object of the present invention is to provide a Sn-based plated steel sheet.
Means to solve problems
[0015]
In order to solve the above problems , as a result of intensive studies by the inventors of the present invention , chromate treatment is achieved by forming a coating layer containing zirconium zirconium oxide and manganese on the surface of the steel sheet . Sn-based plating is superior in terms of yellowing resistance, coating film adhesion, and black discoloration. It was found that the steel plate was
. . The gist of the present invention, which has been completed based on the above knowledge, is the following.
[0016]
(1) A steel sheet, an sn-based plating positioned on at least one of the above-mentioned layers, and a coating layer positioned on the above-mentioned plating layer, wherein the sn-based layer is 215.00 g//m2 or less per side in terms of metal sn The content of the written matter is 0.20 mg//m 2 or more and 50.00 mg/m 2 or less on one side in terms of metal zr , and the manganese compound metal in the film layer is The content in terms of metal mn is 0.01 times or more but not more than 0.01 times the content of zirconium oxide in terms of metal zr on a mass basis , and is ray photoelectron spectroscopy In the lateral elemental analysis by the method , the deep position position a where the element concentration of Mn is the maximum as the manganese oxide, and the element of zr zr as the zirconium oxide is the maximum. It is positioned closer to the surface side of the coating layer than a certain depth position, and the distance in the depth direction between the depth position a and the depth position b is , sn steel plate steel plate.
2)) The mass of the zirconium oxide in the depth elemental analysis by the line ray photoelectron spectroscopy is determined by the x-ray photoelectron spectroscopy depth analysis. The mass of the manganese oxide in the analysis is 0.01 times or less (the sn-based plating described in (1)
(3) The sn-based plated steel sheet, the steel sheet, the steel sheet, the steel sheet according to (2) for 1), wherein the distance between the depth position a and the depth position is equal to or greater than steel plate
(4) The content of the zirconium zirconium oxide in the coating layer is 30.00 mg/mm2 or more per side in terms of metal, (1)) to 33 3, 3, 3, 3, 3, 3, 3, 3, 3, 3 or 4. The sn-based plated steel sheet according to any one of 3, 3, 3, 3, 3, 3, and 3.
(5) The content of the oxide in the coating layer is 2.00 mg//m2 or more and 10.00 mg/2222 or less per side in terms of metal zr, (1 ) to (4).
(The content of the manganese oxide in terms of metal mnmn in the coating layer is at least twice as much as the content of the zirconium oxide oxide metal in terms of zr on a mass basis. The sn-based plated steel sheet according to any one of (11) and (5), wherein the content is 0.40 or less.
(7) The content of the manganese oxide in the coating layer in terms of metal mn is at least 0.10 times the content of the zirconium substance in terms of metal on a mass basis. .20 times or less , , ((((((Sn-based plated steel sheet according to any one of (() to (6).
Effect of the invention
[0017]
As described above , according to the present invention , it is possible to provide a system plated steel sheet which is excellent in resistance to coating film and resistance to oxidation blackening without conventional chromate treatment .it becomes possible to become
Brief description of the drawing
[0018]
[Fig. 1] Fig. 1 schematically shows and explains an example of the structure of the sn-based plating according to one embodiment of the present invention. .
[Fig. This is an example of the element concentration profile in the thickness direction (depth direction) measured by the x-ray photoelectron method of the layer.
MODE FOR CARRYING OUT THE INVENTION
[0019]
Preferred embodiments of the present invention are described in detail below
It should be noted that, in the present specification, the term "" is used not only independently, but also for the intended purpose of the process, even if it cannot be clearly distinguished from other processes. So long as the purpose is achieved, this term will be used. In the specification, the term "steel sheet" means a base material ((((so-called plated base plate) on which an Sn-based plating and a film layer are formed.
[0020]
Further, the present invention described below relates to a sn steel sheet and steel sheet used for cans such as food cans, beverage cans, and the like. Specifically , the present invention relates to a Sn - plated steel sheet which is more excellent in resistance to resistance , paint film adhesion , and resistance to sulfidation black discoloration without performing conventional treatments .
[0021]
<1. Sn-based plated steel sheet >
First, the sn-based plating according to this embodiment will be explained with reference to FIG. 1 . FIG. is.
[0022]
As schematically shown in FIG. 1 , an sn-based plated steel sheet 1 according to the present embodiment, a steel sheet (base material) 10 , and an sn-based plating 20 20 located on at least one surface of the steel sheet . A coating layer 30 is located on the Sn-based plating layer 20 . sn. The sn-based plating layer has a sn of 0.10 g/m2 or more and 15.00 g/m2 or less per side, in terms of metal, and the coating layer 30 contains zirconium oxide and manganese oxide. and the content of zirconium oxide in the coating layer is, in terms of zr, 0.20 mg//m or more per side and m 2 or less, and manganese in the coating layer 30 Oxidized metal Content in terms of metal mn , Zirconium Oxidized metal 0.01 0.01 times the amount in terms of metal zr on a mass basis 0.50 0.50 0.50 0.50 0.50 It is 0.50 0.50 0.50 0.50, and in the depth direction element by x-ray photoelectron spectroscopy, mn mn elements are as manganese oxides, and the maximum depth position is as oxide oxides Assuming that the element concentration of zr is located on the surface side of the coating layer from the maximum maximum depth position b, and the distance in the depth direction between the deep position aa and the deep position b is 2 nm or more
[0023]
(1.1 Steel plate)
The steel sheet used as the base material of the sn-based plated steel sheet according to the present embodiment is not particularly specified, and can be used for general-use sn-based plated steel sheets. , can be anything. Examples of such steel sheets include low-carbon steel and ultra-low-carbon steel.
[0024]
(1.2 sn-based plating layer 20)
At least one side of the steel sheet as described above is plated with a sn system plating system to form an sn system plating layer 20 . . Corrosion resistance of the sn-based plating layer 20 is improved. In addition, the term "sn-based plating layer" as used herein means not only plating by but also alloys of metals and metals, metals, metals, and metals other than sns. It also includes a Sn-based plating layer containing at least one of trace impurities.
[0025]
In the sn-based plating layer 20 according to the present embodiment, the sn content per side is from 15.00 g/m2 to 15.00 g/m2 in terms of sn amount (i.e., sn equivalent amount). If the content per side of the system plating layer 20 is less than 0.10 g/22 in terms of metal sn content, the properties are inferior, and the amount of sn per surface is preferable. Preferably, the amount of metal sn is 1.0 g/m2 or more, while if the amount of metal sn per side of the sn layer 2020 is 15.00 g//m2, the amount of metal sn is 1.0 g/m2 or more. Any improvement in corrosion resistance is possible, but further increases are not desirable for economic reasons. The amount of sn sn per side is preferably less than or equal to 13.00 g of metal sn sn.
[0026]
Here, the metal sn content of the sn-based plating layer (that is, the content per side of the sn-based plating layer is measured, for example, by the electrolytic method described in G3303-3303 or by the fluorescent x-ray method. Or, for example, the amount of metal metal in the sn-based plating layer can be obtained by the following method: Prepare a piece with a good layer formed Prepare the test piece is immersed in 10% nitric acid to dissolve the sn-based plating layer, and the sn in the resulting solution is measured by ICP emission spectrometry (frequency-frequency inductive coupling emission spectrometry), for example as a device Agilent Technologies Use 799ce manufactured by Technology Co., Ltd. (using ar ar ar ar ar ar ar for carrier). Then, the amount of metal sn can be determined from the intensity signal obtained by the analysis, the calibration curve obtained by drawing a solution of concentration, and the formation area of ​​the system plating layer of the test piece. Alternatively, in the case of a piece on which a coating layer is formed, the amount of sn can be obtained by a calibration curve method using gds (glow discharge, discharge light emission), and the method is as follows. is. Using a plating sample with a known amount of metal sn (reference sample), a calibration curve is prepared in advance to determine the relationship between the metal sn intensity signal and speed in the reference sample. Originally, the amount of metal sn can be obtained from the intensity signal of a test piece with an unknown amount of metal. Here, the sn layer is the value of the zr intensity signal, zr, zr signal when analyzing the surface of the sn-based plated steel sheet in the surface-to-surface direction. , fe intensity signal , fe intensity signal is defined as the portion up to the depth where the maximum value of the intensity signal becomes . From the standpoint of measurement accuracy and rapidity, measurement by the fluorescence method is preferable industrially. i want it i want i want i want i want i want i want i want i want i want i want i want i want i want i want i want i wish
[0027]
(1.3 coating layer 30)
A film layer containing a zirconium material and a manganese material is formed on the above - described sn - based plating 2020 . The plating 1 has a coexisting film layer 30 with a coexisting film layer 30 in which the above-described zirconium oxide oxide oxide oxide is quantitatively related to the sn-based plating layer 20 , thereby forming a yellowing resistant coating film. Film Coating Coating Coating Coating Coating Coating It is possible to further improve the resistance to sulfurization and black discoloration of the coating. Zirconium, zirconium oxide, or oxidized oxide alone does not provide sufficient coating layer resistance, coating adhesion, and sulfuration resistance to black discoloration. . . . . . . Although it is not clear, the inventors of the present invention believe as follows based on detailed research.
[0028]
The presence of tin oxide on the surface of the conventional tin-based plating layer increases the amount of the material with the passage of time, resulting in a decrease in yellowing resistance and adhesion, as well as blackening resistance. sex sex sex sex.
[0029]
The surface of the Sn - based plating layer does not contain manganese oxide and contains zirconium oxide . However, tin oxide is heterogeneous in the middle containing zirconium oxide due to the manufacturing process, so that the tin oxide exists in fine particles.Oxygen and oxygen permeate through the cracks and reach the surface of the plating, gradually increasing tin oxide and tin sulfide.
[0030]
On the other hand , when a manganese oxide film exists on the surface of the tin - based plating layer without oxides , the adhesion of the oxide - oxide - tin - plating is insufficient . sex sex sex sex sex.
[0031]
However , when a layer containing zirconium oxide and manganese oxide exists on the surface of the sn - based plating layer 20 , stannous oxide contained in the coating layer 30 is reduced by manganese manganese oxide . Decrease. In addition , manganese oxidation results in oxides of even higher oxidation levels , and a film with high barrier properties is applied to suppress the permeation of oxygen and sulfur , thereby reducing oxides and tin sulfide tin sulfide tin sulfide tin sulfide tin sulfide tin sulfide Tin Tin sulfide Reduces tin sulfide. As a result, the yellowing resistance and paint film adhesion are improved, and the sulfide black discoloration resistance is both improved and improved.
[0032]
In order to achieve the above effects, the coating layer 30 needs to contain 0.20 mg/m2 or more and 0.20 mg/m2 or more of zirconium zirconium oxide in terms of metal amount per one side. When the content of zirconium oxide is 0.20 mg/22 in terms of metal zr content , the barrier property of zirconium acid is sufficient and the adhesion resistance to yellowing resistance of the coating film is sufficient . No improvement in sulfurization resistance to sulfurization and black discoloration One side One side One side One side One side One side One side One side One side / / m or more is more preferable. On the other hand, when the amount of the oxide material per one side exceeds 50.00 mg/m2 in terms of metal zr amount, the amount of oxide material is not present, so the adhesion of the coating film is decreased. The content of the zirconium zirconium oxide is preferably 30.00 mg/m2, preferably 10.00 mg/m2 or less. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
[0033]
In addition, in order to achieve the above-mentioned effect, the content of metal mn of manganic acid in 3030 and the content of zirconium oxide in terms of metal zr should be reduced on a mass basis. It is considered to be more than twice and less than 0.50 times. The amount of manganese manganese oxide on one side is not less than 1/100 1/100 in terms of metal metal mn against the amount of metal zr equivalent of the zirconium oxide, tin contained in the film Further reduction of oxides, manganese manganese oxidation is insufficient, and yellowing resistance, paint film adhesion, and black discoloration cannot be sufficiently improved. The content of manganese oxide in terms of metal mn in the coating layer, the content of zirconium, the content of metal in zirconium oxide, preferably at least twice the mass basis, 0.10 It's better than being twice. On the other hand, if the amount of manganese oxide in , or the amount of metal exceeds 1/2 of the content of zirconium oxide in terms of metal zr, manganese manganese oxide becomes excessive and embrittlement embrittlement occurs. Manganese Manganese oxide metal content in film layer It is preferably 0.40 times or less, more preferably 0.20 times or less, on a mass basis with respect to the zr-equivalent content of the zirconium compound.
[0034]
In addition, in the film layer 30, the manganese oxides are concentrated on the surface side of the film layer 30 (the concentration of the manganese oxides near the surface of the film layer is higher than that of the sn-based plating layer of the film layer 30). 20 20 20 20 20 greater than the manganese oxide concentration near the interface).
[0035]
As a result, the effect of manganese oxide is fully enhanced, so the corrosion resistance after the anti-sulfuration black discoloration coating is further improved. In addition, since the amount of manganese oxide in the film layers 30 and the sn layer 20 is small, the coating film adhesion is further improved.
[0036]
As such a state, specifically, for example, when the film layer 30 is analyzed by depth xx-ray photoelectron (xps xps) analysis, the concentration of the mn element present as manganese oxide varies. Depth position a (in other words, the position where the detection intensity of the mn element is maximized, and the depth position b (in other words, the zr element The distance in the depth direction between the position a and the depth b is 2 nm or more. there is there there is there there is there
[0037]
FIG. 2 is a diagram showing an example of an elemental profile in the thickness direction (thickness direction) of the sn-based plating layer 20 and coating layer of the sn-based plated steel sheet according to the present embodiment. The element profile shown in FIG. 2 is obtained by measuring the distribution of the elements on the surface of the coating layer from the surface of the coating layer to the surface of 10 layers through the Sn-based plating by xps depth direction analysis. is. . In the figure, the surface of the film layer 30 is the position where the "sputtering depth" is 0. The value of "sputter depth" in 2 is synonymous with "depth position".
[0038]
In the example shown in FIG. 2, the depth position a is a sputter depth of 0 nm, and the depth position b is a sputter depth of 4.0 nm. To explain the example of FIG. It is located 4 nm away from the surface of the coating layer 30 in the depth direction (in FIG. 1, 4 nm below the top surface of the coating layer 30). In the example shown in FIG. 2, the distance between the depth and bb is 4 nm.
[0039]
In this case, on the side of the film layer 30 containing both zirconium oxide and manganese oxide, manganese oxide oxide is present in a larger amount than oxide oxide on the standard basis. The fact that these depth directions a and b are separated from the depth position by 2 nm or more means that the surface side of the oxide oxide 30 and 30 is more concentrated than the zirconium oxide. For this reason, the manganese oxide concentrated on the surface of the coating layer becomes a substance with a higher oxidation number, resulting in a coating with a high barrier. The formation of tin oxide and tin sulfide in the Sn-based plating layer is suppressed in order to suppress the permeation of oxygen and sulfur through the film made of this material. Therefore, the change in the sn layer and the adhesion of the coating film to the coating film are improved, and the resistance to sulfurization blackening and blackening is also improved.

The scope of the claims

[Claim 1]
with a steel plate,
a Sn-based plating layer located on at least one surface of the steel sheet;
A film layer located on the Sn-based plating layer,
has
The Sn-based plating layer contains 0.10 g/m 2 or more and 15.00 g/m 2 or less of Sn per side in terms of metal Sn,
The coating layer contains zirconium oxide and manganese oxide,
The content of the zirconium oxide in the coating layer is 0.20 mg/m 2 or more and 50.00 mg/m 2 or less per side in terms of metal Zr,
The content of the manganese oxide in terms of metal Mn in the coating layer is 0.01 times or more and 0.50 times or less on a mass basis with respect to the content of the zirconium oxide in terms of metal Zr,
In the depth direction elemental analysis by X-ray photoelectron spectroscopy, the depth position A where the element concentration of Mn present as the manganese oxide is the maximum is the depth where the element concentration of Zr present as the zirconium oxide is the maximum. A Sn-based plated steel sheet located closer to the surface side of the coating layer than the depth position B, and wherein the distance in the depth direction between the depth position A and the depth position B is 2 nm or more.
[Claim 2]
On the surface of the coating layer, the mass of the zirconium oxide in the depth direction elemental analysis by the X-ray photoelectron spectroscopy is 0.0% of the mass of the manganese oxide in the depth direction elemental analysis by the X-ray photoelectron spectroscopy. The Sn-based plated steel sheet according to claim 1, which is 01 times or less.
[Claim 3]
The Sn-based plated steel sheet according to claim 1 or 2, wherein the distance in the depth direction between the depth position A and the depth position B is 4 nm or more.
[Claim 4]
The content of the zirconium oxide in the coating layer is 1.00 mg/m 2 or more and 30.00 mg/m 2 or less per side in terms of metal Zr, according to any one of claims 1 to 3. The Sn-based plated steel sheet described.
[Claim 5]
The content of the zirconium oxide in the coating layer is 2.00 mg/m 2 or more and 10.00 mg/m 2 or less per side in terms of metal Zr, according to any one of claims 1 to 4 The Sn-based plated steel sheet described.
[Claim 6]
The content of the manganese oxide in the coating layer in terms of metal Mn is 0.05 times or more and 0.40 times or less on a mass basis with respect to the content of the zirconium oxide in terms of metal Zr. The Sn-based plated steel sheet according to any one of Items 1 to 5.
[Claim 7]
The content of the manganese oxide in the coating layer in terms of metal Mn is 0.10 times or more and 0.20 times or less on a mass basis with respect to the content of the zirconium oxide in terms of metal Zr. The Sn-based plated steel sheet according to any one of Items 1 to 6.