JP3706524B2 - Surface-coated metal plate and manufacturing method thereof - Google Patents

Description

【００４２】
表１から明らかなように、本発明の範囲を満足する実施例はいずれも、潤滑性、接着性共に優れた特性を示した。特にりん酸塩量、及びりん酸塩量と二酸化珪素量の比率が本発明の好ましい範囲内である実施例は特に優れた潤滑性、接着性を示した。
【００４３】
一方、本発明を満足しない比較例では、潤滑性、あるいは接着性が劣る。
【００４４】
【発明の効果】
本発明の表面被覆金属板は以上の様に構成されており、金属板あるいはめっき金属板の表面をりん酸塩と二酸化珪素を含む皮膜で被覆することにより、優れた潤滑性と接着性の両特性を兼ね備えた表面被覆金属板が提供できるようになった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a surface-coated metal plate coated with a film having excellent lubricity and adhesion, and a method for producing the same, and the surface-coated metal plate is a field where press formability and workability are required, For example, it can be effectively used in fields such as household electrical appliances, building materials and automobile parts.
[0002]
[Prior art]
2. Description of the Related Art In recent years, plated steel sheets in which zinc-based plating is formed on a steel sheet surface have been widely used as a rust prevention measure for steel sheets used for automobile outer sheet materials and the like. As such a galvanized steel sheet, for example, various galvanized steel sheets such as a hot dip galvanized steel sheet and an electrogalvanized steel sheet are used. However, when these zinc-plated steel sheets are subjected to press forming, etc., the surface layer of the plated layer formed on the surface of the steel sheet has low lubricity, and since zinc is soft and easily adheres to the mold surface, press forming Occasionally, the sliding deformation resistance of the surface layer portion of the plating layer is increased, and there is a problem that cracking occurs particularly in a part where the processing conditions are severe.
[0003]
In addition, zinc alloy-plated steel sheets such as alloyed hot-dip galvanized steel sheets and Zn-Ni alloy electroplated steel sheets have excellent corrosion resistance, paintability and meltability, and the hardness of the plating layer is pure zinc. Although it is higher than the above, it is impossible to eliminate cracks that occur during press molding.
[0004]
Thus, various techniques have been developed for the purpose of preventing cracking during press molding. For example, Japanese Patent Application Laid-Open No. 58-15554 proposes a method for improving the surface lubricity by applying hard Fe-based flash plating to the surface of a zinc-based plating layer. However, although this method improves the lubricity, it requires a special equipment for flash plating, so that the manufacturing cost increases significantly.
[0005]
In addition, a method for improving lubricity by applying press oil or lubricating oil to the surface of the zinc-based plating layer has been proposed, but this method can reduce the manufacturing cost, but press oil is a fluid. Uneven coating amount and evaporation of oil are unavoidable, and stable lubricity cannot always be obtained.
[0006]
Therefore, in order to give stable lubricity, attempts have been made to increase the viscosity of the oil used, or to add extreme pressure additives, but these methods have deteriorated rust prevention properties, Degreasing has become difficult, causing problems such as poor chemical conversion treatment and poor coating.
[0007]
On the other hand, as a method for solving the above problems and imparting stable lubricity, for example, Japanese Patent Publication No. 7-13306 discloses an anhydrous alkali of a semi-metal oxide such as B, P, Si or the like on a zinc-based plating film. A technique for containing a metal salt is proposed, and Japanese Patent Application Laid-Open No. 6-116746 proposes a technique for containing an oxide such as Ni, Mn, Co, V, and W in a zinc-based plating film. . Further, Japanese Patent Publication No. 7-13308 proposes a steel sheet in which a coating containing Zn oxide, Mn oxide and one or more oxides of P, Mo, W, and V is formed on a zinc-based plated steel sheet. Has been. Furthermore, Japanese Patent Laid-Open No. 9-111473 proposes a technique for improving lubricity by forming a film of phosphorus compound or zinc compound with a thickness of 100 to 1000 nm on a zinc-based plated steel sheet.
[0008]
In addition, the applicant of the present application coats the surface of the zinc-plated steel sheet with a phosphate coating, and by specifying the amount of phosphate coating deposited and the center line average roughness of the coating layer, excellent lubricity Has applied for a patent (Japanese Patent Application No. 10-147966).
[0009]
As described above, for the purpose of improving the press formability of galvanized steel sheets, techniques for applying various coatings on the plating layer have been proposed. In addition, excellent properties such as chemical conversion properties, paintability, corrosion resistance, adhesion, and weldability are required. In particular, adhesiveness is greatly affected by the properties of the plating layer surface. For example, if the plating layer surface is coated with a solid lubricating film, there is a problem that sufficient adhesion strength between the film and the adhesive cannot be secured. It was. For this reason, it is sufficient if the surface of the plating layer is covered with a solid lubricating film even if bonding of difficult-to-weld parts using adhesives, prevention of water and dust intrusion into the gap, and reinforcement of the hollow frame Because there was a problem that it was not possible to obtain a good adhesiveness, its use was limited.
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a surface-coated metal plate having excellent lubricity and adhesiveness, and a method for efficiently producing such a surface-coated metal plate. Is to provide.
[0011]
[Means for Solving the Problems]
The surface-coated metal plate of the present invention has a gist in that the surface of a metal plate or a plated metal plate is coated with a film containing phosphate and silicon dioxide and has both excellent lubricity and adhesiveness.
[0012]
The phosphate amount a (mg / m ² ) contained in the film is in the range of 10 to 1600, and the relationship between the phosphate amount a and the silicon dioxide amount b (mg / m ² ) ( It is desirable to contain so that b / a) may be 0.01 or more.
[0013]
In the method for producing the surface-coated metal plate of the present invention, a mixed solution containing a phosphate and silicon dioxide having an average particle size of 80 nm or less (preferably colloidal silica) is applied to the surface of the metal plate or the plated metal plate, It is a manufacturing method characterized by including the process of drying.
[0014]
The metal plate used in the present invention is preferably a plated metal plate, and it is recommended that the plated metal plate is a zinc-based plated metal plate.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The type of the metal plate used in the present invention is not particularly limited, and a metal plate such as a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a titanium plate, or a single metal or various alloys plated thereon. However, it is preferable to use a plated metal plate from the viewpoint of corrosion resistance, and the use of a galvanized steel plate or a zinc alloy plated steel plate is recommended. Examples of metal plates on which zinc-based plating has been applied include various types of zinc-based plated steel sheets such as alloyed hot-dip galvanized steel sheets, Zn-Ni alloy electroplated steel sheets, hot-dip galvanized steel sheets, and electrogalvanized steel sheets, as well as various zinc alloy types. It can be applied to plated steel sheets. Of course, in the present invention, the type of metal plate to be plated, the plating method, the composition and configuration of the plating layer, etc. are not particularly limited.
[0016]
Hereinafter, although an alloyed hot-dip galvanized steel sheet will be described as a representative example in the present invention, the present invention is not limited to the type of plating and the presence or absence of plating, and can be applied to various metal plates.
[0017]
The present inventors have found that excellent lubricity can be obtained by coating the surface of the plating layer with phosphate, and have previously filed a patent application (Japanese Patent Application No. 10-147966).
[0018]
As a result of intensive studies on a method capable of imparting further excellent adhesion, the present inventors have coated the surface of the plating layer with a mixed film containing phosphate and silicon dioxide, while maintaining excellent lubricity, The inventors have found that the adhesiveness can be remarkably improved and have reached the present invention. Hereafter, each requirement which comprises the membrane | film | coat of this invention is demonstrated in detail.
[0019]
In the present invention, “excellent lubricity” refers to a coating composition (for example, a plating layer or a coating layer) applied to the sliding portion and a mold by heat or pressure generated in the sliding portion of the steel sheet during press forming, or This means that no adhesion occurs between the underlying steel plate and the mold, and no cracks occur in the steel plate (in the present invention, it may be expressed as “press formability”).
[0020]
Further, in the present invention, “excellent adhesion” means that the steel sheet is bonded to each other with an adhesive interposed between the steel sheets, and is difficult to peel off at the interface between the adhesive and the steel sheet when a shear tensile test is performed. The area of the peeled part (the part where cohesive failure occurred) inside the adhesive when peeled is larger than the area of the peeled part (the part where interface peeling occurred) at the interface between the steel sheet surface and the adhesive If it is wide, it can be evaluated that it has excellent adhesiveness.
[0021]
In the present invention, the film forming the surface coating layer contains phosphate and silicon dioxide as essential components, and the type of the phosphate is not particularly limited. For example, hopite [Zn ₃ (PO ₄ ) _2. 4H ₂ O], phosphophyllite [Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O], or the like can be used. The type of silicon dioxide is not particularly limited, and for example, completely crystallized dry silica, water-dispersed silica, and the like can be used, and it is particularly recommended to use colloidal silica.
[0022]
The properties of phosphate may be crystalline and / or amorphous. Among these, amorphous materials are less likely to generate powdering and are excellent in a small content compared to crystalline materials. It is desirable because it exhibits excellent lubricity. The crystal structure of the film can be examined using X-ray diffraction. For example, X-ray diffraction can be performed using Cu—Kα as a target, and the crystal structure can be examined from the position and intensity of the diffraction peak.
[0023]
The amount of phosphate contained in the film effectively works to improve lubricity, but is a component that adversely affects adhesion. From the viewpoint of improving adhesion, the amount of phosphate is preferably small. The lower limit of the preferred phosphate weight 10 mg / m ^2, more preferably from 50 mg / m ^2, and as the preferable upper limit 1600 mg / m ^2, more preferably from 800 mg / m ^2. If it is in the said range, the especially outstanding lubricity and adhesiveness can be ensured.
[0024]
Such excellent lubricity and adhesion are not only achieved by specifying the amount of phosphate, but it is extremely important that silicon dioxide coexists in the film together with phosphate, and the purpose is achieved. Therefore, it is desirable that the above-mentioned phosphate amount is satisfied and the relationship between the phosphate amount and silicon dioxide amount described below satisfies 0.01 ≦ b / a.
[0025]
The amount of silicon dioxide in the film is not particularly limited, but the relationship between the amount of phosphate a (mg / m ² ) and the amount of silicon dioxide b (mg / m ² ) in the film is 0.01 ≦ b / a. It is desirable that the content satisfies the expression expressed. A more preferable lower limit of b / a is 0.02, and if such a lower limit is satisfied, better adhesiveness and lubricity can be secured. Moreover, although an upper limit is not specifically limited, Since an adhesive improvement effect will be saturated and chemical conversion treatment property may deteriorate when it exceeds 0.2, a preferable upper limit is 0.2, More preferably, it is 0.1.
[0026]
The reason why the adhesion improvement effect is obtained by the film containing phosphate and silicon dioxide is not clear, but when silicon dioxide is added, the bonding force between the adhesive and the film is increased, and without reducing the lubricity, It is considered that excellent adhesiveness is given.
[0027]
In this way, if the film contains appropriate phosphate and silicon dioxide, the steel sheet can be given excellent adhesion and lubricity, so the film thickness of the film is not particularly limited, The thickness of the coating can be adjusted as appropriate according to the purpose.
[0028]
The amount of phosphate and silicon dioxide contained in the film can be measured using a quantitative analysis method such as fluorescent X-ray analysis. In this analysis, a calibration curve prepared in advance is used, and a quantitative analysis of each element may be performed on the surface-coated metal plate sample on which the film is applied. For the fluorescent X-ray analysis, for example, MULTI-CHANNNEL X-RAY FLUORESCENCE SPECTROMETER “MFX-2100” manufactured by Shimadzu Corporation can be used.
[0029]
The composition of the film is not particularly limited, but in order to further improve various properties such as paintability, corrosion resistance, and lubricity, for example, Zn, Ni, Mn, Mg, Co, Fe, Ti, Al ₂ O ₃ , TiO _2. It is also effective to contain one or more selected from metal elements such as oxides or oxides.
[0030]
Hereinafter, a method for producing the surface-coated metal plate of the present invention will be described. In carrying out the present invention, a treatment solution containing phosphate and silicon dioxide may be applied to a metal plate to form a film on the surface. The silicon dioxide used in this case preferably has an average particle size of preferably 80 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. If silicon dioxide having a small average particle size is used, A great effect of improving adhesiveness is obtained. In particular, it is desirable to use colloidal silica as silicon dioxide.
[0031]
As a method for coating the surface of the metal plate or the plated metal plate with the treatment liquid, in addition to a method of applying using a coating type treatment liquid, an immersion treatment method using a reactive treatment solution, a roll coater method, or a spray method. The coating method is not particularly limited and may be arbitrarily selected from known coating methods, but in order to uniformly mix silicon dioxide (colloidal silica) into the coating, a coating type It is desirable to adopt the coating method.
[0032]
The drying temperature of the coated film is not particularly limited, and is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, preferably 150 ° C. or lower, more preferably 100 ° C. or lower.
[0033]
【Example】
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are not intended to limit the present invention, and any modifications may be made without departing from the spirit of the present invention. Included in range.
[0034]
〔Test method〕
The test methods used in the following examples are as follows.
[0035]
(1) Lubricating test material (25 × 100 mm) was coated with rust-preventive oil (1.5 g / m ² ), a flat tool pull-out test was performed under the following conditions, and lubricity was evaluated with a friction coefficient μ.
・ Tool: Flat tool (18 × 18mm)
・ Pressure: 3000kgf
・ Sliding speed: 300mm / min
・ Sliding distance: 150mm
Based on the obtained coefficient of friction (μ), the following criteria are used for evaluation.
A: μ <0.10
○: 0.10 ≦ μ <0.12
Δ: 0.12 ≦ μ <0.135
×: 0.135 ≦ μ
[0036]
(2) Adhesive test material (25 × 100 mm) After applying antirust oil (1.5 g / m ² ) to the surface, adhesive (paste-like, highly foamed type) is applied to the surface in a range of 25 × 25 mm Prepare two sheets coated on the surface, put the specimens on top of each other with a spacer (thickness 1 mm), and bake them (180 ° C. × 20 minutes), then shear pull at a shear pulling rate of 50 mm / min. A test was conducted, and the adhesiveness was evaluated according to the fracture mode of the adhesive surface.
After the shear tensile test, the area ratio of the region in which the fracture mode was cohesive failure (breakage inside the adhesive) was measured (the remaining portion was the interface failure between the adhesive and the steel sheet surface). The evaluation criteria for adhesiveness are shown below.
◎: Cohesive fracture area ratio is 90% or more ○: Cohesive fracture area ratio is 70% or more and less than 90% Δ: Cohesive fracture area ratio is 50% or more and less than 70% ×: Cohesive fracture area ratio is less than 50% ]
First, in this example, IF steel (plate thickness: 0.8 mm) was added to a hot dip galvanizing bath (temperature: 460 ° C., component composition: Al: 0.1%, Fe: 0.02%, with the balance being substantially Zn. ) Is applied by a continuous hot dip galvanizing line (CGL) having an adhesion amount of 45 g / m ² , followed by alloying in a direct-fired alloying furnace, and galvannealed steel sheet (GA ) (45 g / m ² ).
[0038]
Similarly, in a continuous hot dip galvanizing line (CGL), hot dip galvanized steel sheet (GI) (70 g / m ² ), hot dip Zn-5% Al alloy plated steel sheet (GF) (70 g / m ² ), electro-Zn plating An electric Zn-plated steel sheet (EG) (20 g / m ² ) and an electric Zn-Ni alloy-plated steel sheet (N) (20 g / m ² ) were produced on the line and used as test materials.
[0039]
As a method for coating the surface of the test material, a coating type or reactive type processing solution is used, and the phosphate concentration, the amount of colloidal silica added, the particle size, and the coating amount in the processing solution are shown in Table 1. As shown, the surfaces of various galvanized steel sheets were coated while being changed. The amount of phosphate and the amount of silicon dioxide in the film of each steel sheet were measured using the fluorescent X-ray method.
[0040]
The obtained results are shown in Table 1.
[0041]
[Table 1]

[0042]
As is clear from Table 1, all the examples satisfying the scope of the present invention exhibited excellent characteristics in terms of both lubricity and adhesion. In particular, the examples in which the phosphate amount and the ratio between the phosphate amount and the silicon dioxide amount were within the preferred range of the present invention showed excellent lubricity and adhesion.
[0043]
On the other hand, in the comparative example not satisfying the present invention, the lubricity or adhesiveness is inferior.
[0044]
【The invention's effect】
The surface-coated metal plate of the present invention is configured as described above. By coating the surface of the metal plate or plated metal plate with a film containing phosphate and silicon dioxide, both excellent lubricity and adhesiveness are achieved. A surface-coated metal sheet having characteristics can be provided.

Claims (5)

The surface of the metal plate is coated with a film containing phosphate and silicon dioxide , and the amount of phosphate a (mg / m ² ) and the amount of silicon dioxide b (mg / m ² ) contained in the film are as follows ( 1. A surface-coated metal plate excellent in lubricity and adhesion, characterized by satisfying the formulas 1) and (2) .
10 ≦ a ≦ 1600 (1)
0.01 ≦ b / a ≦ 0.2 (2) The surface-coated metal plate according to claim 1, wherein the metal plate is a plated metal plate. The surface-coated metal plate according to claim 2 , wherein the plated metal plate is a zinc-based plated metal plate. It is a manufacturing method of the surface covering metal plate in any one of Claims 1-3 , Comprising: The liquid mixture containing a phosphate and silicon dioxide with an average particle diameter of 80 nm or less is apply | coated to the metal plate surface, and it dries then. The manufacturing method of the surface covering metal plate characterized by including a process. The manufacturing method according to claim 4 , wherein the silicon dioxide is colloidal silica.