WO2007061011A1 - Chemical conversion coated metal plate and method for producing same - Google Patents

Abstract

Disclosed is a chemical conversion coated metal plate having a self-deposited or electrolytically deposited surface chemical conversion layer on the surface of a metal plate. The surface chemical conversion layer contains at least one compound (a) containing at least one element selected from the group consisting of Zr, Ti, Hf and Si. Consequently, there is provided a metal plate having a surface chemical conversion layer which has corrosion resistance (particularly corrosion resistance in a processed portion and a damaged portion) and coating adhesion equivalent to those of a chromate coating film without containing chromium.

Description

 Specification

 Chemical conversion treated metal plate and manufacturing method thereof

 Technical field

 The present invention relates to a chemical conversion treated metal plate and a method for producing the same.

 Background art

 [0002] Not only zinc-plated steel sheets, but also almost all metallic materials, when left in the atmospheric environment, in the presence of moisture that has been physically adsorbed by atmospheric forces, SO, NO

 2 2. Corrosion occurs on the surface due to the action of corrosion-promoting substances such as flying sea salt particles.

 In order to prevent this corrosion, as a conventional method of preventing corrosion of metallic materials such as zinc-based plated steel sheets, the surface of the metallic material is brought into contact with a treatment liquid containing chromium such as chromate chromate to form a mate film. There is a method of forming a chromate film on the surface of a metal material by depositing or applying and drying.

[0003] Typical examples of depositing a chromate film by bringing the surface of a metal material into contact with a treatment solution include a chromate chromate conversion treatment and a phosphoric acid chromate conversion treatment.

 The former chromate chromate conversion treatment was put into practical use around 1950 and is still widely used in zinc-based steel sheets. The treatment liquid used for the chromate chromate conversion treatment contains chromic acid (CrO) and hydrofluoric acid (HF) as the main components, and an accelerator is added.

 Three

 Therefore, it is possible to form a deposited film containing hexavalent chromium.

[0004] The latter phosphoric acid chromate chemical conversion treatment is based on the method described in Patent Document 1 proposed in 1945, and this chemical conversion treatment solution contains chromic acid (CrO 2), phosphoric acid (H 3 PO 4), and

 3 3 4 The deposited film containing hydrofluoric acid (HF) is hydrated chromium phosphate (CrPO 4

 Four

Ο Ο) as a main component.

 2

 [0005] In many cases, these chromate type surface treatment liquids contain harmful hexavalent chromium.

The surface treatment method using such a treatment liquid containing hexavalent chromium is not only a problem in terms of environment and safety, but also the use of not only hexavalent chromium but also trivalent chromium. Non-chromate type surface, which is a method that does not contain any chromium Conversion to treatment method is desired!

 [0006] Non-chromate type surface treatment methods include precipitation type and coating type. Precipitation type has already been proven as a surface treatment method for aluminum-containing metal materials.

 The reason why non-chromate type treatment solutions have been applied to aluminum-containing metal materials from a relatively early stage is that this metal material has been widely used as a material in contact with food such as aluminum cans.

 [0007] A typical example of a non-chromate type chemical precipitation surface treatment solution for an aluminum-containing metal material is a treatment solution described in Patent Document 2.

 This treatment solution is an acidic aqueous surface treatment solution containing zirconium or titanium, or a mixture thereof, phosphate and fluoride, and having a pH of about 1.0 to 4.0. When treatment is performed using this chemical conversion treatment solution, a deposited film mainly composed of zirconium or titanium phosphorus compound is formed on the surface of the aluminum-containing metal material.

 [0008] Compared with such a chemical precipitation type surface treatment liquid for aluminum-containing metal materials, there are few existing technologies and achievements for a non-chromate type chemical precipitation type surface treatment liquid for zinc-based plated steel sheets.

 [0009] Further, in the sheet coil manufacturers of zinc-based plated steel sheets, the coating-type surface treatment is now becoming the mainstream rather than the precipitation-type surface treatment. However, depending on the sheet coil manufacturer's line, the introduction of coating-type surface treatment may not be possible due to equipment costs and locational reasons. There is a strong demand to replace it with treatment.

 [0010] In addition, the precipitation-type surface treatment can simultaneously treat both surfaces of a metal plate such as a zinc-based plated steel plate, and the soluble component can be removed in a subsequent cleaning step, so that an improvement effect such as corrosion resistance can be expected. As a result, the pretreatment liquid is brought into the treatment liquid of the next process very little by the cleaning.

It has many attractive merits such as V and points.

Patent Document 3 discloses an aqueous composition for coating aluminum, iron, or magnesium alloys, including titanium, zirconium, etc., magnesium and calcium, dissolved fluorine ions, pH Describes an aqueous composition that forms a film so that little or no etching occurs. But this water The application of the composition to galvanized steel sheets is described.

 Patent Document 1: U.S. Pat.No. 2,438,877

 Patent Document 2: JP-A-52-131937

 Patent Document 3: Japanese Patent Publication No. 9 503823

 Disclosure of the invention

 Problems to be solved by the invention

[0012] The present invention is for solving the above-mentioned problems of the prior art, and specifically, the same corrosion resistance as that of the chromate film (particularly the corrosion resistance of the processed part and the heel part) and the adhesion of the coating film. It aims at providing the chemical conversion treatment metal plate which has and does not contain chromium.

[0013] Further, on the chromate film formed by the conventional precipitation type surface treatment, about 1 to 3 more rosin-based film layers are formed as an upper layer to provide high functionality such as corrosion resistance and fingerprint resistance. A metal plate having a multi-layer coating film having the above has been formed.

 An object of the present invention is to provide a non-chromate type chemical conversion treated metal plate that can be used as a substitute for a chromate film layer used for the base of such a resin coating.

 Another object of the present invention is to provide an upper coated metal sheet having a resin layer on the upper surface of the chemical conversion treated metal sheet.

 Another object of the present invention is to provide a production method capable of producing such a chemical conversion-treated metal plate and an upper-layer coated metal plate, and a surface chemical conversion solution that can be used in these production methods.

 Means for solving the problem

 [0014] The above problems can be solved by the present invention described below.

 The present invention includes the following (1) to (20).

[0015] (1) A chemically treated metal plate, comprising at least one compound (a) containing at least one element selected from the group force of Zr, Ti, Hf and S, and is self-deposited or electrolytically deposited The total amount of Zr, Ti, Hf, and Si elements contained in the surface chemical conversion treatment layer on the surface of the metal chemical conversion layer is 5 to 50 mgZm ² per unit area of the metal chemical conversion treatment metal plate . (2) The chemical conversion treated metal plate according to (1), wherein the metal plate is a zinc-based plated steel plate.

[0016] (3) An upper coated metal plate comprising the chemical conversion treated metal plate according to any one of (1) and (2) above and a resin layer on the upper side of the surface chemical conversion treated layer of the chemical conversion treated metal plate .

 (4) The upper coated metal sheet according to (3), wherein the resin layer is a resin layer having fingerprint resistance.

 (5) The upper coated metal sheet according to (3) or (4), wherein the resin layer includes at least two layers of a layer having a non-chromate primer coating power and a layer having a top coat coating.

(6) The above (3) to (3), wherein the resin layer includes at least one selected from the group consisting of acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin and polyolefin resin. The upper coated metal sheet according to any one of 5).

 (7) The upper coated metal sheet according to any one of (3) to (6), wherein the thickness of the resin layer is 0.1 to 5 / ζ πι.

 [0017] (8) A surface chemical conversion liquid for surface treatment of a metal plate, comprising at least one compound (a) containing at least one element selected from the group force consisting of Zr, Ti, Hf and Si, and fluorinated Hydrochloric acid, nitric acid, sulfuric acid, and their group strength consisting of at least one acid group (b) selected from the group consisting of Fe, Mn, Ni, Co, Ag, Mg, Al, Zn, Cu, and Ce And at least one of the compounds (c) containing at least one element selected from: the free fluorine ion concentration is 1 to 30 mgZL, and Fe, Mn, Ni, Co, Ag, Mg in the compound (c) CZA, which is the ratio of the total mass concentration C of the elements Al, Zn, Cu and Ce to the total mass concentration A of the elements Zr, Ti, Hf and Si in the compound (a) is 1 to 200 Surface formation by contact with the surface of the metal plate satisfying pH ≤ — 0.02 X (C / A) +6. The physical layer to autodeposition, or electroless deposited surface chemical conversion layer by contact with the surface of the metal plate as the cathode, the surface chemical conversion treatment solution.

 [0018] (9) The compound (a) and the compound (c) are at least one of an organic complex compound, a fluoride complex, a sulfate group, and a group force that also includes a nitrate power, according to the above (8). Surface chemical conversion solution.

(10) Content power of the compound (a) The amount of the element in the compound (a) is 0.01 to: LOg Zl, and the content of the acidic component (b) is 0.05 to 200 gZl. Yes, (8) or (9 ) Surface chemical conversion treatment liquid.

 (11) Further, the Si-containing additive (d) is contained, and the content is 0.02 to 20 gZl in terms of the amount of Si element in the Si-containing additive (d). The surface chemical conversion treatment liquid according to any one of 10).

 (12) The surface chemical conversion liquid according to any one of (8) to (11), further comprising 0.01 to 20 gZl of an organic compound (e) having an amino group.

 (13) Power of the organic compound (e) Vinylamine, polyvinylamine, allylamamine, diarylamine, polyallylamine, polyamine polyamide, amamine-modified phenolic resin, amine-modified polyvinylphenol, and their derivative power Group power of at least one selected The surface chemical conversion treatment liquid according to (12) above.

(14) A method for producing a chemical conversion-treated metal plate, wherein a non-coating surface chemical conversion treatment layer is formed on the surface of a metal plate using the surface chemical conversion treatment liquid according to any one of (8) to (13).

 (15) The surface chemical conversion treatment liquid according to any of (8) to (13) is brought into contact with the surface of the metal plate, and the surface chemical conversion treatment layer is self-deposited on the surface of the metal plate, and then washed with water. The manufacturing method of the chemical conversion treatment metal plate as described in said (14).

 (16) The surface chemical conversion treatment liquid according to any one of (8) to (13) is brought into contact with the surface of the metal plate as a cathode, and the surface chemical conversion treatment layer is electrolytically deposited on the surface of the metal plate. Then, the method for producing a chemical conversion-treated metal sheet according to the above (15), which is washed with water.

(17) The surface chemical conversion treatment liquid at a temperature of 30 to 70 ° C. is brought into contact with the surface of the metal plate for 0.5 to 20 seconds, and Zr in the compound (a) is brought into contact with the surface of the metal plate. The method for producing a chemical conversion treated metal plate according to any one of (14) to (16) above, wherein a surface chemical conversion treatment layer of 5 to 50 mgZm ² is formed in a total amount of elements of Ti, Hf and Si.

 (18) The method for producing a chemical conversion treated metal plate according to any one of the above (14) to (17), further comprising a step of forming the resin layer on the upper surface of the surface chemical conversion treatment layer A method for producing a metal plate.

 (19) A chemical conversion treated metal plate produced by the method for producing a chemical conversion treated metal plate according to any one of (14) to (17).

(20) Upper layer coating metal produced by the method for producing an upper layer coated metal sheet according to (18) above Genus plate.

 The invention's effect

 [0020] According to the present invention, there is provided a chemical conversion-treated metal sheet having corrosion resistance (particularly corrosion resistance of a processed part and a heel part) and coating film adhesion comparable to that of a chromate film and containing no chromium. Togashi.

 Furthermore, it is possible to provide an upper coated metal plate having a corrosion layer on the upper surface of the chemical conversion treated metal plate and having excellent corrosion resistance.

 Further, it is possible to provide a production method capable of producing such a chemical conversion treatment metal plate and an upper-layer coated metal plate, and a surface chemical treatment solution usable in this production method.

 [0021] Further, when this surface chemical conversion treatment liquid is applied to a zinc-based plated steel sheet, a film with a high adhesion amount can be formed in a short time. A coating with a high adhesion amount can be formed in a short time by the production method capable of producing the chemical conversion-treated metal plate and the upper-layer coated metal plate of the present invention using this surface chemical conversion treatment solution.

 Cited Document 3 does not describe the use for galvanized steel sheets. When the present inventor applied the aqueous composition described in Reference 3 to a zinc-plated steel sheet, it was found that a film having a high adhesion amount cannot be formed in a short time. In contrast, the present invention can form a film with a high adhesion amount in a short time.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0022] The present invention will be described below.

The present invention relates to a chemical conversion-treated metal plate, comprising at least one compound (a) containing at least one element selected from the group force of Zr, Ti, Hf, and S, and subjected to self-precipitation or electroanalysis. It is a chemical conversion treatment metal plate which has a layer on the surface of a metal plate, and the total amount of elements of Zr, Ti, Hf and Si contained in the surface chemical treatment layer is 5 to 50 mgZm ² per unit area of the metal plate.

 Hereinafter, such a chemical conversion-treated metal plate is also referred to as “the chemical conversion-treated metal plate of the present invention”.

[0023] Further, the present invention is an upper-layer coated metal plate having the chemical conversion-treated metal plate of the present invention and a resin layer on the upper side of the surface chemical conversion-treated layer. Hereinafter, such an upper-layer coated metal plate is also referred to as “an upper-layer coated metal plate of the present invention”.

 [0024] Further, the present invention provides a surface chemical conversion treatment solution for metal plate surface treatment, wherein at least one of the compounds (a) containing at least one element selected from the group force consisting of Zr, Ti, Hf and Si. One, hydrofluoric acid, nitric acid, sulfuric acid, and their group power of at least one selected from the acid component (b), Fe, Mn, Ni, Co, Ag, Mg, Al, Zn, And containing at least one compound (c) containing at least one element selected from the group force consisting of Cu and Ce, free fluorine ion is 1 to 30 mgZL, and Fe, Mn, Ni in the compound (c), CZA is the ratio of the total mass concentration C of the elements Co, Ag, Mg, Al, Zn, Cu and Ce to the total mass concentration A of the elements Zr, Ti, Hf and Si in the compound (a). 1 to 200, the pH is 2.0 or more, and the surface of the metal plate satisfying pH≤—0.02 X (C / A) +6 is satisfied. In that autodeposition surface chemical conversion layer, or electrolyte to deposit surface chemical conversion layer by contact with the surface of the metal plate as the cathode, a surface chemical conversion treatment solution. Hereinafter, such a surface chemical conversion treatment liquid is also referred to as a “treatment liquid of the present invention”.

 [0025] The present invention is also a method for producing a chemical conversion-treated metal plate, wherein a non-coating surface chemical conversion treatment layer is formed on the surface of the metal plate using the treatment liquid of the present invention.

 Hereinafter, such a method for producing a chemical conversion-treated metal plate is also referred to as “a method for producing a chemical conversion-treated metal plate of the present invention”.

 [0026] Further, the present invention provides a method for producing an upper-layer coated metal sheet, further comprising the step of forming the resin layer on the upper surface of the surface chemical treatment layer in the method for producing a chemical conversion-treated metal sheet of the present invention. It is.

 Hereinafter, such a method for producing an upper coated metal sheet is also referred to as “a method for producing an upper coated metal sheet of the present invention”.

 [0027] The chemical conversion-treated metal plate of the present invention can be produced by the method for producing a chemical conversion-treated metal plate of the present invention using the treatment liquid of the present invention.

 Moreover, the upper layer metal plate of the present invention can be produced by the method for producing the upper layer metal plate of the present invention using the treatment liquid of the present invention.

[0028] First, the chemical conversion treated metal plate of the present invention will be described.

The chemical conversion treated metal plate of the present invention has at least a group force selected from Zr, Ti, Hf and S. In addition, at least one compound (a) containing one element is included, and a self-deposited or electrolytically deposited surface chemical conversion treatment layer is provided on the surface of the metal plate.

 [0029] Here, the compound (a) contains at least one element selected from the group force of Zr, Ti, Hf and S, for example, an oxide, a hydroxide, a complex compound, an inorganic acid, or an organic acid. Such as salt. The compound (c) described later is similarly such a compound. Among these, at least one selected from the group consisting of organic complex compounds, fluoride complexes, sulfates and nitrates is preferable. The same applies to the compound (c) described later. This is because the acid and the cation component of these salts can be easily removed in the washing step after the chemical conversion treatment, and even if they remain slightly, they do not adversely affect the corrosion resistance.

 [0030] Examples of the compound (a) include zirconyl nitrate, zirconyl acetate, zirconyl sulfate, zirconium carbonate ammonium, zircon hydrofluoric acid, titanium sulfate, lactic acid and titanium alkoxide. And various reactants such as titanium laurate, titanium hydrofluoric acid, caffeine hydrofluoric acid, tetraethoxysilane, and the like, and lactic acid-norfunum, nitrate-nitrium, hafnium fluoride, and hafnium hydrofluoric acid.

 [0031] In the chemical conversion treated metal sheet of the present invention, the surface chemical conversion treatment layer contains at least one of such compounds (a).

Further, the total amount of Zr, Ti, Hf and Si elements contained in this surface chemical conversion treatment layer is 5 to 50 mgZm ² per metal plate unit area. Preferably, this range is the preferred instrument 20～30MgZm ² it is 10~40mgZm ^2. If it is 5 mgZm ² or more, the corrosion resistance will be sufficient, and if it is 50 mgZm ² or less, the elasticity will be sufficient, and the adhesion of the heat treatment layer will be sufficient.

 [0032] The surface chemical conversion treatment layer preferably further contains a Si-containing additive (d). When the Si-containing additive (d) is contained, the adhesion of the surface chemical conversion treatment layer to the metal plate surface is improved.

 [0033] Preferred examples of the Si-containing additive (d) include silane coupling agents and water-dispersible silica.

Examples of silane coupling agents include N-β (aminoethyl) _{Ύ -aminopropyltrimethoxysilane} , N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, Ν- β (Aminoethynole) γ-Aminopropyltriethoxysilane, N-j8 (Aminoethynole) γ-Aminopropylmethyljetoxysilane, γ-Aminopropyltriethoxysilane, γ-Aminopropyltrimethoxysilane, Ν Phenol Γ-Aminopropyltrimethoxysilane, Ν-Pheninole γ-Aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxy Silane, _{メ タ -Methacryloxypropylmethyl jetoxysilane} , N—j8— (Ν—Bulbenylaminoethyl) γ—Aminopropyltrimethoxysilane, N—j8— (Ν—Bulbendylaminoethyl) γ —Aminopropylmethyldimethoxysilane, N—j8 -(N Bulbendylaminoethyl) γ-Aminopropyltriethoxysilane, Ν- β-(Ν Bulbendylaminoethyl) γ-Aminopropylmethyl jetoxysilane, Silane, γ-Glycidoxypro _{Pinoletriethoxysilane} , γ-glycidoxypropinolemethinorediethoxysilane, _Ί —Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, _{γmercaptopropyltriethoxysilane} , _{γmercaptopropylpyrumethylmethoxysilane} , Methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyljetoxysilane, vinyltriacetoxysilane, γ-chloropropylpropylmethoxysilane, γ-chloropropylmethyldimethoxysilane, γchloropropyl Tokishishiran, _I black port propyl methyl jet silane, to Kisamechiruji silazane, .gamma. § two Reno trimethoxysilane, .gamma. § two Reno methyldiethoxy methoxamine Shishiran, .gamma. § two Reno triethoxysilane, _I - § D Linopropylmethyljetoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, butylmethyljetoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [ 3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methylethoxysilyl) mouth pill Ammoxidation - Umukuroraido, gamma black port methyl dimethoxy silane, gamma-mercaptopropyl methyl dimethoxy silane, methyl trichlorosilane, dimethyl dichlorosilane

And trimethylchlorosilane. [0034] In addition, preferred examples of the water-dispersible silica include liquid phase silica (colloidal silica) and gas phase silica.

 Examples of liquid phase silica include Snowtex C, Snowtex 0, Snowtex N, Snowtex S, Snowtex UP, Snowtex PS—M, Snowtex PS—L, Snowtex 20, Snowtex 30, Snowtex. 40 (all of which are manufactured by Nissan Chemical Industries, Ltd.) The power is not limited to these.

 Examples of the gas phase silica include, but are not limited to, Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil ΜΟΧ80, Aerosil MOX170 (all manufactured by Nippon Aerosil). It is not something.

 [0035] The Si-containing additive (d) is preferably at least one selected from the group force consisting of these silane coupling agents and water-dispersible silica.

 [0036] The surface chemical conversion treatment layer preferably contains such a Si-containing additive (d). Although the content is not particularly limited, the surface chemical conversion treatment layer contains Zr, Ti, Hf. And 0.1 to 300% by mass with respect to the total amount of elements of Si and 1 to 100% by mass is more preferable, and 5 to 50% by mass is most preferable. . Within such a range, the adhesiveness to both interfaces with the plating base and the resin layer is improved, and further, the height of the surface chemical conversion treatment layer is improved.

 [0037] Further, the surface chemical conversion treatment layer further includes an amino group (imino group, a functional group having a structure of -NRIT, a functional group having a structure of N + RITR ~ (R, RR \ IT It is preferable to contain an organic compound (e) having the same group. This is because when the organic compound (e) is contained, the structure of the surface chemical conversion treatment layer becomes dense and the corrosion resistance is further improved. The reason why the corrosion resistance is improved in this way is considered to be due to the action of these functional group S inhibitors.

 [0038] The organic compound (e) having an amino group may be an organic polymer having an amino group or an organic resin.

The organic compound (e) having an amino group is not particularly limited. Preferably, bullamine, polyvinylamine, arylamine, diarylamine, polyallylamine, polyamine polyamide, It is at least one organic compound selected from the group power consisting of min-modified phenol resin, amine-modified polyvinyl phenol, and derivatives thereof. Among these, at least one selected from the group strength of allylamin, polyallylamine, and derivatives thereof is more preferable.

 [0039] Here, as the derivative, for example, at least one selected from the group force of buramin, polyburamin, allylamamine, diarylamine, polyallylamine, polyamine polyamide, amine-modified phenolic resin and amine-modified polyvinylphenol is used in the molecule. And compounds derived from this compound, and salts of these compounds. Specifically, for example, a buramine salt, a maleic acid-diallylamine copolymer, and a diallylamine monodioic acid sulfur copolymer may be mentioned.

 [0040] The surface chemical conversion treatment layer preferably contains such an organic compound (e), and the content is not particularly limited, but Zr, Ti, Hf and the surface chemical conversion treatment layer contain. And 0.5 to 120% by mass, more preferably 2 to 80% by mass, and most preferably 10 to 50% by mass with respect to the total amount of elements of Si and Si. Within such a range, the structure of the surface chemical conversion treatment layer becomes denser, and there is an effect that the corrosion resistance is further improved.

 [0041] The surface chemical conversion treatment layer may further contain a water-soluble resin and Z or emulsion resin. If these are contained, the surface chemical conversion treatment layer becomes more flexible, and even if the chemical conversion treatment metal plate of the present invention and the upper metal plate of the present invention having such a surface chemical conversion treatment layer are formed and processed, The surface chemical conversion treatment layer formed on the surface of the film becomes more difficult to peel off.

 [0042] Examples of the water-soluble resin or emulsion resin include acrylic resin, alkyd resin, epoxy resin, urethane resin, polyester resin, epoxy polyester resin, acetic acid Water-soluble ones that are compatible, such as vinyl resin and styrene-butadiene resin.

[0043] It is preferable that the surface chemical conversion treatment layer contains such a water-soluble resin and Z or emulsion resin, but the content is not particularly limited, but the Zr contained in the surface chemical conversion treatment layer is not particularly limited. 0.5 to 300% by mass with respect to the total amount of Ti, Hf and Si elements 2 to 150% by mass is more preferable 5 to: LOO% by mass is most preferable. Within such a range, the surface chemical conversion treatment layer becomes more flexible, and even if the chemical conversion treatment metal plate of the present invention and the upper coating metal plate of the present invention having such a surface chemical conversion treatment layer are molded, The surface chemical conversion treatment layer formed on the surface of the metal plate has an effect that it is more difficult to peel off. Moreover, when it is in such a range, there exists an effect that corrosion resistance improves.

[0044] The surface chemical conversion treatment layer may contain a component of the metal plate on which the surface chemical conversion treatment layer is formed. For example, if Ni, Co, Cu, Sn, etc. are contained in the surface chemical conversion treatment solution used to form this surface chemical conversion treatment layer and Zn or A1 is present on the surface of the metal plate, these elements are replaced. In some cases, these surface chemical conversion treatment layers contain these Zn and A1 elements. As described above, the total amount of elements existing on the surface of the metal plate and existing in the surface chemical conversion treatment layer is 0.1 to 50 mgZm per unit area of the metal plate. ² is preferred 0.5 to ²⁰ mgZm ² is more preferred 1 to 5 mgZm ² is most preferred.

 [0045] Further, the surface chemical conversion treatment layer may contain an element of the component (c) described later.

[0046] The chemical conversion treatment metal plate of the present invention has such a surface chemical conversion treatment layer on the surface of the metal plate.

[0047] Here, the metal plate is not particularly limited! Examples thereof include zinc-based plated steel sheets, aluminum-plated steel sheets, tin-plated steel sheets, cold-rolled steel sheets, and aluminum sheets.

 Moreover, this zinc-based plated steel sheet is a steel sheet having a plated layer containing zinc. Examples include galvanized steel sheets, zinc alloy galvanized steel sheets, 55% aluminum galvanized steel sheets, 5% aluminum galvanized steel sheets, tin zinc galvanized steel sheets, zinc nickel plated steel sheets, and iron and zinc galvanized steel sheets. It is done.

 Of these, zinc-plated steel sheets or zinc alloy-plated steel sheets are preferred. The reason is that the surface chemical conversion treatment layer formed on the surface becomes denser and the adhesion between the metal plate and the surface chemical conversion treatment layer is improved as compared with other metal plates.

[0049] The method for producing the metal plate itself is not particularly limited, and for example, it can be produced by a known method. In the case of galvanized steel sheet or zinc alloy galvanized steel sheet, In addition, a known steel plate can be processed by a known electrogalvanizing method or hot dip galvanizing method.

 [0050] Further, the size and thickness of the metal plate are not limited.

 For example, in the case of a zinc-based steel sheet treated by the electrogalvanizing method, for example, a coil-shaped steel sheet having a thickness of 0.4 to 2.3 mm and a width of 500 to 2080 mm may be mentioned.

The thickness of the electrogalvanized layer is not limited. Usually, it is about 1-50gZm ^{2 on} one side. Further, for example, in the case of a zinc-based steel sheet treated by the hot dip galvanizing method, for example, a coil-shaped one having a thickness of 0.23 to 3.2 mm and a width of 500 to 1850 mm may be mentioned. The thickness of the hot dip zinc plating layer is not limited. Usually, it is about 20-150gZm ^{2 on} one side.

 According to the method for producing a chemical conversion-treated metal plate of the present invention described later or the method for producing an upper-layer coated metal plate of the present invention, such a coil-shaped metal plate can be continuously processed.

[0051] The chemical conversion metal plate of the present invention has a surface chemical conversion treatment layer containing at least one of the compound (a) on the surface of such a metal plate, and this surface chemical conversion treatment layer is self-deposited or electro-deposited. Analyze.

 Here, the self-deposition means that the surface chemical conversion treatment layer is formed only by bringing the treatment liquid containing the compound (a) into contact with the metal plate, for example, the surface chemical treatment liquid of the present invention described later. It means that.

 [0053] Here, the electrolytic deposition means that the surface treatment is performed by bringing a treatment solution containing the compound (a), for example, a surface chemical treatment solution of the present invention described later, into contact with the metal plate as a cathode. A formation layer will be formed!

[0054] Next, the upper coated metal sheet of the present invention will be described.

 The upper-layer coated metal sheet of the present invention has the chemical conversion-treated metal sheet of the present invention and a resin layer on the upper side of the surface chemical conversion-treated layer.

 The upper layer coated metal plate of the present invention preferably has the chemical conversion treated metal plate of the present invention and a resin layer on the upper surface of the surface chemical conversion treated layer.

[0055] The resin layer may be composed of a plurality of resin layers.

In addition, it is preferable that the resin layer is a resin layer having fingerprint resistance. In addition, it is preferable to include at least two layers of a layer having a non-chromate primer coating strength and a layer having a top coat coating strength.

 Moreover, it is preferable that this resin layer is a coating layer for laminated steel sheets.

[0056] The material of the resin layer is not particularly limited. For example, a coating agent for the purpose of imparting corrosion resistance, fingerprint resistance or lubricity which is applied to the upper surface of the chromate pretreatment film! It can be formed using.

[0057] When the resin layer is a resin layer having fingerprint resistance, the material of the resin layer is not particularly limited as long as it imparts fingerprint resistance to the resin layer.

 For example, it is preferable to include at least one selected from the group strength consisting of acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin and polyolefin resin. This is because the fingerprint resistance of the resin layer is improved.

[0058] Further, the resin layer in which the resin layer has fingerprint resistance preferably further contains silica sol. This is because fingerprint resistance and corrosion resistance are well balanced in this case.

 Furthermore, 20 to 97% by mass of at least one selected from the group strength consisting of acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin and polyolefin resin

Further, it is preferable to contain 2 to 50% by mass of silica sol and 1 to 30% by mass of water-based wax. This is because, in this case, fingerprint resistance and corrosion resistance S are particularly well balanced.

[0059] The thickness of the resin layer having such fingerprint resistance is preferably 0.1 to 5 μm in terms of dry thickness, and preferably 0.4 to 5 μm. More preferred 0.4-4 μm is even more preferred. This resin layer may include a plurality of layers.

[0060] Further, between the chemical conversion-treated metal plate of the present invention of the upper-layer coated metal plate of the present invention and the resin layer having fingerprint resistance on the surface chemical conversion-treated layer, an inorganic substance and Z Alternatively, it is preferable to have a layer made of an organic material. This layer is preferably 0.01 to 0.2 m thick. This layer preferably contains chromium-free metal cations. Examples of the organic material that can be used here include the organic compound (e), the water-soluble resin, the emulsion resin, and the like.

[0061] The resin layer preferably includes at least two layers, ie, a layer having a non-chromate primer coating strength and a layer having a topcoat coating strength. [0062] Here, as the non-chromate primer coating, a non-chromate primer coating which does not contain a chromate-type anti-glare pigment can be used.

 The non-chromate primer contains rosin and may contain a coloring pigment, an antifungal pigment, and the like as necessary. The resin may be in any form such as water, solvent, and powder. Examples of the types of resin are generally known, such as polyacrylic resin, polyolefin resin, polyurethane resin, epoxy resin, polyester resin, polypropylene resin, and melamine resin. It is possible to use fluorine-based resin as it is or in combination.

 [0063] Further, as the coloring pigment, titanium oxide (TiO 2), zinc oxide (ZnO), zirconium oxide

 2

 Hum (ZrO), calcium carbonate (CaCO), barium sulfate (BaSO), alumina (Al 2 O 3),

 2 3 4 2 3 Inorganic pigments such as kaolin clay, carbon black, iron oxide (Fe 2 O 3), and Hansa

 2 3 3 4

 Known coloring pigments such as organic pigments such as yellow, pyrazolone orange and azo pigments can be used. Commonly known anti-fouling pigments, for example, phosphoric acid-based anti-fouling pigments such as zinc phosphate, iron phosphate, and aluminum phosphate, and molybdate-based defensive pigments such as calcium molybdate, aluminum molybdate, and barium molybdate. In addition, vanadium type antifouling pigments such as vanadium oxide, finely divided silica such as water-dispersible silica and fumed silica, and the like can also be used. However, it is desirable not to use chromate type antifouling pigments such as strontium chromate, zinc chromate, calcium chromate, potassium chromate and normochromate because they are environmentally toxic. In addition, additives such as an antifoaming agent, a dispersion aid, and a diluent for lowering the viscosity of the paint may be appropriately blended.

 [0064] The thickness of the non-chromate primer coating layer is preferably 1 to 30 µm after drying, more preferably 2 to 20 µm. If it is 1 μm or more, the corrosion resistance is high, and if it is 30 m or less, the adhesion is high.

 [0065] Here, the top coat paint is not particularly limited, and an ordinary top coat for painting can be used.

For example, it contains rosin, and if necessary, it can further contain a coloring pigment or an antifungal pigment. As the resin, coloring pigment and anti-bacterial pigment, and additives, those similar to those used in the non-chromate primer can be used. [0066] The thickness of such a layer serving as a top coat paint strength is preferably 3 to 50 µm after drying, and more preferably 5 to 40 / ζ πι. In such a range, the corrosion resistance is high V, and it is preferable because it has a positive effect. If this thickness is too thick, the adhesion tends to decrease.

 [0067] The upper coated metal sheet of the present invention having a resin layer including at least two layers of a non-chromate primer coating force and a top coat coating force has excellent corrosion resistance and coating film adhesion. Non-chromate high performance coated metal plate, non-chromate pre-coated metal plate. The resin layer having these two layers usually further has alkali resistance, lubricity, and slip resistance (coin scratch resistance).

 [0068] Next, a method for producing the chemical conversion metal plate of the present invention will be described.

 The manufacturing method of the chemical conversion treatment metal plate of the present invention uses the processing liquid of the present invention.

 [0069] The treatment liquid of the present invention contains at least one of the compounds (a).

 Here, water or an organic solvent can be used as the solvent, and a mixture thereof can also be used. Examples of the organic solvent include ethanol and acetone. The solvent is preferably water.

 For this compound (a), preferred embodiments and the like are the same as described above.

Here, the content of the compound (a) in the treatment liquid of the present invention is not particularly limited. Force The total amount of Zr, Ti, Hf and Si elements in the compound (a) in the treatment liquid The concentration (total mass concentration A) is preferably 0.01 to 10 gZl, more preferably 0.05 to 5 gZl, and more preferably 0.1 to LgZl. When it is at least OlgZl, the formation rate of the surface chemical conversion treatment layer becomes faster, which is preferable for industrial use. Moreover, it is preferable that it is not more than lOgZl because the dissolution stability of the compound (a) can be more easily maintained in the treatment liquid of the present invention.

[0071] Further, the treatment liquid of the present invention contains an acid component (b) that is at least one selected from the group consisting of hydrofluoric acid, nitric acid, sulfuric acid, and salts thereof.

Here, the acid component (b) includes hydrofluoric acid, nitric acid, sulfuric acid, and these which can etch the surface of the metal plate when the treatment liquid of the present invention is applied to the surface of the metal plate. There is no particular limitation as long as it is at least one group power that is also salt power. For example, hydrofluoric acid (HF), zircon hydrofluoric acid (H ZrF), titanium hydrogen fluoride

 2 6

 Acids with fluoride complexes such as acid (H TiF) or hafnium hydrofluoric acid (H HfF)

2 6 2 6

 These include nitric acid, sulfuric acid or salts thereof.

[0072] In the treatment liquid of the present invention, it can be used as such an acid component (b). That is, a plurality of inorganic acids may be mixed and used, or one or more inorganic acids and one or more organic acids may be mixed and used.

 [0073] Since the acidic component (b) is at least one selected from hydrofluoric acid, nitric acid, sulfuric acid, and their salt strength, it has an appropriate etching property, and further includes a cleaning step after chemical conversion treatment. Can be easily removed, and even if it remains slightly, it is difficult to adversely affect the corrosion resistance!

 [0074] The content of the acid component (b) in the treatment liquid of the present invention is not particularly limited, but is preferably 0.05 to 200 gZl, more preferably 0.2 to LOOgZl. . When the amount is 0.5 gZl or more, sufficient etching ability for the surface of the metal plate to which the treatment liquid of the present invention is applied can be expected. When it is 200 gZl or less, the etching ability becomes moderate, and a uniform surface chemical conversion treatment layer can be deposited.

[0075] Further, the treatment liquid of the present invention contains at least one compound (c) containing at least one element selected from the group force consisting of Fe, Mn, Ni, Co, Ag, Mg, Al, Zn, Cu and Ce. Contains one. In particular, a compound containing at least one element selected from the group power consisting of Mg, Al, Cu and Zn is preferable. This is because it easily forms a complex with free fluorine ions. Examples of the compound (c) include permanganic acid, potassium permanganate, sodium permanganate, manganese nitrate, manganese sulfate, manganese fluoride, manganese carbonate, manganese acetate, magnesium nitrate, and oxidation. Magnesium, Magnesium hydroxide, Magnesium sulfate, Magnesium acetate, Aluminum nitrate, Aluminum oxide, Aluminum hydroxide, Aluminum sulfate, Aluminum acetate, Cerium acetate (111), Cerium acetate (IV), Cerium nitrate (ΠΙ), Cerium (IV) nitrate, nickel chloride, nickel sulfate, nickel nitrate, nickel fluoride, nickel oxide, nickel hydroxide, cobalt chloride, cobalt sulfate, cobalt nitrate, FUJI Cobalt, cobalt oxide, hydroxy-cobalt, silver chloride , Silver sulfate, silver nitrate, silver fluoride, acid silver, silver hydroxide, Examples include zinc chloride, zinc sulfate, zinc nitrate, zinc fluoride, zinc oxide, and zinc hydroxide. [0076] Further, the treatment liquid of the present invention has a free fluorine ion concentration of 1 to 30 mgZL, and Fe, Mn, Ni, Co, Ag, Mg, Al, Zn, Cu, and Ce in the compound (c). CZA, which is the ratio of the total mass concentration C, which is the concentration of the total amount of elements in the processing solution, to the total mass concentration A of the elements Zr, Ti, Hf and Si in the compound (a) is 1 ˜200, pH is 2.0 or more, and further satisfies pH ≦ —0.02 X (CZA) +6. The present inventor has found that the effect of the present invention becomes remarkable when all of these conditions are satisfied.

 Here, the free fluorine ion concentration can be adjusted to 1 to 30 mgZL by adjusting the amount of the element added in the compound (c) (that is, the total mass concentration C).

 [0078] The pH of the treatment solution of the present invention can be adjusted by the content of the acid component (b) and the addition of an alkaline substance. The alkaline substance is not limited as long as it can adjust the pH without greatly degrading the performance of the treatment liquid of the present invention. Preferred examples of such an alkaline substance include ammonia, sodium carbonate, organic amines (such as ethanolamine and triethylamine), and inorganic hydroxides (such as sodium hydroxide and potassium hydroxide).

 [0079] The treatment liquid of the present invention preferably further contains the Si-containing additive (d). When this Si-containing additive (d) is contained, the adhesion of the surface chemical conversion treatment layer formed by the treatment liquid of the present invention to the metal plate surface is improved.

 The preferred embodiment of this Si-containing additive (d) is the same as described above.

[0080] Here, the content of the treatment solution of the present invention, the Si-containing additive (d) is that the force ^s preferably 0. 02～20GZl in an amount of Si element in the Si-containing additive, More preferably, it is from 1 to 5 gZl. When the Si-containing additive (d) is contained in such a content, the adhesion of the surface chemical conversion treatment layer formed by the treatment liquid of the present invention to the metal plate surface is further improved.

 [0081] The treatment liquid of the present invention preferably further contains the organic compound (e). When this organic compound (e) is contained, the structure of the surface chemical conversion treatment layer formed by the treatment liquid of the present invention becomes denser and the corrosion resistance is further improved.

 With respect to this organic compound (e), preferred embodiments and the like are the same as described above.

[0082] Here, the content of the organic compound (e) is preferably 0.01 to 20 g / l. More preferred is 5 to 10 gZl. Most preferred is 0.1 to 1. OgZl. With such a content, the structural strength of the surface chemical conversion treatment layer formed from the treatment liquid of the present invention becomes dense, and the corrosion resistance is further improved.

 [0083] The treatment liquid of the present invention may generate sludge depending on the use conditions. For example, when a zinc-based plated steel plate is used as a metal plate to which the treatment liquid of the present invention is applied, and the pH of the treatment liquid of the present invention is about 4.5 or more, Zn ion force generated by elution into the treatment liquid of the invention In some cases, sludge is formed in the treatment liquid of the present invention by forming a salt such as a hydroxide salt.

 In such a case, it is preferable to add a sequestering agent having chelating ability to eluted ions, for example, Zn ions eluted in the above cases, to the treatment liquid of the present invention. Here, this addition amount is preferably added so as to be 0.01 to 50 gZl in the treatment liquid of the present invention.

 [0084] Examples of the sequestering agent include hydrofluoric acid, darconic acid, peptogluconic acid, oxalic acid, tartaric acid, organic phosphonic acid, ethylenediamine tetraacetic acid (EDTA), glycol etherdiamine tetraacetic acid (GEDTA), and triethylene. Examples include tetramine hexaacetic acid (TTHA), diethylenetriaminepentaacetic acid (DTPA), and ditrimethyl acetate (NTA). These sequestering agents can be used in combination. The sequestering agents exemplified here are particularly preferable for the ability to exert chelating ability against Zr, Ti, Hf and Si, and to exhibit the chelating ability against Zn ions.

 [0085] The treatment liquid of the present invention preferably further contains an oxidizing agent. In addition, when the metal plate to which the treatment liquid of the present invention is applied is a metal plate having a plating film, it can contain a metal ion (hereinafter also referred to as an accelerator) that is more noble than the material of the plating. By containing this oxidizing agent and accelerator, the reaction for forming the surface chemical conversion treatment layer can be promoted. As this oxidizing agent, HCIO, HBrO, HNO, HMnO, HVO, H 2 O, H 2 WO

 3 3 2 4 3 2 2 2 4

, H MoO and their salts. These oxidizing agents are used to etch the metal plate surface.

twenty four

 It is considered that the formation reaction of the surface chemical conversion treatment layer is promoted (the deposition efficiency of the surface chemical conversion treatment layer is increased).

[0086] When a zinc-based steel plate is used as the metal plate, examples of the accelerator include compounds containing Ni, Co, Cu, Sn, and the like. These are plating materials It is deposited on the plating surface by substituting the metal forming the metal and promotes etching by the action of forming an infinite number of micro galvanic cells, thereby promoting the formation reaction of the surface chemical conversion treatment layer (deposition of the surface chemical conversion treatment layer). To increase efficiency).

 These oxidizing agents and accelerators are effective when the contact time between the metal plate and the treatment liquid of the present invention cannot be provided for a long time because of production line facilities.

 [0087] The treatment liquid of the present invention may further contain the water-soluble resin and Z or emulsion resin. When these are contained, the surface chemical conversion treatment layer formed using the treatment liquid of the present invention becomes more flexible. And even if the chemical conversion treatment metal plate of this invention manufactured using the processing liquid of this invention and the upper coating metal plate of this invention are shape-processed, the surface chemical conversion treatment layer formed in the surface of a metal plate becomes more difficult to peel.

 Preferred embodiments of the water-soluble rosin and Z or emulsion resin are the same as described above.

 [0088] Here, the content of the water-soluble resin and Z or emulsion resin is preferably 0.1 to 200 g Zl. 0.5 to: More preferably LOOgZl. 1 to 50 gZl Most preferably. Such a range is preferable because the surface chemical conversion treatment layer formed using the treatment liquid of the present invention becomes more flexible.

 [0089] The treatment liquid of the present invention further includes at least one surface active selected from the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant. It is preferable to contain an agent. As a result, even if the surface of the metal plate to which the treatment liquid of the present invention is applied is cleaned by degreasing in advance, a good film (surface chemical treatment layer) can be formed. . That is, the treatment liquid of the present invention containing a surfactant can be used as a surface treatment liquid for degreasing conversion.

[0090] Here, the content of the surfactant is preferably 0.05 to 50 g / l, more preferably 0.5 to 3 OgZl, and most preferably l to 20 gZl. preferable. Such a range is preferable because an effect of exerting sufficient degreasing properties is also obtained. If it is larger than such a range, foaming during degreasing tends to become intense, and the detergency with respect to the amount of the surfactant used tends to be difficult to increase. In this case, there is a tendency to become an IJ that is costly. The treatment liquid of the present invention is considered to be mixed from a metal plate in consideration of long-term running properties. For example, metal ions such as Zn and Al can be appropriately added to the treatment liquid in advance. As a result, there is a tendency to have a certain etching property from the early stage of the bath, and it is effective to form a surface chemical conversion treatment layer of a certain quality.

 [0092] Here, although the content of this metal ion is determined for each line depending on the operating conditions, it is usually preferably 0.1 to 50 gZl, and preferably 0.5 to 25 gZl. Most preferred is 1 to 15 g / l. Within such a range, there is a tendency to have a certain etching property from the beginning of the bath, and when a surface chemical conversion treatment layer having a certain quality is easily formed, the effect is obtained.

 [0093] As described later, such a treatment liquid of the present invention causes the surface chemical conversion treatment layer to self-deposit by contacting the surface of the metal plate, or by contacting the surface of the metal plate as a cathode. It is a surface chemical conversion treatment solution for electrolytically depositing a chemical treatment layer.

 [0094] The chemical conversion treatment metal plate production method of the present invention is a production method in which a non-coating surface chemical conversion treatment layer is formed on the surface of the metal plate using the treatment liquid of the present invention.

 Here, the “non-coating surface chemical conversion treatment layer” refers to a surface chemical conversion treatment layer that self-deposits by contacting the surface of the metal plate or an electric analysis by contacting the surface of the metal plate as a cathode. It means a surface chemical conversion treatment layer.

 [0095] The metal plate used in the method for producing a chemical conversion-treated metal plate of the present invention is not particularly limited, and is as described above.

 Preferred embodiments, sizes, etc. are also as described above.

 [0096] In the method for producing a chemical conversion-treated metal plate of the present invention, it is preferable to form a non-coating surface chemical conversion treatment layer after cleaning the surface of the metal plate.

 This cleaning method is a method of cleaning by removing oil and dirt adhering to the surface of the metal plate, and is not particularly limited, and a known method can be applied. For example, a method of washing with an alkaline degreasing agent or an acidic degreasing agent, hot water washing or solvent washing may be mentioned.

[0097] Further, before and after cleaning the surface of the metal plate, the surface may be adjusted with an acid, an alkali, or the like. The reason is that the adhesion of the surface chemical conversion treatment layer formed by applying the treatment liquid of the present invention to the surface of the metal plate is improved. Also In addition, it is a force that improves the formation (precipitation) efficiency per hour of the surface chemical conversion treatment layer. In addition, after such cleaning of the surface of the metal plate and Z or surface adjustment, it is preferable to further wash with water so that no detergent or the like remains on the surface of the metal plate.

In the chemical conversion treatment metal plate production method of the present invention, preferably, a non-coating surface chemical conversion treatment layer is formed on the surface of the metal plate subjected to such treatment using the treatment liquid of the present invention.

 Specifically, the surface chemical conversion treatment layer is formed by bringing the treatment liquid of the present invention into contact with the surface of the metal plate to cause the surface chemical conversion treatment layer to self-deposit on the surface of the metal plate and then washing with water. .

 Alternatively, the surface chemical conversion treatment layer is formed by bringing the treatment liquid of the present invention into contact with the surface of the metal plate serving as a cathode, electrolytically depositing a surface chemical conversion treatment layer on the surface of the metal plate, and then washing with water. .

 These two methods will be described more specifically below.

 [0099] The method of bringing the treatment liquid of the present invention into contact with the surface of the metal plate and causing the surface chemical conversion treatment layer to self-deposit on the surface of the metal plate is not particularly limited. A spray method can be applied.

 Here, the contact time between the treatment liquid of the present invention and the metal plate is not particularly limited, but is preferably 0.5 to 20 seconds, and more preferably 1 to 10 seconds. More preferably, it is 5 to 5 seconds. If the contact time is too short, the treatment liquid of the present invention and the surface of the metal plate do not sufficiently react, and a surface chemical conversion treatment layer having excellent corrosion resistance may not be obtained! /. In addition, if the contact time is too long, the performance of the obtained surface chemical conversion treatment layer is not improved, and the point of operation efficiency in the line is also favorable.

 [0100] Here, in the case of the spray method, the formation efficiency (precipitation efficiency) of the surface chemical conversion treatment layer tends to be increased by applying the intermittent spraying twice or more at intervals of 0.2 to 5 seconds. In this case, when the treatment liquid of the present invention foams and causes a problem, it is preferable to add an antifoaming agent to the treatment liquid of the present invention. There are no particular limitations on the type of antifoaming agent, and any known one can be used as long as it does not impair the adhesion of the paint afterwards.

[0101] In the present invention, the contact time between the treatment liquid of the present invention and the metal plate is, for example, in the case of an immersion method, wherein the metal plate is immersed in the treatment liquid of the present invention. Time means. In the case of the spray method, it means the time during which the treatment liquid of the present invention is sprayed on the surface of the metal plate.

 [0102] By such a method, the treatment liquid of the present invention is brought into contact with the surface of the metal plate, and the surface chemical conversion treatment layer can be self-deposited on the surface of the metal plate.

 Then, it is washed with water.

 The method of washing with water is not particularly limited, but can be performed by, for example, a known dipping method or spray method. The washing temperature (the temperature of the washing water) is not particularly limited and may be a commonly applied temperature, but it is preferably 5 to 60 ° C, more preferably 15 to 40 ° C. This is because the cleaning efficiency is high at such a temperature.

 As washing water used for washing, drain water, industrial water, brine, and deionized water can be suitably used!

 Also, the cleaning time is not particularly limited. For example, in the case of an immersion method or a spray method, 0.1 to 10 seconds is preferable, and 1 to 5 seconds is more preferable. If the washing time is too short, the excessive soluble reactive treatment liquid component remaining on the surface of the metal plate may not be sufficiently removed, and a surface chemical conversion treatment layer having excellent corrosion resistance may not be obtained. In addition, even if the washing time is too long, no improvement in the performance of the surface chemical conversion treatment layer obtained can be seen, and it is also preferable from the viewpoint of operation efficiency in the line.

 [0103] Note that this cleaning time means, for example, the time during which the metal plate is immersed in washing water in the case of the immersion method. Moreover, in the case of the spray method, it means the time during which flush water is sprayed on the surface of the metal plate.

 [0104] After such washing with water, the surface is preferably dried. When removing only adhering water, physical removal such as air drying or air blow may be used. In order to make the formed surface chemical conversion treatment layer firmly adhere to the surface of the metal plate and to make it chemically stable, a heat drying treatment is effective. In this case, the heating conditions are preferably calorie heat drying so that the maximum temperature (PMT) of the surface of the metal plate on which the surface chemical conversion treatment layer is formed is 30 to 250 ° C. More preferably, the temperature is 40 to 150 ° C.

[0105] Further, the method of bringing the treatment liquid of the present invention into contact with the surface of the metal plate as the cathode and electrolytically depositing the surface chemical conversion treatment layer on the surface of the metal plate is not particularly limited, and is known electrolysis. The law can be applied. For example, electrolytic deposition can be performed by using the metal plate as a cathode and applying a current of 0.05 to 50 AZdm ² for 0.2 to LO seconds. This current value is 0. 5~ 20AZdm ² is it is preferred instrument 1: more preferably LOAZdm ^2. If this current value is too low, the formation (precipitation) rate of the surface chemical conversion treatment layer tends to be slow. Also, if this current value is too high, the formation (deposition) efficiency of the surface chemical conversion treatment layer with respect to the amount of electricity will decrease, and if it becomes uneconomical, the thickness of the surface chemical conversion treatment layer will tend to be difficult to be uniform. . Moreover, the preferable range of energization time is 0.5 to 5 seconds.

 Further, the counter electrode is not particularly limited as long as it does not dissolve in the treatment liquid of the present invention in such electrolytic treatment. For example, platinum or a platinum-coated metal, various stainless steels, or carbon can be used.

 [0106] By such a method, the surface chemical conversion treatment layer can be electrolytically deposited on the surface of the metal plate by bringing the treatment liquid of the present invention into contact with the surface of the metal plate as the cathode.

 And after this, it is washed with water.

 As the water washing method, the method described in the method of bringing the treatment liquid of the present invention into contact with the surface of the metal plate and self-depositing the surface chemical conversion treatment layer on the surface of the metal plate can be applied.

 The same applies when drying after washing with water.

 [0107] The two methods described above, that is, the treatment solution of the present invention is brought into contact with the surface of the metal plate, the surface chemical conversion treatment layer is self-deposited on the surface of the metal plate, and then washed with water. A method for forming a surface chemical conversion treatment layer, and a surface of the metal plate used as a cathode is contacted with the treatment liquid of the present invention, and the surface chemical conversion treatment layer is electrolytically deposited on the surface of the metal plate, and then washed with water. In the method for forming the surface chemical conversion treatment layer, the temperature of the treatment liquid of the present invention is not particularly limited as long as the metal plate and the treatment liquid of the present invention react with each other, but is 5 ° C to 70 ° C. Preferably there is. More preferably, the temperature is 30 to 70 ° C, more preferably 40 to 60 ° C, and even more preferably 30 to 55 ° C. This is because at such a temperature, an appropriate reaction rate can be maintained, energy efficiency is further increased, and cost disadvantages are unlikely to occur.

[0108] By the method for producing a chemical conversion-treated metal sheet of the present invention, the chemical conversion-treated metal sheet of the present invention. In the chemical conversion treatment metal plate of the present invention, the total amount of Zr, Ti, Hf and Si elements contained in the surface chemical conversion treatment layer is 5 to 50 mgZm ² per unit area of the metal plate. In the method for producing a chemical conversion-treated metal sheet of the present invention as described above, it is adjusted to change the concentration, temperature, and line speed of the surface chemical conversion solution in such a range. That is, the higher the concentration of the surface chemical conversion treatment liquid, the higher the temperature, and the slower the line speed, the higher the total amount of the elements contained in the surface chemical conversion treatment layer.

 [0109] In the method for producing a chemical conversion treated metal plate of the present invention, the mechanism by which the surface chemical conversion treated layer is deposited on the surface of the metal plate is considered as follows. First, the surface of the metal plate is etched by the acid component (b) contained in the treatment liquid of the present invention. As a result, the pH at the interface between the surface of the metal plate and the treatment liquid of the present invention locally increases, and the compound (a), which has been dissolved in the treatment liquid of the present invention (a), and further fits. Metal plate force such as a steel plate, etc. The metal ions that have been eluted dissolve only in the treatment liquid of the present invention at the interface, and an unbalanced state occurs. The insoluble complex (compound etc.) formed at this time is considered to precipitate on the surface of the metal plate to form a surface chemical conversion treatment layer.

 [0110] The component of the deposited film (surface chemical conversion treatment layer) obtained in this way is not mainly speculated, but is mainly the hydroxide or acid of compound (a). Metal plate strength of zinc-based plated steel plates, etc. It is considered that the dissolved zinc oxides or oxides such as zinc are in the form. In addition, in the case of a combination that generates an insoluble salt with the cation of the metal-ion acid component (b) of the compound (a), the deposited film (surface chemical conversion treatment layer) is a mixture of the insoluble salt and hydroxide. It is thought that it may become the form which I did.

 [0111] The chemical conversion-treated metal sheet of the present invention can be manufactured by such a method of manufacturing a chemical conversion-treated metal sheet of the present invention.

 [0112] Next, a method for producing the upper coated metal sheet of the present invention will be described.

 The manufacturing method of the upper coated metal sheet of the present invention includes the step of forming the resin layer on the upper surface of the surface chemical conversion treatment layer in addition to the method of manufacturing the chemical conversion treatment metal sheet of the present invention. It is.

[0113] The material of the resin layer is the same as described above. For example, from the group consisting of acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin and polyolefin resin An aqueous treatment agent containing at least one selected is applied by a known method, for example, a dipping method, a spray method, a roll coating method, an air spray method, an airless spray method, etc., and then dried to form. be able to.

 [0114] The aqueous treatment agent used here is 20 to 97% by mass of at least one selected from the group consisting of acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin and polyolefin resin, An aqueous treatment agent containing 2 to 50% by mass of silica sol and 1 to 30% by mass of aqueous wax is preferable. In this case, fingerprint resistance and corrosion resistance are particularly well-balanced.

 [0115] The resin layer preferably includes at least two layers of a non-chromate primer coating layer and a top coat coating layer.

 [0116] Here, as the non-chromate primer coating, a non-chromate primer coating which does not contain a chromate type anti-fouling pigment can be used.

 In addition, the top coat paint is not particularly limited, and can be formed using a normal coating top coat.

[0117] There are no particular limitations on the method of forming the layer having both of these strengths and the non-chromate primer coating strength, and the layer composed of the top cord coating, and a commonly used roll coat method, air spray method, airless spray method, etc. should be used. Can do.

 The baking and drying conditions of the non-chromate primer paint and top coat paint are not limited.For example, a layer and top coat that can also be used as a non-chromate primer paint by treating at 130 to 250 ° C for 10 seconds to 5 minutes. It is possible to form a layer having a coating power.

[0118] With the method for producing an upper layer coated metal sheet of the present invention, the upper layer coated metal sheet of the present invention can be produced.

[0119] Further, the present invention is a chemical conversion treated metal plate produced by the method for producing a chemical conversion treated metal plate of the present invention.

 Moreover, this invention is an upper layer covering metal plate manufactured by the manufacturing method of the upper layer covering metal plate of this invention.

[0120] The chemical conversion treatment metal plate of the present invention and the upper coated metal plate of the present invention may have the surface chemical conversion treatment layer on one side or both sides of the metal plate. Depending on the application You can select single-sided or double-sided. The same applies to the resin layer in the upper coated metal sheet of the present invention.

 Furthermore, in the manufacturing method of the chemical conversion treatment metal plate of the present invention and the manufacturing method of the upper coated metal plate of the present invention, the surface chemical conversion treatment layer may be formed on one side or both sides of the metal plate. . One side or both sides can be selected according to the application. The same applies to the resin layer in the method for producing an upper coated metal sheet of the present invention.

 Example

 [0121] The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.

[0122] 1. Test material

 The following commercially available materials were used as test materials.

 • Hot-dip galvanized steel sheet (GI)

Plate thickness = 0.5mm, basis weight = 90/90 (g / m ² )

 • Electro-galvanized steel sheet (EG)

Plate thickness = 0.5mm, basis weight = 30/30 (g / m ² )

 • Hot-dip galvanized steel sheet (GF) containing 5% aluminum

Plate thickness = 0.5mm, basis weight = 90/90 (g / m ² )

 • Molten 55% zinc alloy plated steel sheet (GL)

Plate thickness = 0.8mm, basis weight = 90/90 (g / m ² )

The weight per unit area indicates the amount per unit area on one and the other main surfaces. For example, 90/90 (g / m ² ) means that each side has a 90 g / m ² finish.

[0123] 2. How to clean zinc-based steel sheets

The surface (both sides) of the above four test materials was treated with a medium alkaline degreasing agent (Fine Cleaner 4336 (registered trademark), manufactured by Nihon Parkerizing Co., Ltd.) to remove dusty oil adhering to the surface. . Here, the alkali degreasing agent was dissolved in tap water so as to have a concentration of 20 gZl, and then adjusted to 60 ° C. before use. The treatment was performed for 20 seconds using a spray. The components of the medium alkaline degreasing agent remaining on the surface were washed with tap water to clean the surface of the test material. [0124] 3. Preparation of surface chemical treatment solution

 Table 1 shows the composition of the surface chemical conversion treatment solution. The concentrations of component (a), component (b), and component (c) were adjusted to be those shown in Table 1. Table 1 also shows the CZA calculation results. In Example 10 and Comparative Examples 5 and 9, liquid phase silica was adjusted to 500 mgZL in terms of Si as component (d). In Example 11 and Comparative Examples 6 and 11, as component (e), polyallylamine (PAA: weight average molecular weight 6000) was adjusted to 200 mgZL. Furthermore, after adjusting to a predetermined pH with ammonia, the solution was treated, and the free fluorine ion concentration (FF) was measured with a fluorine ion meter.

 In Comparative Example 20, a reaction type chromate (Jinchrome 3367 manufactured by Nihon Parkerizing Co., Ltd.) was used to prepare a treatment liquid under a predetermined condition according to the product manual.

[0125] 4. Preparation of chemical conversion treated metal sheet

 4.1 Preparation of chemical conversion treated metal sheet

 The sample material after the cleaning was treated with a surface chemical treatment solution. Table 1 shows the processing conditions (liquid temperature, processing time, processing method) and the types of specimens. Thereafter, the surface was cleaned by spraying 25 ° C. water for 5 seconds, drained using a roll squeezer, and dried at an ultimate plate temperature of 50 ° C. on the surface of the chemical conversion treated metal plate. The amount of component (a) attached was measured by fluorescent X-ray. Table 1 shows the measurement results of the amount of adhesion.

 The processing method is specifically as follows.

 • Immersion treatment

 The zinc-based plating material was immersed in a predetermined metal surface treatment solution and held for a predetermined time. • Spray treatment

A predetermined metal surface treatment solution was treated at a spray pressure of 0.5 kgfZcm ² for a predetermined time.

 , Electrolytic treatment

At the same time as immersion of the test material on the cathode side and immersion in a predetermined metal surface treatment solution, 2. OAZdm ² current was applied to the test material and held for a predetermined time.

[0126] 4.2 Formation of upper-layer coated metal sheet

A part of the above chemical conversion treated metal plate is cut out, and on its upper surface (one side: evaluation surface), 80 parts by mass of urethane resin, 15 parts by mass of silica powder (Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.), aqueous system An aqueous rosin composition containing 5 parts by mass of wax was applied by bar coating. Here, the film thickness was set to 1 μm after drying. Then, it was dried at a reaching plate temperature of 150 ° C. to obtain an upper coated metal plate.

 In this way, in each of the examples and comparative examples, a chemical conversion treated metal plate and an upper coated metal plate treated with the same treatment liquid were produced.

[0127] 5. Evaluation method

 5.1 Stability evaluation of surface chemical treatment solution

 The appearance of the surface chemical conversion treatment liquid was visually observed to confirm the presence or absence of precipitation. The evaluation criteria are as follows.

 ○: No precipitation, processing possible

 X: Precipitation occurs, unsuitable for processing

 The results are shown in Table 1 as liquid stability.

[0128] 5.2 Evaluation of corrosion resistance and coating film adhesion of chemical conversion treated metal sheet

 The corrosion resistance and coating film adhesion of the chemical conversion treated metal plate were evaluated.

 (1) Flat surface corrosion resistance test

 The salt spray test specified in JIS-Z2371 was conducted on each chemical conversion metal plate for 24 hours. And it evaluated by measuring the white-spot generation | occurrence | production area ratio visually. Here, the area ratio of white birch generation area is the percentage of the area of the white birch generation area with respect to the area of the observation area. The evaluation criteria are as follows.

 ◎: White birch occurrence area ratio less than 5%

 ◯: Area ratio of white birch occurrence 5% or more, less than 10%

 △: Area ratio of white birch occurrence 10% or more, less than 50%

 X: White birch occurrence area ratio 50% or more

[0129] (2) Processed part corrosion resistance test

 For each chemical conversion treated metal plate, 5 mm extrusion was carried out with Erichsen, and the salt spray test specified in JISZ2371 was carried out for 24 hours, and the rate of occurrence of white glaze in the processed part was measured visually. . The evaluation criteria are as follows.

◎: White birch occurrence area ratio less than 10% 〇 ： Birch generation area ratio 10% or more, less than 30%

 Δ: Area ratio of white birch occurrence 30% or more, less than 50%

 X: White birch occurrence area ratio 50% or more

[0130] (3) Cut corrosion resistance test

 For each chemical conversion metal plate, a cross cut was made with an NT cutter, a salt spray test specified in JISZ2371 was conducted for 24 hours, and the maximum width of one side of the cut part was measured with a loupe.

. The evaluation criteria are as follows.

 : Less than 3mm

 ○: 3mm or more, 5mm or less

 △: 5mm or more, less than 10mm

 X: 10mm or more

[0131] (4) Paint primary adhesion test

 Each chemical conversion treated metal plate was painted using a paint (Amirac # 1000 (white paint) manufactured by Kansai Paint Co., Ltd.). The coating was performed by bar coating, followed by baking at 140 ° C for 20 minutes to form a 25 m film after drying. The product obtained here is called “Metal plate A after painting”.

 Thereafter, 100 mm grids of 1 mm square were cut into each post-painted metal plate A with an NT cutter, and this was subjected to a peel test using an adhesive tape and evaluated by the number of peeled films. The evaluation criteria are shown below.

 ◎: No peeling

 ◯: Number of peeled 1 or more, less than 10

 △: Number of peeled 11 or more, less than 50

 X: 51 or more peeled

[0132] (5) Paint secondary adhesion test

5.2 (4) Painted metal plate A obtained by painting under the same conditions as in the primary adhesion test was immersed in boiling water for 2 hours and left in a room temperature room for 24 hours. Thereafter, 100 squares of 1 mm square were cut with an NT cutter, and this was subjected to a peel test using an adhesive tape, and evaluated by the number of peeled films. The evaluation criteria were the same as those in 5.2 (4). [0133] 5.3 Evaluation of upper-layer coated metal sheet

 (1) Corrosion resistance on flat surface

 A salt spray test specified in JISZ2371 was performed on each upper-layer coated metal plate for 120 hours. The area ratio of white birch generation was measured visually. The evaluation criteria are as follows.

 ◎: White birch occurrence area ratio less than 5%

 ◯: Area ratio of white birch occurrence 5% or more, less than 10%

 △: Area ratio of white birch occurrence 10% or more, less than 50%

 X: White birch occurrence area ratio 50% or more

[0134] (2) Processed part corrosion resistance

 Extrusion force of 7mm was applied to each upper layer coated metal plate with Erichsen, and the salt spray test specified in JISZ2371 was conducted for 120 hours. The evaluation criteria were the same as those in 5.3 (1).

[0135] (3) Corrosion resistance after alkaline degreasing

After degreasing the alkaline degreasing agent (CL-364S, manufactured by Nihon Parkerizing Co., Ltd.) with 20gZL, 60 ° C, 10 seconds spray, spray pressure 0.5kgZcm ² using each upper layer coated metal plate, spray water washing for 10 seconds, The salt spray test specified in JIS-Z2371 was conducted for 120 hours. The evaluation criteria were the same as those in 5.3 (1).

[0136] (4) Paint primary Eriksen adhesion test

 Each upper layer coated metal plate was painted using a paint (Amirac # 1000 (white paint) manufactured by Kansai Paint Co., Ltd.). The coating was performed by bar coating, followed by baking at 140 ° C for 20 minutes, and after drying, a film with a thickness of 25 m was formed. This is called “Metal plate B after painting”.

 After that, after painting, cut 1mm square, 100 grids with an NT cutter, and extrude it 5mm with an Erichsen tester. And evaluated by the number of peeled coating films. The evaluation criteria are shown below. ◎: No peeling

 ◯: Number of peeled 1 or more, less than 10

△: Number of peeled 11 or more, less than 50 X: Number of peeled pieces 51 or more

 [0137] (5) Paint secondary Eriksen adhesion test

 After coating obtained under the same conditions as in 5.3 (4) Coating primary Erichsen adhesion test, metal plate B was immersed in boiling water for 2 hours and left in a room temperature room for 24 hours. After that, 100 square grids of lm m square were cut with an NT cutter and pushed out 5mm with an Eriksen tester. A peel test using an adhesive tape was performed on the extruded protrusion, and the number of peeled films was evaluated. The evaluation criteria were the same as those in 5.3 (4).

 [0138] (6) Corrosion resistance after painting

 5.3 (4) After coating, scratches that reach the test material are placed on the coating film of the metal plate obtained by painting under the same conditions as in the primary Erichsen adhesion test, and are specified in JIS Z2371. A salt spray test was conducted for 240 hours. Then, the cut part was peeled off with the adhesive tape, and the peeling width was measured. The evaluation standard was the coating film peeling width (mm) from the cut part.

 : Less than 3mm

 ○: 3mm or more, 5mm or less

 △: 5mm or more, less than 10mm

 X: 10mm or more

 [0139] (7) Fingerprint resistance

 Fingers were pressed against each upper-layer coated metal plate, and the trace state of fingerprints was visually observed to evaluate fingerprint resistance. The evaluation criteria are as follows.

 A: No trace of fingerprints left.

 ○: A trace of fingerprints remains.

 Δ: A trace of a fingerprint remains slightly.

 X: Fingerprint traces remain clear.

[0140] As can be seen from Table 1, when the metal surface treatment was carried out under the predetermined conditions using the surface chemical conversion treatment liquid of the present invention, a high adhesion amount chemical conversion metal plate could be obtained in a short time. . The chemical conversion-treated metal plate thus produced exhibited good corrosion resistance and coating film adhesion, and had the same performance as the general-purpose reaction type chromate treatment of Comparative Example 20. In addition, the upper coated metal plate with a resin film formed on the upper surface of the chemical conversion treated metal plate has good corrosion resistance, paint adhesion, and fingerprint resistance. And had the same performance as the test plate of Comparative Example 20 in which the resin film was formed on the upper layer of the steel plate treated with the general-purpose reaction type chromate. However, Comparative Examples 1 to 19, which are outside the scope of the present invention, did not satisfy the corrosion resistance and coating film adhesion of the chemical conversion treated metal plate, and further the corrosion resistance and paint adhesion of the upper coated metal plate. In Comparative Examples 2 to 6, since component (a), component (b) or component (c) was not added, a sufficient adhesion amount could not be obtained. In Comparative Examples 7 to 9, CZA was 1, the free fluorine ion concentration exceeded 30 mgZL, and a sufficient amount of adhesion was not obtained. Since Comparative Examples 10 to 12 had pH <2, the etching amount of the test material increased, and a sufficient adhesion amount could not be obtained. In Comparative Examples 13 to 19, since pH> —0.02 X (C / A) +6, precipitation occurred in the surface chemical conversion treatment solution, which was inappropriate for metal surface treatment. Even if metal surface treatment is performed, the concentration of component (a) is significantly reduced due to precipitation, so that a sufficient amount of adhesion cannot be obtained.

[0141] [Table 1]

 Table

[0142] [Table 2] One

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Claims

The scope of the claims

 [1] Chemical conversion treated metal plate,

A group force consisting of Zr, Ti, Hf and S, which has at least one compound (a) containing at least one element selected, and has a surface chemical conversion treatment layer formed by auto-deposition or electrolytic deposition on the surface of the metal plate, The chemical conversion treatment metal plate whose total amount of the elements of Zr, Ti, Hf, and Si which a surface chemical conversion treatment layer contains is 5-50 mgZm < ² > per metal plate unit area.

 2. The chemical conversion treated metal plate according to claim 1, wherein the metal plate is a zinc-based plated steel plate.

 [3] An upper-layer coated metal sheet comprising the chemical conversion-treated metal sheet according to any one of claims 1 and 2, and a resin layer on the upper side of the surface chemical conversion-treated layer of the chemical conversion-treated metal sheet.

 4. The upper coated metal sheet according to claim 3, wherein the resin layer is a resin layer having fingerprint resistance.

[5] The upper coated metal sheet according to claim 3 or 4, wherein the resin layer includes at least two layers of a layer having a non-chromate primer coating power and a layer of a top coat coating.

[6] The claim 3, wherein the resin layer includes at least one selected from the group consisting of acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin and polyolefin resin. The upper coated metal sheet described in 5!

[7] The upper coated metal sheet according to any one of [3] to [6], wherein the thickness of the resin layer is 0.1 to 5 μm.

 [8] A surface chemical treatment liquid for metal plate surface treatment,

 A group force of Zr, Ti, Hf and S, and at least one of the compounds (a) containing at least one selected element;

 Hydrofluoric acid, nitric acid, sulfuric acid and their salt strength group power at least one selected from the acid component (b),

 At least one compound (c) containing at least one element selected from the group consisting of Fe, Mn, Ni, Co, Ag, Mg, Al, Zn, Cu and Ce;

 Containing

 Free fluoride ion concentration is 1-30mgZL,

Of the elements of Fe, Mn, Ni, Co, Ag, Mg, Al, Zn, Cu and Ce in the compound (c) CZA which is a ratio of the total mass concentration C and the total mass concentration A of the elements of Zr, Ti, Hf and Si in the compound (a) is 1 to 200,

 pH is 2.0 or more, and

 Meet pH≤-0. 02 X (CZA) +6,

 A surface chemical conversion treatment solution for self-depositing a surface chemical conversion treatment layer by being in contact with the surface of the metal plate, or electrolytically depositing a surface chemical conversion treatment layer by being in contact with the surface of the metal plate as a cathode.

 [9] The surface chemical conversion treatment solution according to claim 8, wherein the compound (a) and the compound (c) are at least one selected from the group consisting of organic complex compounds, fluoride complexes, sulfates, and nitrates. .

 [10] The content of the compound (a) is 0.01 to LOgZl in the amount of the element in the compound (a),

 The content of the acidic component (b) is 0.05 to 200 gZl.

 The surface chemical conversion treatment liquid according to claim 8 or 9.

[11] The method according to claim 8, further comprising Si-containing additive (d), wherein the content is 0.02 to 20 gZl in terms of the amount of Si element in Si-containing additive (d). The surface chemical conversion treatment liquid according to any one of the above.

 [12] Further, the organic compound (e) having an amino group is contained in an amount of 0.01 to 20 gZl.

1. The surface chemical conversion treatment liquid according to 1 above.

[13] The above-mentioned organic compound (e) strength buramine, polybulamine, allylamin, diarylamine, polyallylamine, polyamine polyamide, ammine-modified phenol resin, ammine-modified polyvinyl

13. The surface chemical conversion treatment liquid according to claim 12, which is at least one selected from the group force consisting of sulfonol and derivatives thereof.

[14] A method for producing a chemical conversion-treated metal plate, wherein the surface chemical conversion treatment solution according to any one of claims 8 to 13 is used to form a non-coating-type surface chemical conversion treatment layer on the surface of the metal plate.

[15] The surface chemical conversion liquid according to any one of claims 8 to 13 is brought into contact with the surface of the metal plate.

The surface chemical conversion treatment layer is self-deposited on the surface of the metal plate, and then washed with water.

14. A method for producing a chemical conversion treated metal plate according to 14.

[16] The surface chemical conversion treatment liquid according to any one of claims 8 to 13 is brought into contact with the surface of the metal plate as a cathode, and a surface chemical conversion treatment layer is electrolytically deposited on the surface of the metal plate, and then 16. The method for producing a chemical conversion-treated metal sheet according to claim 15, wherein the metal sheet is washed with water.

[17] The surface chemical conversion treatment solution at a temperature of 30 to 70 ° C. is brought into contact with the surface of the metal plate for 0.5 to 20 seconds, and Zr in the compound (a) is brought into contact with the surface of the metal plate. The method for producing a chemical conversion treated metal sheet according to any one of claims 14 to 16, wherein a surface chemical conversion treatment layer of 5 to 50 mgZm ² is formed in a total amount of elements of Ti, Hf and Si.

[18] The method for producing a chemical conversion treated metal plate according to any one of claims 14 to 17, further comprising a step of forming the resin layer on an upper surface of the surface chemical conversion treatment layer. Production method.

 [19] A chemical conversion-treated metal sheet produced by the method for producing a chemical conversion-treated metal sheet according to any one of claims 14 to 17.

 [20] The upper coated metal sheet produced by the method for producing an upper coated metal sheet according to claim 18.