JP2001011645A - Organic-coated steel sheet excellent in corrosion resistance and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a harmless steel sheet good in corrosion resistance by providing a galvanized or Al plated steel sheet with a 1st layer film contg. oxide grains and phosphoric acid and/or a phosphoric compd., and in which film thickness or the total coating weight of both is specified and a 2nd layer film of a specified film thickness composed of an organic polymer resin having an OH group and/or a COOH group as a substrate resin. SOLUTION: The surface of a galvanized steel sheet or an aluminum plated steel sheet is provided with, as a 1st film, a multiple oxide film contg. oxide grains and phosphoric acid and/or a phosphoric compd., in which film thickness is controlled to 0.005 to 3 μm or the total coating weight of the oxide grains and the phosphoric acid and/or a phosphoric compd. expressed in terms of P2O5 is controlled to 6 to 3600 mg/m2, and the upper part is provided with, as a 2nd layer film, an organic film of 0.1 to 5 μm film thickness composed of an organic polymer resin having an OH group and/or a COOH group as a substrate resin. Preferably, the organic film of 0.1 to 5 μm film thickness contg. 1 to 100 pts.wt. inorganic rust preventive pigment to 100 pts.wt. of the substrate resin is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic-coated steel sheet most suitable for use in automobiles, home appliances, building materials, and the like. Environmentally-friendly surface treatment that does not contain any heavy metals such as chromium, lead, cadmium, and mercury that are harmful to the environment and humans during production and in products, in order to adapt to environmental issues such as volatilization and elution of harmful substances from products. It relates to a steel plate.

[0002]

2. Description of the Related Art Steel sheets for home appliances, building materials, and automobiles have been used to improve the corrosion resistance (white rust resistance, red rust resistance) on the surface of a zinc-based steel sheet or an aluminum-based steel sheet. A steel sheet that has been subjected to chromate treatment with a treatment liquid containing chromic acid, dichromic acid or salts thereof as a main component is widely used. This chromate treatment is an economical treatment method that has excellent corrosion resistance and can be performed relatively easily.

[0003] Chromate treatment uses hexavalent chromium, which is a pollution control substance. This hexavalent chromium is treated in a closed system in the treatment process, is completely reduced and recovered, and is not released to nature. In addition, since the chromium elution from the chromate film can be reduced to almost zero by the sealing action of the organic film,
Practically, the environment and the human body are not polluted by hexavalent chromium. However, due to recent global environmental issues,
There is a growing movement to voluntarily reduce the use of heavy metals, including hexavalent chromium. Further, in order to prevent the environment from being polluted when dumping shredder dust of waste products, there has been a movement to minimize or reduce heavy metals in products as much as possible.

[0004] In view of the above, in order to prevent the generation of white rust on a galvanized steel sheet, a number of pollution-free treatment techniques not based on chromate treatment have been proposed. Among them, several methods using an organic compound or an organic resin have been proposed, and examples thereof include the following methods.

(1) A method using tannic acid (for example,
(2) A method of using a thermosetting paint in which an epoxy resin, an amino resin and tannic acid are mixed (for example, JP-A-63-971).
(0581) (3) A method using a mixed composition of an aqueous resin and a polyhydric phenol carboxylic acid (for example, JP-A-8-325760)
(4) A surface treatment method of applying an aqueous solution of a hydrazine derivative to the surface of a tin or zinc iron plate (for example, Japanese Patent Publication No.
No. 27694, No. 56-10386)

(5) A method using a rust inhibitor containing an amine addition salt obtained by adding an amine to a mixture of acylsarcosine and benzotriazole (for example, Japanese Patent Application Laid-Open No.
130284) (6) A method using a treating agent obtained by mixing a heterocyclic compound such as a benzothiazole compound and tannic acid (for example, JP-A-57-198267). (7) An organic compound containing a hydroxyl group-containing monomer as a copolymerization component A method using a composition for surface treatment comprising a resin and a phosphoric acid compound of phosphoric acid and metal (for example, JP-A-9-208)
No. 859, JP-A-9-241856)

[0007]

However, these prior arts have the following problems. First, all of the above methods (1) to (4) have a problem in corrosion resistance and the like. That is, the method (1) is insufficient in corrosion resistance and cannot provide a uniform appearance after the treatment. In addition, the method (2) is particularly suitable for forming a thin film (0.1 to 5 μm) directly on a zinc-based or aluminum-based plating surface.
m) is not intended to form a rust-preventive film. Therefore, even when applied in a thin film form to a zinc-based or aluminum-based plating surface, a sufficient anticorrosion effect cannot be obtained. In addition, the method (3) also has insufficient corrosion resistance.

Further, the method (4) is not applied to a zinc-based or aluminum-based steel sheet, and even if applied to a zinc-based or aluminum-based steel sheet, the obtained film has a network structure. It does not have sufficient barrier properties due to lack of corrosion resistance, and therefore has insufficient corrosion resistance. Also, Japanese Patent Publication No. 53-23772
And JP-B-56-10386, in which a water-soluble polymer compound (polyvinyl alcohol, maleic ester copolymer, acrylate copolymer, etc.) is mixed with an aqueous solution of a hydrazine derivative in order to improve the uniformity of the film. However, a simple mixture of an aqueous solution of a hydrazine derivative and a water-soluble polymer compound does not provide sufficient corrosion resistance.

Further, the methods (5) and (6) are not aimed at forming a rust-preventive film on the surface of a zinc-based or aluminum-based plated steel sheet in a short time.
Even if a treating agent is applied to the surface of the plated steel sheet, excellent corrosion resistance cannot be obtained because there is no barrier to corrosion factors such as oxygen and water. In the method (6), as an additive, a resin (epoxy resin, acrylic resin, urethane resin, nitrocellulose resin, vinyl chloride resin, etc.)
However, a simple mixture of a heterocyclic compound such as a benzothiazole compound and a resin cannot provide sufficient corrosion resistance. The method (7) relates to a technique for forming a single-layer film composed of an organic resin and a phosphoric acid-based inorganic component. However, such a single-layer film alone has insufficient barrier properties. Therefore, sufficient corrosion resistance cannot be obtained.

In any of the above methods (1) to (7), practical conditions such as performing alkaline degreasing at a pH of about 9 to 11 by spraying or the like to remove oil applied to the surface by press working or the like. However, there is a problem that the film is peeled or damaged by alkali degreasing, and the corrosion resistance cannot be maintained. Therefore, these methods are not practically suitable as methods for forming a rust preventive film.
Therefore, an object of the present invention is to solve such problems of the prior art, and does not include heavy metals such as hexavalent chromium in a film,
It is an object of the present invention to provide an organic-coated steel sheet which is safe and harmless even in the manufacturing process and in use, and has excellent corrosion resistance.

[0011]

Means for Solving the Problems As a result of intensive studies by the present inventors to solve the above-mentioned problems, a specific composite oxide was formed on the surface of a zinc-based steel sheet or an aluminum-based steel sheet as a first layer film. By forming an organic film having a specific organic polymer resin as a basic resin as a second layer film thereon, it is further preferable to add an appropriate amount of a specific rust inhibitor to the organic film. It has been found that by blending, it is possible to obtain an organic-coated steel sheet which is non-polluting and extremely excellent in corrosion resistance without performing a chromate treatment which may adversely affect the environment and the human body. The present invention has been made based on such knowledge, and the characteristic configuration thereof is as follows.

[1] A (α) oxide fine particle and (β) phosphoric acid and / or a phosphoric acid compound are contained as a first layer film on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet, A composite oxide film having a thickness of 0.005 to 3 μm or a total adhesion amount of the above component (α) and the above component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ^2; Excellent in corrosion resistance, characterized in that the second layer film has an organic film having a thickness of 0.1 to 5 μm using an organic polymer resin (A) having an OH group and / or a COOH group as a base resin. Organic coated steel sheet.

[2] As a first layer film, (α) oxide fine particles and (β) phosphoric acid and / or a phosphoric acid compound are contained on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet; A composite oxide film having a thickness of 0.005 to 3 μm or a total adhesion amount of the above component (α) and the above component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ^2; As the second layer coating, an organic polymer resin (A) having an OH group and / or a COOH group is used as a base resin, and an inorganic rust preventive pigment (a) is added to 100 parts by weight (solid content) of the base resin. An organic coated steel sheet having excellent corrosion resistance, comprising an organic film having a thickness of 0.1 to 5 μm containing 1 to 100 parts by weight (solid content).

[3] As a first layer film, (a) oxide fine particles and (β) phosphoric acid and / or a phosphoric acid compound are contained on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet; A composite oxide film having a thickness of 0.005 to 3 μm or a total adhesion amount of the above component (α) and the above component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ^2; As the second layer coating, an organic polymer resin (A) having an OH group and / or a COOH group is used as a base resin, and the solid lubricant (b) is added in an amount of 1 to 100 parts by weight (solid content) of the base resin. An organic coated steel sheet having excellent corrosion resistance, characterized by having an organic film containing 80 parts by weight (solid content) and having a film thickness of 0.1 to 5 μm.

[4] As a first layer film, (α) oxide fine particles and (β) phosphoric acid and / or a phosphoric acid compound are contained on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet; A composite oxide film having a thickness of 0.005 to 3 μm or a total adhesion amount of the above component (α) and the above component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ^2; As a second layer coating, an organic polymer resin (A) having an OH group and / or a COOH group is used as a base resin, and an inorganic rust preventive pigment (a) is added to 100 parts by weight (solid content) of the base resin. Excellent corrosion resistance characterized by having an organic film having a thickness of 0.1 to 5 μm containing 1 to 100 parts by weight (solid content) and 1 to 80 parts by weight (solid content) of the solid lubricant (b). Organic coated steel sheet.

[5] In the organic coated steel sheet according to any one of the above [1] to [4], the inorganic rust preventive pigment (a) in the organic film is selected from a silica compound, a phosphate and a calcium compound. An organically coated steel sheet having excellent corrosion resistance, characterized in that it is at least one kind. [6] The organic coated steel sheet having excellent corrosion resistance, wherein the inorganic rust preventive pigment (a) in the organic film is ion-exchanged silica. [7] The organic coated steel sheet having excellent corrosion resistance, wherein the inorganic rust preventive pigment (a) in the organic film is fine-particle silica in the organic coated steel sheet according to the above [5].

[8] In the organic coated steel sheet according to the above [5], the inorganic rust preventive pigment (a) in the organic film comprises ion-exchange silica (c) and fine-particle silica (d), ) And fine silica (d) content (solid content)
Wherein the weight ratio (c) / (d) is from 1/99 to 99/1. [9] The organic steel sheet according to the above [5], wherein the inorganic rust preventive pigment (a) in the organic film is zinc phosphate (e) and / or aluminum phosphate (f). Excellent organic coated steel sheet.

[10] In the organic coated steel sheet of the above [5], the inorganic rust preventive pigment (a) in the organic film is composed of zinc phosphate (e) and / or aluminum phosphate (f) and a calcium compound (g). And the weight ratio (e, f) / to the total content (solid content) of zinc phosphate (e) and / or aluminum phosphate (f) and the content (solid content) of calcium compound (g) (G) is 1 / 99-99 / 1, The organic coating steel sheet excellent in corrosion resistance characterized by the above-mentioned. [11] The organic-coated steel sheet according to any of [5], [6] and [8], wherein the ion-exchange silica (c) in the organic film is Ca ion-exchange silica, and has excellent corrosion resistance. Organic coated steel sheet.

[12] The organic-coated steel sheet according to the above [11],
An organic coated steel sheet having excellent corrosion resistance, wherein the Ca ion-exchanged silica has an average particle diameter of 4 μm or less. [13] The organic-coated steel sheet according to the above [11] or [12], wherein C
(a) An organic-coated steel sheet having excellent corrosion resistance, wherein the Ca concentration of ion-exchanged silica is 2 to 8 wt%. [14] The organic coated steel sheet according to any one of [1] to [13], wherein the organic polymer resin (A) having an OH group and / or a COOH group is a thermosetting resin. Excellent organic coated steel sheet.

[15] In the organic coated steel sheet according to any one of the above [1] to [14], the organic polymer resin (A) having an OH group and / or a COOH group is an epoxy resin and / or a modified epoxy resin. Organic coated steel sheet with excellent corrosion resistance. [16] The organic coated steel sheet excellent in corrosion resistance, wherein the component (α) contained in the composite oxide film is silicon oxide in the organic coated steel sheet according to any of [1] to [15]. [17] The organic-coated steel sheet according to the above [16], wherein the primary particle diameter of silicon oxide is 8 nm or less, the organic-coated steel sheet having excellent corrosion resistance. [18] In the organic-coated steel sheet according to the above [16] or [17], the amount of silicon oxide in terms of SiO ₂ contained as the component (α) in the composite oxide film is a weight ratio with respect to the total adhesion amount of the composite oxide film. An organic-coated steel sheet having excellent corrosion resistance, characterized in that the content is 5 to 95 wt%.

[19] The organic coating according to any one of the above [16] to [18]
In the coated steel sheet, the composite oxide film contains the component (α) and
As (β), (α) SiO₂Fine particles of SiO₂Conversion amount
0.01 to 3000 mg / m², (Β) phosphate and
And / or phosphate compound₂O₅0.01-3 in conversion amount
000mg / m²And the components (α) and (β)
Is 6 to 3600 mg / m ²Is
Organic coated steel sheet with excellent corrosion resistance, characterized by:

[20] In the organically coated steel sheet according to any one of the above [1] to [19], the composite oxide film further comprises (γ) M
g, one or two or more metals selected from Ca, Sr, and Ba (including the case where they are included as a compound and / or a composite compound), and the film thickness is 0.00
5 to 3 μm or the total adhesion amount of the component (α), the component (β) in terms of P ₂ O ₅ and the component (γ) in terms of metal is 6
Excellent organic coated steel sheet in corrosion resistance, which is a ~3600mg / ^{m 2.}

[21] In the organically coated steel sheet according to any one of the above [1] to [19], the composite oxide film further comprises (δ) L
i, Mn, Fe, Co, Ni, Zn, Al, La, Ce
And at least one metal selected from the group consisting of a compound and / or a complex compound, and having a film thickness of 0.005 to 3 μm or the component (α) and P ₂ An organically coated steel sheet having excellent corrosion resistance, characterized in that the total adhesion amount of the component (β) in terms of O ₅ and the component (δ) in terms of metal is 6 to 3600 mg / m ² .

[22] In the organically coated steel sheet according to any one of the above [1] to [19], the composite oxide film further comprises (γ) M
g, Ca, Sr, and Ba, one or more metals selected from the group consisting of a compound and / or a complex compound, and (δ) Li, Mn, F
e, Co, Ni, Zn, Al, La, Ce, one or more metals selected from the group consisting of compounds and / or
Or a compound compound is included), and the film thickness is 0.005 to 3 μm or the component (α) and P
The total adhesion amount of the component (β) in terms of ₂ O ₅ , the component (γ) in terms of metal, and the component (δ) in terms of metal is 6
Excellent organic coated steel sheet in corrosion resistance, which is a ~3600mg / ^{m 2.}

[23] In the organically coated steel sheet of the above [20] or [22], the component (γ) contained in the composite oxide film is M
g (including the case where it is contained as a compound and / or a complex compound). An organic-coated steel sheet having excellent corrosion resistance. [24] In the organically coated steel sheet according to the above [21] or [22], the component (δ) contained in the composite oxide film is Ni, Mn (including a case where both are contained as a compound and / or a composite compound). ), Which is one or two selected from the group consisting of:

[25] In the organically coated steel sheet of the above [20],
When the composite oxide film has components (α), (β) and (γ), (α) SiO ₂ fine particles are 0.01% in terms of SiO _2.
3,000 mg / m ² , 0.01 to 3000 mg of (β) phosphoric acid and / or phosphate compound in terms of P ₂ O ₅
/ M ² , (γ) Mg (including the case where it is included as a compound and / or a complex compound) in an amount of 0.1 in terms of Mg.
0.1 to 1000 mg / m ² , and component (α),
(Β) and (γ) in an amount of 6 to 3600
mg / m ² , an organic-coated steel sheet having excellent corrosion resistance.

[26] In the organic-coated steel sheet of the above-mentioned [21] or [24], the composite oxide film has components (α), (β) and (δ), and (α) SiO ₂ fine particles are converted into SiO ₂ equivalents. 0.01 to 3000 mg / m ² , and (β) phosphoric acid and / or a phosphoric acid compound in an amount of 0.01 to 3 in terms of P ₂ O _5.
000 mg / m ² , (δ) Li, Mn, Fe, Co, N
One or more metals selected from i, Zn, Al, La, and Ce (including the case where they are included as a compound and / or a composite compound) in a metal conversion amount of 0.0
1 to 1000 mg / m ² , wherein component (α)
(Β) and (δ) have a total of 6 to 3600
mg / m ² , an organic-coated steel sheet having excellent corrosion resistance.

[27] In the organic-coated steel sheet of the above-mentioned [22] or [24], the composite oxide film comprises the components (α), (β),
As (γ) and (δ), (α) SiO ₂ fine particles
iO 0.01~3000mg ^{/ m} 2 in ₂ equivalent amounts, (beta)
Phosphoric acid and / or a phosphoric acid compound is 0.01 to 3000 mg / m ^{2 in} terms of P ₂ O ₅ , and (γ) Mg (including the case where it is contained as a compound and / or a complex compound) is in terms of Mg. 0.01 to 1000 mg / m ² ,
(Δ) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, one or two or more metals selected from Ce (including those contained as compounds and / or composite compounds) in an amount of 0.01 to 1000 mg in terms of metal.
/ ^{M 2,} containing the component (α), (β), (γ) and ([delta]) excellent organic coating in corrosion resistance, wherein the sum of the coating weight is 6~3600mg / ^{m 2} steel sheet.

[28] In the organic-coated steel sheet of any one of the above [20], [22], [24] to [27], the component (γ) in the composite oxide film is Mg (provided that the compound and / or And the ratio of the component (γ) to the component (α) is the molar ratio of the component (γ) in terms of Mg and the component (α) in terms of SiO ₂ [ Mg / SiO ₂ ]
An organic-coated steel sheet having excellent corrosion resistance, characterized by being in the range of 1/100 to 100/1.

[29] In the organic-coated steel sheet of any one of the above [20], [22], [24] to [28], the component (γ) in the composite oxide film is Mg (provided that the compound and / or And the ratio of the component (β) to the component (γ) is the mole of the component (β) in terms of P ₂ O ₅ and the component (γ) in terms of Mg. Ratio [P ₂ O ₅ / Mg]
An organic-coated steel sheet having excellent corrosion resistance, characterized by being in the range of 1/100 to 100/1.

[30] In the organic-coated steel sheet according to any one of the above [21] to [24] and [26] to [29], the ratio of the component (δ) to the component (α) in the composite oxide film is And the molar ratio [Me / of the component (δ) in terms of metal (in the case of including two or more metals, the total amount thereof) and the component (α) in terms of SiO _2.
SiO ₂ ] in the range of 1/100 to 100/1.

[31] In the organic-coated steel sheet according to any one of [21] to [24] and [26] to [30], the ratio of the component (β) to the component (δ) in the composite oxide film is , P ₂ O ₅ of component (β)
The molar ratio [P ₂ O ₅ ] between the conversion amount and the metal conversion amount Me of the component (δ) (when two or more metals are contained, the total amount thereof).
/ Me] in the range of 1/2 to 2/1. [32] The organic-coated steel sheet according to any one of the above [1] to [31], wherein the composite oxide film further contains an organic resin, and has excellent corrosion resistance.

[33] The surface of the zinc-based steel sheet or the aluminum-based steel sheet is coated with at least (a) 0.001-3.0 mol / L of oxide fine particles, and (b) phosphoric acid and / or a phosphoric acid compound. In terms of P ₂ O ₅
To 6.0 mol / L, followed by drying by heating to form a first layer coating on the surface of the plated steel sheet, (α) oxide fine particles, (β) phosphoric acid and / or Or a phosphoric acid compound, and the film thickness is 0.00
5 to 3 μm or a composite oxide film having a total adhesion amount of the component (α) and the component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ² is formed.
An organic film having a film thickness of 0.1 to 5 μm is formed by applying a coating composition for forming an organic film containing any of the organic film constituents described in [1] to [15] and drying by heating. A method for producing an organically coated steel sheet having excellent corrosion resistance.

[34] The surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet is coated with at least (a) 0.001-3.0 mol / L of oxide fine particles, (b) phosphoric acid and / or a phosphoric acid compound. In terms of P ₂ O ₅
-6.0 mol / L, (c) each metal ion of Mg, Ca, Sr, Ba, a water-soluble ion containing at least one of the metals, a compound containing at least one of the metals, PH 0.5 containing one or more selected from composite compounds containing at least one of the metals in a total amount of 0.001-3.0 mol / L in terms of metal amount of the metal. (A) oxide fine particles, (β) phosphoric acid and / or a phosphoric acid compound, as a first layer coating on the surface of the plated steel sheet by heating and drying after drying. γ) Mg, Ca, Sr,
One or two or more metals selected from Ba (including the case where they are contained as a compound and / or a complex compound), and a film thickness of 0.005 to 3 μm or the above component (α) And the above component (β) in terms of P ₂ O ₅
And the total adhesion amount of the above component (γ) in terms of metal is 6 to 36.
A composite oxide film having a thickness of 00 mg / m ² is formed, and then a coating composition for forming an organic film containing any of the organic film constituents described in the above [1] to [15] is applied thereon. A method for producing an organic coated steel sheet having excellent corrosion resistance, comprising forming an organic film having a thickness of 0.1 to 5 μm by heating and drying.

[35] The surface of the zinc-coated steel sheet or the aluminum-coated steel sheet is coated with at least (a) 0.001 to 3.0 mol / L of oxide fine particles, and (b) phosphoric acid and / or a phosphoric acid compound. In terms of P ₂ O ₅
6.0 mol / L, (d) Li, Mn, Fe, Co, N
i, each of metal ions of Zn, Al, La, and Ce, a water-soluble ion containing at least one of the metals, a compound containing at least one of the metals, and containing at least one of the metals 1 selected from complex compounds
PH of 0.5 to 1.0 containing at least 0.001 to 3.0 mol / L of the metal or two or more species in terms of the metal amount of the metal.
5 and then dried by heating to form a first layer film on the surface of the plated steel sheet, (α) oxide fine particles, (β) phosphoric acid and / or a phosphate compound, and (δ) ) Li, Mn, Fe, Co, Ni, Zn, A
One, two or more metals selected from l, La, and Ce (including the case where they are included as a compound and / or a composite compound), and have a film thickness of 0.005 to 0.005.
3 μm or a composite oxide film having a total adhesion amount of 6 to 3600 mg / m ² of the component (α), the component (β) in terms of P ₂ O ₅ , and the component (δ) in terms of metal is formed. Then, a coating composition for forming an organic film containing any of the organic film components described in the above [1] to [15] is applied to the upper portion thereof, and dried by heating to have a thickness of 0.1. ~
A method for producing an organic-coated steel sheet having excellent corrosion resistance, comprising forming an organic film having a thickness of 5 μm.

[36] The surface of the zinc-based steel sheet or the aluminum-based steel sheet is coated with at least (a) 0.001-3.0 mol / L of oxide fine particles, and (b) phosphoric acid and / or a phosphoric acid compound. In terms of P ₂ O ₅
6.0 mol / L, (c) Mg, Ca, Sr, Ba metal ions, water-soluble ions containing at least one of the above metals, compounds containing at least one of the above metals, One or two or more compounds selected from composite compounds containing at least one of the metals are added in an amount of 0.001 to 3.0 mol / L in terms of the metal amount of the metal,
(D) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, each metal ion of Ce, a water-soluble ion containing at least one of the above metals, a compound containing at least one of the above metals, and a composite compound containing at least one of the above metals. One or two or more of these metals in a total of 0.001-3.0 in terms of the metal amount of the metal.
Mol / L, and then treated with an acidic aqueous solution having a pH of 0.5 to 5 and then heated and dried to form (a) oxide fine particles as a first layer film on the surface of the plated steel sheet;
(Β) phosphoric acid and / or a phosphate compound, and (γ) M
g, Ca, Sr, and Ba, one or more metals selected from the group consisting of a compound and / or a complex compound, and (δ) Li, Mn, F
e, Co, Ni, Zn, Al, La, Ce, one or more metals selected from the group consisting of compounds and / or
Or the case where it is contained as a composite compound), and the film thickness is 0.005 to 3 μm or the above component (α)
And a composite oxide film having a total adhesion amount of 6 to 3600 mg / m ² of the component (β) in terms of P ₂ O ₅ , the component (γ) in terms of metal, and the component (δ) in terms of metal. Is formed, and then a coating composition for forming an organic film containing any of the organic film components described in [1] to [15] above is applied thereon, and dried by heating to obtain a film thickness. 0.1 ~
A method for producing an organic-coated steel sheet having excellent corrosion resistance, comprising forming an organic film having a thickness of 5 μm.

[37] The method according to any one of [33] to [36], wherein the additive component (a) in the aqueous solution for forming a composite oxide film is silicon oxide, and has excellent corrosion resistance. Manufacturing method of organic coated steel sheet. [38] In the production method according to any one of the above [33] to [37],
A method for producing an organically coated steel sheet having excellent corrosion resistance, characterized in that an additive component (b) in an aqueous solution for forming a composite oxide film is ammonium phosphate.

[39] In the production method according to any one of the above [34], [36] to [38], the additive component (c) in the acidic aqueous solution for forming a composite oxide film is a solution containing Mg ions and Mg. A method for producing an organically coated steel sheet having excellent corrosion resistance, characterized in that it is at least one member selected from the group consisting of a compound ion, a compound containing Mg, and a composite compound containing Mg. [40] In the production method according to any one of the above [35] to [39],
Additives in acidic aqueous solution for complex oxide film formation (d)
Are Ni ions, Mn ions, water-soluble ions containing Ni,
Excellent corrosion resistance characterized in that it is at least one selected from water-soluble ions containing Mn, compounds containing Ni, compounds containing Mn, compound compounds containing Ni, and compound compounds containing Mn. Manufacturing method of organic coated steel sheet.

[41] In the method of any one of the above [34], [36] to [38], and [40], the additive component (c) in the acidic aqueous solution for forming the composite oxide film is Mg ion, One or more selected from water-soluble ions containing Mg, compounds containing Mg, and composite compounds containing Mg, and the ratio of the additive component (c) to the additive component (a) is not more than the additive component The molar ratio [Mg / SiO ₂ ] between the amount of Mg in (c) and the amount of SiO _{2 in the} additive component (a) is 1/100 to 100 /.
1. A method for producing an organically coated steel sheet having excellent corrosion resistance, which is characterized by being in the range of 1.

[42] The above [34], [36] to [38], [40], [41]
Wherein the additional component (c) in the acidic aqueous solution for forming a composite oxide film is selected from Mg ions, water-soluble ions containing Mg, compounds containing Mg, and composite compounds containing Mg. One or two or more kinds, and the ratio of the additive component (b) to the additive component (c) is the ratio of the additive component (b) in terms of P ₂ O ₅ and the additive component (c) in terms of Mg. 1/100 to 100 in molar ratio [P ₂ O ₅ / Mg]
/ 1. A method for producing an organic-coated steel sheet having excellent corrosion resistance, characterized by being in the range of / 1.

[43] In the production method according to any one of the above [35] to [42], the ratio of the additional component (d) to the additional component (a) in the acidic aqueous solution for forming the composite oxide film is The molar ratio [Me / SiO ₂ ] of the metal conversion amount Me of the component (d) to the SiO ₂ conversion amount of the additional component (a) is 1/100 to 10
A method for producing an organic-coated steel sheet having excellent corrosion resistance, characterized by being in the range of 0/1.

[44] In the production method according to any one of the above [35] to [43], the ratio of the additive component (b) to the additive component (d) in the acidic aqueous solution for forming the composite oxide film is and characterized in that the _P 2 _{O 5} molar ratio range of _{[P 2} O 5 / Me] 1/2 to 2/1 of a metal equivalent amount Me of equivalent amount and an additive component (d) of the component (b) For producing organic-coated steel sheets with excellent corrosion resistance. [45] In the production method according to any one of the above [33] to [44],
A method for producing an organically coated steel sheet having excellent corrosion resistance, wherein an aqueous solution for forming a composite oxide film further contains an organic resin.

The basic features of the organic coated steel sheet of the present invention are as follows:
(Α) oxide fine particles as a first layer film on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet;
(Β) phosphoric acid and / or a phosphoric acid compound,
More preferably, (γ) one or two or more metals selected from Mg, Ca, Sr, and Ba (including the case where they are included as compounds and / or composite compounds), and / or (δ) Li, Mn, Fe, Co,
Contains one or more metals selected from Ni, Zn, Al, La, and Ce (including the case where they are included as compounds and / or composite compounds) (preferably as main components A) an organic polymer resin (A) having an OH group and / or a COOH group (preferably a thermosetting resin, more preferably an epoxy resin and / or Or a modified epoxy resin) as a base resin.

The composite oxide film as the first layer film has a specific adhesion amount of SiO ₂ fine particles as the component (α) and a specific adhesion of phosphoric acid and / or a phosphoric acid compound as the component (β). It is preferable to include each in an amount. When the composite oxide film further contains the component (γ) and / or the component (δ), SiO ₂ fine particles are used as the component (α), and phosphoric acid and / or
Alternatively, a phosphoric acid compound is contained in a specific adhesion amount, and one or more (magnesium component) selected from Mg, a compound containing Mg, and a composite compound containing Mg as the component (γ) are specified. In terms of the adhesion amount, the component (δ) (particularly preferably, Ni, Mn, a compound containing Ni, a compound containing Mn, a compound containing Ni, Mn
One or more selected from among multiple compounds containing
Is preferably contained in specific adhesion amounts.

Although the mechanism of corrosion prevention by such a two-layer film structure composed of a specific composite oxide film and an organic film is not always clear, the corrosion inhibitory effect of the first layer film of the composite oxide film as described below is not improved. By combining the barrier action of the film-forming resin of the second layer film with the barrier function, it is possible to obtain corrosion resistance comparable to that of a chromate film even though it is a thin film.

Although the mechanism of corrosion prevention of the composite oxide film as the first layer film is not necessarily clear, the dense and hardly soluble composite oxide film acts as a barrier film to block corrosion factors, and to prevent silicon oxide (SiO ₂ Oxide particles such as fine particles) form a stable and dense barrier film together with a metal and phosphoric acid and / or a phosphoric acid compound, and are released from silicon oxide when the oxide fine particles are silicon oxide (SiO ₂ fine particles). It is considered that excellent anticorrosion performance can be obtained by, for example, improving the barrier property by forming basic zinc chloride in a corrosive environment. In addition, phosphoric acid and / or a phosphoric acid compound contribute to the improvement of the denseness of the composite oxide film, and the phosphoric acid component captures zinc ions dissolved by an anodic reaction, which is a corrosion reaction, at a film defect portion, thereby causing poor solubility. It is believed that a zinc phosphate compound forms a precipitation product there.

Further, as described above, the effect of the present invention is that, as described above, a specific amount of SiO ₂ fine particles is deposited as the component (α) of the composite oxide film, and phosphoric acid and / or
Alternatively, it is particularly effective when the phosphoric acid compound is contained in a specific adhesion amount.

The anticorrosion mechanism when the composite oxide film as the first layer film contains the above component (γ) is as follows.
As described above, the dense and hardly soluble composite oxide film acts as a barrier film to block corrosion factors, and the oxide fine particles such as silicon oxide (SiO ₂ fine particles) are mixed with an alkaline earth metal such as Mg and phosphoric acid. And / or forming a stable and dense barrier film with the phosphoric acid compound,
When the oxide fine particles are silicon oxide (SiO ₂ fine particles), the silicate ions released from the silicon oxide form basic zinc chloride in a corrosive environment to improve barrier properties, and the like, and thereby provide excellent anticorrosion performance. Is obtained,
Further, even when a defect occurs in the film, OH ions are generated by the cathode reaction and the interface becomes alkaline, so that Mg ions and Ca ions, which are soluble components of the alkaline earth metal, become Mg (OH) ₂ , Ca (OH) ₂
It is thought to precipitate as a dense, hardly soluble product, block defects, and suppress corrosion reactions. Further, as described above, the phosphoric acid and / or the phosphoric acid compound contribute to the improvement of the denseness of the composite oxide film, and the phosphoric acid component captures zinc ions dissolved by an anodic reaction that is a corrosion reaction at a film defect portion. However, it is considered that a precipitate product is formed there as a hardly soluble zinc phosphate compound. As described above, alkaline earth metal and phosphoric acid and / or
Alternatively, the phosphoric acid compound is considered to exhibit a self-healing action at the film defect.

Further, among the above-mentioned components (γ), when a magnesium component is contained, particularly excellent corrosion resistance can be obtained. This is considered to be because Mg has a lower solubility of hydroxide than other alkaline earth metals and easily forms a hardly soluble salt. In addition, as described above, the effect of the present invention is that, as described above, the component (α) of the composite oxide film has a specific adhesion amount of SiO ₂ fine particles, and the component (β) contains phosphoric acid and / or a phosphoric acid compound. It is particularly remarkable when the magnesium component is contained as the component (γ) in a specific adhesion amount.

The anticorrosion mechanism when the composite oxide film as the first layer film contains the above component (δ) is as follows.
As described above, the dense and hardly soluble composite oxide film acts as a barrier film to block corrosion factors, and oxide fine particles such as silicon oxide (SiO ₂ fine particles) are stable together with metal and phosphoric acid and / or a phosphoric acid compound. To form a dense barrier film, and when the oxide fine particles are silicon oxide (SiO ₂ fine particles), silicate ions released from silicon oxide form basic zinc chloride in a corrosive environment to improve barrier properties. In addition to the above, excellent anticorrosion performance can be obtained, and the above component (δ) can easily form a poorly soluble metal salt with a phosphoric acid component in an alkaline region. As a result, when an OH ion is generated and the environment becomes an alkaline environment, the metal salt blocks the corrosion site and brings about a high barrier effect. it is considered as. Further, as described above, the phosphoric acid and / or the phosphoric acid compound contribute to the improvement of the denseness of the composite oxide film, and the phosphoric acid component captures zinc ions dissolved by an anodic reaction that is a corrosion reaction at a film defect portion. However, it is considered that a precipitate product is formed there as a hardly soluble zinc phosphate compound.

Further, among the above-mentioned components (δ), particularly good corrosion resistance is obtained when a manganese component and / or a nickel component is contained. This is probably because the metal salt formed by the metal component and the phosphoric acid component is particularly difficult to dissolve in an alkaline environment. Further, since the phosphate of the above-mentioned component (δ) is hardly soluble in an alkali region, this component (δ) is also effective in improving the corrosion resistance after alkali degreasing. By combining the composite oxide film containing such a component (δ) with the second layer film, remarkable improvements in corrosion resistance and corrosion resistance after alkali degreasing are recognized as compared with the case of the composite oxide film alone. This is considered to be due to the synergistic effect of the composite oxide film component and the second layer film component exhibiting excellent corrosion resistance and corrosion resistance after alkali degreasing. Further, as described above, the function and effect of the component (α)
Is particularly remarkable when SiO ₂ fine particles are contained in a specific adhesion amount as component (β), phosphoric acid and / or a phosphoric acid compound are contained in a specific adhesion amount as component (β), and component (δ) is contained in a specific adhesion amount. Is obtained. Further, from the viewpoint of the above-mentioned effects, particularly excellent corrosion resistance can be obtained by adding the above component (γ) and component (δ) in combination.

Although the mechanism of anticorrosion of the organic film as the second layer film is not necessarily clear, it is not limited to organic polymer resin (A) having OH group and / or COOH group (preferably thermosetting resin, more preferably epoxy resin). Resin and / or a modified epoxy resin) forms a dense barrier film by reaction with a crosslinking agent. This barrier film has excellent ability to suppress permeation of corrosive factors such as oxygen and OH in the molecule.
It is considered that particularly excellent corrosion resistance is obtained because a strong bonding force with the substrate is obtained by the group or the COOH group.

Further, in the organic coated steel sheet of the present invention, the anticorrosive performance is further enhanced by adding an inorganic rust preventive pigment (a), preferably a specific inorganic rust preventive pigment as described below, to the organic film. . First, in the organic-coated steel sheet of the present invention, an appropriate amount of ion-exchange silica (c) as an inorganic rust-preventive pigment (a) is blended in an organic film composed of the above-mentioned specific organic polymer resin (A). Further, it is possible to obtain more excellent anticorrosion performance (self-healing action at a film defect portion). It is considered that the anticorrosion mechanism obtained by blending the ion-exchanged silica (c) into the specific organic film is as follows.

That is, when cations such as Na ions enter in a corrosive environment, Ca ions and Mg ions on the silica surface are released by ion exchange, and OH ions are generated by a cathode reaction in a corrosive environment. When the pH in the vicinity of the plating interface increases, Ca ions (or Mg ions) released from the ion-exchanged silica become Ca
(OH) ₂ or Mg (OH) ₂ precipitates near the plating interface and blocks defects as a dense and poorly soluble product;
Suppress corrosion reaction. The eluted zinc ions are Ca
The effect of being exchanged with ions (or Mg ions) and fixed on the silica surface is also considered.

Further, in the organic coated steel sheet of the present invention, an appropriate amount of fine-particle silica (b) as an inorganic rust-preventive pigment (a) is blended in the organic film composed of the specific organic polymer resin (A) as described above. Can also improve the corrosion resistance. That is, fine silica having a large specific surface area such as fumed silica or colloidal silica (average primary particle diameter 5 to 50 nm, preferably 5
(20 to 20 nm, more preferably 5 to 15 nm) promotes the formation of dense and stable corrosion products such as basic zinc chloride, and suppresses the generation of zinc oxide (white rust).

Further, in the organic coated steel sheet of the present invention,
By adding ion exchange silica (a) and fine particle silica (b) as inorganic rust preventive pigments (a) in an organic film composed of the specific organic polymer resin (A) as described above, the corrosion resistance is further improved. Is obtained. Ion exchange silica is mainly composed of porous silica and generally has a relatively large particle diameter of 1 μm or more, so that after the release of Ca ions, the rust-preventing effect of silica cannot be expected much.
For this reason, fine particle silica having a large specific surface area such as fumed silica or colloidal silica (primary particle diameter of 5 to 50).
nm, preferably 5 to 20 nm, more preferably 5 to 20 nm.
15 nm) is considered to promote the formation of dense and stable corrosion products such as basic zinc chloride and suppress the formation of zinc oxide (white rust). It is presumed that a particularly excellent anticorrosion effect can be obtained by the composite rust prevention mechanism of the fine particle silica.

Further, in the organic coated steel sheet of the present invention,
Zinc phosphate (e) as an inorganic rust preventive pigment (a) in an organic film made of the above specific organic polymer resin (A)
Also, by adding an appropriate amount of aluminum phosphate (f), particularly excellent anticorrosion performance (self-healing action at a film defect portion) can be obtained. The anticorrosion mechanism obtained by blending zinc phosphate (e) and / or aluminum phosphate (f) into this specific organic film is considered to proceed in the following reaction steps.

[First step]: In a corrosive environment,
Zinc and aluminum, which are plating metals, elute. [Second step]: Zinc phosphate and / or aluminum phosphate undergo a hydrolysis reaction and dissociate into phosphate ions. [Third step]: The eluted zinc ions and aluminum ions undergo a complexing reaction with phosphate ions to form a dense and hardly soluble protective film, which closes a film defect portion,
Suppress corrosion reaction.

Further, in the organic coated steel sheet of the present invention,
Zinc phosphate (e) as an inorganic rust preventive pigment (a) in an organic film made of the above specific organic polymer resin (A)
And / or by adding aluminum phosphate (f) and calcium compound (g) in combination, a further effect of improving corrosion resistance can be obtained. The reason is considered as follows. As described above, the self-healing effect of zinc phosphate and / or aluminum phosphate is triggered by the elution of the plating metal (the first step). Cannot be completely suppressed. On the other hand, by using a calcium compound, which is a metal lower than zinc and aluminum, in combination, preferential elution of calcium, not plating metal, acts as a trigger as described above, thereby corroding without depending on elution of plating metal. The reaction can be suppressed. It is considered that such a mechanism can provide a composite rust preventive effect by the combined use of zinc and / or aluminum phosphate and a calcium compound.

[0060]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention and the reasons for limiting the same will be described below. The zinc-based coated steel sheet as a base of the organic coated steel sheet of the present invention includes a zinc-coated steel sheet, Zn-Ni
Alloy plated steel sheet, Zn-Fe alloy plated steel sheet (electroplated steel sheet and galvannealed steel sheet), Zn-Cr
Alloy plated steel sheet, Zn-Mn alloy plated steel sheet, Zn-C
o alloy plated steel sheet, Zn-Co-Cr alloy plated steel sheet,
Zn-Cr-Ni alloy plated steel sheet, Zn-Cr-Fe alloy plated steel sheet, Zn-Al alloy plated steel sheet (for example, Z
n-5% Al alloy plated steel sheet, Zn-55% Al alloy plated steel sheet), Zn-Mg alloy plated steel sheet, Zn-Al-
Mg alloy plated steel sheets, and zinc-based composite plated steel sheets (eg, Zn—SiO ₂ dispersed plated steel sheets) in which metal oxides, polymers, and the like are dispersed in the plating films of these plated steel sheets can be used.

Further, among the above-mentioned platings, a multi-layer plated steel sheet obtained by plating two or more layers of the same type or different types may be used. In addition, as the aluminum-plated steel sheet serving as the base of the organic-coated steel sheet of the present invention, an aluminum-plated steel sheet, an Al—Si alloy-plated steel sheet, or the like can be used. Further, as the plated steel sheet, a steel sheet surface may be preliminarily subjected to thin plating such as Ni, and then various platings as described above may be applied thereon. As a plating method, any practicable method can be adopted among an electrolysis method (electrolysis in an aqueous solution or electrolysis in a non-aqueous solvent), a melting method, and a gas phase method.

In order to prevent the occurrence of film defects and unevenness when a two-layer film as described later is formed on the surface of the plating film, if necessary, the surface of the plating film is previously subjected to alkaline degreasing, solvent degreasing, A treatment such as a conditioning treatment (an alkaline surface conditioning treatment or an acidic surface conditioning treatment) can be performed. In addition, in order to prevent blackening (a kind of oxidation phenomenon on the plating surface) in the usage environment of organic coated steel sheets,
If necessary, add iron group metal ions (N
A surface conditioning treatment with an acidic or alkaline aqueous solution containing i ions, Co ions, and Fe ions can also be performed. When an electrogalvanized steel sheet is used as a base steel sheet, iron group metal ions (Ni ions, Co ions, Fe ions) are added to an electroplating bath for the purpose of preventing blackening, and these are added to the plating film. 1 ppm metal
The above can be contained. In this case, there is no particular upper limit on the iron group metal concentration in the plating film.

Next, the composite oxide film which is the first layer film formed on the surface of the zinc-based steel sheet or the aluminum-based steel sheet will be described. This composite oxide film is completely different from a conventional alkali silicate-treated film represented by a film composition composed of lithium oxide and silicon oxide, and contains (α) oxide fine particles (preferably SiO ₂ fine particles) and (β ) Phosphoric acid and / or a phosphate compound;
Further, if necessary, one or more metals selected from (γ) Mg, Ca, Sr, and Ba (including the case where they are included as a compound and / or a complex compound), and / or (Δ) Li, Mn, Fe, C
1 selected from o, Ni, Zn, Al, La, and Ce
A complex oxide film containing (preferably containing as a main component) a metal or two or more metals (including the case where the metal is included as a compound and / or a composite compound).

As the oxide fine particles as the component (α), silicon oxide (SiO ₂ fine particles) is particularly preferable from the viewpoint of corrosion resistance. Colloidal silica is most preferable among such silicon oxides. Examples of the colloidal silica include, for example, Snowtex O, Snowtex OS, Snowtex OXS, Snowtex OUP, Snowtex AK, manufactured by Nissan Chemical Industries, Ltd.
Snowtex O40, Snowtex OL, Snowtex OL40, Snowtex OZL (above, acidic solution), Snowtex XS, Snowtex S, Snowtex NXS, Snowtex NS, Snowtex N, Snowtex QAS-25, Snowtex LS
S-35, Snowtex LSS-45, Snowtex LSS-75 (the above is an alkaline solution), Cataloid S, Cataloid SI-350, manufactured by Catalyst Chemical Industry Co., Ltd.
Cataroid SI-40, Cataloid SA (the above is an alkaline solution), Cataloid SN (an acidic solution), Adelaite AT-20-50 manufactured by Asahi Denka Kogyo KK, Adelaite A
T-20N, Adelite AT-300, Adelite AT
-300S (above, alkaline solution), Adelite AT
20Q (acidic solution) or the like can be used.

Among these silicon oxides (SiO ₂ fine particles), those having a particle diameter of 14 nm or less, more preferably 8 nm or less are desirable from the viewpoint of corrosion resistance.
Further, as the silicon oxide, a material obtained by dispersing dry silica fine particles in a coating composition solution can also be used. As the fumed silica, for example, Aerosil 200, Aerosil 3000, Aerosil 300CF, Aerosil 380, etc., manufactured by Nippon Aerosil Co., Ltd. can be used. Is desirable.

As the oxide fine particles, in addition to the above silicon oxides, colloidal solutions of aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, antimony oxide and the like, fine powders and the like can be used. One or more kinds can be used. Preferred coating weight of the corrosion resistance and weldability viewpoint from the component (alpha) is 0.01~3000mg / ^{m 2,} more preferably 0.1 to 1000 mg / ^{m 2,} more preferably 1 to 5
00 mg / m ² .

The phosphoric acid and / or phosphoric acid compound as the component (β) is, for example, one or more of metal salts and compounds thereof such as orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid and metaphosphoric acid. It can be blended as a film component by adding it to the film composition. Further, one or more of organic phosphoric acid and salts thereof (for example, phytic acid, phytate, phosphonic acid, phosphonate and metal salts thereof) may be added to the coating composition. Among them, primary phosphates are preferred from the viewpoint of the stability of the coating composition solution.

Also, when one or more of ammonium phosphate monobasic, ammonium phosphate dibasic, and ammonium phosphate tribasic were added to the coating composition solution, the corrosion resistance tended to be improved. Although the reason is not clear, when these ammonium salts are used, the solution does not gel even if the pH of the coating composition solution is increased. In general, metal salts become insoluble in an alkaline region, and it is considered that, when a film is formed from a film composition solution having a high pH, a compound that is less soluble is generated in a drying process.

Existence of phosphoric acid and phosphoric acid compound in the film
The state is not particularly limited, and it may be crystalline or amorphous.
Whether or not. Also, phosphoric acid, phosphoric acid in the film
There are no special restrictions on the ionicity or solubility of compounds.
No. The above component (β) from the viewpoint of corrosion resistance and weldability
Is preferably P₂O ₅0.01 to 300 in terms of quantity
0mg / m², More preferably 0.1 to 1000 mg /
m², More preferably 1 to 500 mg / m²It is.

It is necessary that at least one of the specific alkaline earth metal components (Mg, Ca, Sr, Ba) as the component (γ) is incorporated in the coating. The form in which the alkaline earth metal is present in the film is not particularly limited, and may be present as a metal or as a compound or a complex compound such as an oxide, a hydroxide, a hydrated oxide, a phosphate compound, and a coordination compound. Good. The ionicity, solubility, and the like of these compounds, hydroxides, hydrated oxides, phosphate compounds, coordination compounds, and the like are not particularly limited.

Among these alkaline earth metal components, it is most preferable to use Mg (magnesium component) in order to obtain particularly excellent corrosion resistance. It is considered that the reason why the addition of Mg most remarkably improves the corrosion resistance is that Mg has a lower solubility of hydroxide than other alkaline earth metals and easily forms a hardly soluble salt. As a method for introducing the component (γ) into the film, a phosphate, a sulfate, a nitrate, a chloride, or the like of Mg, Ca, Sr, or Ba may be added to the film composition. From the viewpoints of corrosion resistance and prevention of deterioration of the film appearance, the preferred amount of the component (γ) is 0.01 to 1000 mg / m ² , more preferably 0.1 in terms of metal amount.
５００500 mg / m ² , more preferably 1-100 mg
A / ^{m 2.}

The specific metal component (L) which is the component (δ)
i, Mn, Fe, Co, Ni, Zn, Al, La, C
e) requires that one or more of these are incorporated in the film. The form in which these metals are present in the film is not particularly limited, and may be present as a metal, or a compound such as an oxide, a hydroxide, a hydrated oxide, a phosphate compound, or a composite compound. The ionicity, solubility, and the like of these compounds, hydroxides, hydrated oxides, and phosphate compounds are not particularly limited.

Among these metal components, it is most preferable to use Mn (manganese component) and / or Ni (nickel component) for obtaining particularly excellent corrosion resistance.
The addition of Mn and / or Ni most effectively improves the corrosion resistance because the metal salt formed by these metal components and the phosphoric acid component has a lower solubility in an alkaline environment than that of other metals. It is considered to be.
As a method for introducing the component (δ) into the film, Li, M
One or more of phosphates, sulfates, nitrates, chlorides, and the like of n, Fe, Co, Ni, Zn, Al, La, and Ce may be added to the coating composition. Preferred adhesion amount of the components from the viewpoint of preventing deterioration in corrosion resistance and film appearance ([delta]) is 0.01 to 1000 / ^{m 2} by metal weight basis, more preferably 0.1 to 500 mg / ^{m 2,} more preferably 1 to 100 mg / m ² . In the present invention, the component (γ) and the component (δ) may be added in combination under the conditions described above.

An organic resin can be further added to the composite oxide film for the purpose of improving the workability and corrosion resistance of the film. As the organic resin, an epoxy resin, a urethane resin, an acrylic resin, an acrylic-ethylene copolymer, an acrylic-styrene copolymer, an alkyd resin, a polyester resin, an ethylene resin, or the like can be used. These can be introduced into the film as a water-soluble resin and / or a water-dispersible resin. Further, in addition to these water-based resins, water-soluble epoxy resins, water-soluble phenol resins, and water-soluble butadiene rubbers (SBR, NBR, M
It is effective to use BR), a melamine resin, a blocked isocyanate, an oxazoline compound or the like as a crosslinking agent.

In the composite oxide film, as an additive for further improving the corrosion resistance, a polyphosphate,
Phosphates (e.g., zinc phosphate, aluminum dihydrogen phosphate, zinc phosphite, etc.), molybdates, phosphomolybdates (e.g., aluminum phosphomolybdate, etc.), organic phosphoric acids and salts thereof (e.g., Phytic acid,
Phytate, phosphonic acid, phosphonate and their metal salts, alkali metal salts, etc.), organic inhibitors (eg, hydrazine derivatives, thiol compounds, dithiocarbamates, etc.), organic compounds (eg, polyethylene glycols, etc.) One or more kinds may be blended.

Further, as other additives, organic coloring pigments (for example, condensed polycyclic organic pigments, phthalocyanine organic pigments, etc.), coloring dyes (for example, organic solvent-soluble azo dyes, water-soluble azo metal dyes, etc.) ), Inorganic pigments (eg, titanium oxide), chelating agents (eg, thiol), conductive pigments (eg, zinc, aluminum,
Metal powders such as nickel, iron phosphide, antimony tin oxide, etc.), coupling agents (eg, silane coupling agents, titanium coupling agents, etc.), melamine
One or more kinds of cyanuric acid adducts can be added.

The composite oxide film contains iron group metal ions (Ni ions, Ni ions, etc.) for the purpose of preventing blackening (a kind of oxidation phenomenon on the plating surface) under the use environment of the organic coated steel sheet.
One or more of Co ions and Fe ions) may be added. Above all, addition of Ni ions is most preferable. In this case, the desired effect can be obtained if the concentration of the iron group metal ion is 1/10000 mol or more with respect to 1 mol of component (γ) or 1 mol of component (δ) in terms of the amount of metal in the treatment composition. Can be The upper limit of the iron group ion concentration is not particularly limited, but it is preferable that the upper limit does not affect the corrosion resistance as the concentration increases.

The thickness of the composite oxide film is 0.005 to 3 μm.
m, preferably 0.01 to 2 μm, more preferably 0.1 μm.
The thickness is 1 to 1 μm, more preferably 0.2 to 0.5 μm. When the thickness of the composite oxide film is less than 0.005 μm, the corrosion resistance is reduced. On the other hand, when the film thickness exceeds 3 μm, conductivity such as weldability is reduced. In the case where the composite oxide film is defined by the adhesion amount, the total adhesion amount of the component (α) and the component (β) in terms of P ₂ O ₅ , and the composite oxide film has the components (γ) and And / or when the component (δ) is contained, the total adhesion amount including these metal conversion amounts is 6
３3600 mg / m ² , preferably 10-1000 mg
/ ^{M 2,} more preferably 50 to 500 mg / ^{m 2,} particularly preferably 100 to 500 mg / ^{m 2,} most preferably suitable to be 200 to 400 mg / ^{m 2.}
If the total adhesion amount is less than 6 mg / m ² , the corrosion resistance is reduced. On the other hand, if the total adhesion amount is more than 3600 mg / m ² , the conductivity is reduced and the weldability and the like are reduced.

Hereinafter, preferred conditions of the composite oxide film for obtaining particularly excellent performance in the present invention will be described. First, in order to obtain excellent corrosion resistance, silicon oxide is used as the component (α) in the composite oxide film, and its SiO ₂ equivalent amount is 5 to 95% by weight based on the total coating amount of the composite oxide film. It is appropriate to set the range, preferably 10 to 60 wt%. The reason why particularly excellent corrosion resistance is obtained when the amount of silicon oxide is in the above range is not necessarily clear, but a phosphoric acid component complements the barrier property that cannot be obtained with silicon oxide alone to form a dense film,
Further, it is considered that excellent corrosion resistance is exhibited by the synergistic effect of the respective corrosion inhibiting actions of the phosphoric acid component and silicon oxide.

When the component (γ) and / or component (δ) is further added to the composite oxide film,
The component (α) contains the SiO ₂ fine particles in a specific adhesion amount, and the component (β) contains phosphoric acid and / or a phosphoric acid compound in a specific adhesion amount.
Preferably, Mg (including the case where it is contained as a compound and / or a complex compound) is contained in a specific amount, and the component (δ) is preferably contained in a specific amount.

First, preferable conditions for the SiO ₂ fine particles as the component (α) are as described above. This SiO
₂ The adhesion amount of the fine particles in the film is 0.01 in terms of SiO _2.
３3000 mg / m ² , more preferably 0.1-100
0 mg / m ² , more preferably 1 to 500 mg /
m ² , particularly preferably 5 to 100 mg / m ² . If the adhered amount of SiO ₂ fine particles in terms of SiO ₂ is less than 0.01 mg / m ² , the contribution of the silicon component released from silicon oxide to the corrosion resistance is small, and sufficient corrosion resistance cannot be obtained. On the other hand, the adhesion amount in terms of SiO ₂ is 30
If it exceeds 00 mg / m ² , the conductivity will decrease and the weldability will deteriorate. In order to introduce the component (α) into the film, a silicate sol such as colloidal silica may be added to the film-forming composition. Suitable colloidal silica is as exemplified above.

As described above, there is no particular restriction on the method of introducing the above-mentioned component (β) phosphoric acid and / or a phosphoric acid compound into the film and the form of the component (β) in the film.
In addition, when a magnesium component coexists as a component (γ) in the composite oxide film, the phosphate compound in the film may be in the form of magnesium phosphate phosphate or condensed phosphate. It is. As a method for introducing such a phosphate compound into a film, a phosphate, an organic phosphoric acid and a salt thereof (for example, phytic acid, phytate, phosphonic acid, phosphonate and One or more of these metal salts) can be added.

The adhesion amount of phosphoric acid and / or phosphoric acid compound in the film is 0.01 to 3000 mg in terms of P ₂ O _5.
/ M ² , more preferably 0.1 to 1000 mg / m ² ,
More preferably, the concentration is 1 to 500 mg / m ² . P ₂ O _{5 of} phosphoric acid and / or phosphoric acid compound
If the conversion amount is less than 0.01 mg / m ² , the corrosion resistance is reduced. On the other hand, the adhesion amount in terms of P ₂ O ₅ is 3000 m.
If it exceeds g / m ² , the conductivity of the film will decrease, and the weldability will deteriorate.

The form in which the magnesium component (γ) is present in the film is not particularly limited.
Or oxides, hydroxides, hydrated oxides, phosphate compounds,
It may be present as a compound such as a coordination compound or a complex compound. The ionicity, solubility, and the like of these compounds, hydroxides, hydrated oxides, phosphate compounds, coordination compounds, and the like are not particularly limited. The adhesion amount of this magnesium component in the film is 0.01 to 1000 mg / mg in terms of Mg.
m ^2, more preferably 0.1 to 500 mg / ^{m 2,} yet more preferably be 1 to 100 mg / ^{m 2.} The adhesion amount of magnesium component in terms of Mg is 0.01
If it is less than mg / m ² , the contribution of the magnesium component to the corrosion resistance is small, and sufficient corrosion resistance cannot be obtained. On the other hand, if the amount of adhesion in terms of Mg exceeds 1000 mg / m ² , excess magnesium is present as a soluble component in the film, causing a deterioration in the film appearance.

In order to introduce the magnesium component (γ) into the film, one or more kinds of Mg phosphates, sulfates, nitrates, chlorides and fine particles of magnesium oxide are used to form the film. What is necessary is just to add to a composition. In particular,
Since the composite oxide film of the present invention contains a phosphoric acid component as a component, a phosphate such as magnesium phosphate may be added to the treatment composition. In this case, the form of magnesium phosphate is not particularly limited, but any form such as orthophosphate, pyrophosphate, tripolyphosphate, phosphite, and hypophosphite is possible.

The form of the metal component (δ) in the film and the method of introducing each metal component into the film are as described above. As described above, the amount of the component (δ) deposited in the film is 0.01 as a metal amount.
１０００1000 mg / m ² , more preferably 0.1-500
mg / m ² , more preferably 1 to 100 mg / m ² , and when the adhesion amount is 0.01 mg / m ² , sufficient contribution to the corrosion resistance of the metal component is not obtained, while sufficient corrosion resistance cannot be obtained. If the amount exceeds 1000 mg / m ² , an excess metal component is present as a soluble component in the coating, causing a deterioration in the appearance of the coating. In addition, as the component (δ), one or two selected from Ni and Mn (including the case where both are included as a compound and / or a composite compound) are particularly preferable from the viewpoint of corrosion resistance.

In order to obtain particularly excellent corrosion resistance when a magnesium component is contained as the component (γ), the magnesium component as the component (γ) and the SiO _{2 as the} component (α) in the composite oxide film are required. the molar ratio of the proportion between the fine particles, and Mg in terms of quantity and in terms of SiO ₂ of the component (alpha) component (gamma) [Mg / SiO _2] 1/100 to 100 /
1, more preferably 1/10 to 10/1, further preferably 1/2 to 5/1. The reason why particularly excellent corrosion resistance is obtained when the ratio between the magnesium component and the SiO ₂ fine particles is in the above range is not necessarily clear, but when the ratio between the magnesium component and the SiO ₂ fine particles is in the above range, It is presumed that the synergistic effect of the respective corrosion inhibiting actions of the silicon component and the magnesium component released from the SiO ₂ fine particles is particularly remarkably exhibited.

From the same point of view, the ratio of phosphoric acid and / or a phosphoric acid compound as the component (β) in the composite oxide film to the magnesium component as the component (γ) is calculated as P of the component (β). A molar ratio [P ₂ O ₅ / Mg] of the converted amount of ₂ O _{5 and the} converted amount of Mg of the component (γ) is 1/100 to 100/1,
More preferably, it is 1/10 to 10/1, and further preferably, it is 1/2 to 2/1. The reason why particularly excellent corrosion resistance is obtained when the ratio of the phosphoric acid and / or the phosphoric acid compound to the magnesium component is in the above range is not necessarily clear. It is presumed that when the ratio is in the above range, the synergistic effect of the respective corrosion inhibiting actions of the phosphoric acid and / or the phosphoric acid compound and the magnesium component is particularly remarkably exhibited.

In order to obtain the most excellent corrosion resistance,
The ratio of the magnesium component as the component (γ) and the SiO ₂ fine particles as the component (α) in the composite oxide film was calculated by the molar ratio between the Mg equivalent amount of the component (γ) and the SiO ₂ equivalent amount of the component (α). 1/100 to 100/1 in a ratio [Mg / SiO ₂ ],
It is more preferably in the range of 1/10 to 10/1, still more preferably in the range of 1/2 to 5/1, and phosphoric acid and / or a phosphoric acid compound as component (β) in the composite oxide film and component (γ). ) Is 1/100 to 100/1 by the molar ratio [P ₂ O ₅ / Mg] between the P ₂ O ₅ equivalent of the component (β) and the Mg equivalent of the component (γ). ,
More preferably, it is 1/10 to 10/1, and further preferably, it is 1/2 to 2/1.

The reason why the most excellent corrosion resistance is obtained when the ratio of the magnesium component, the SiO ₂ fine particles and the phosphoric acid and / or the phosphoric acid compound is in the above-mentioned range is that the above-mentioned respective components have a corrosion inhibiting action. That the synergistic effect is particularly remarkably expressed, and that the film morphology resulting from the reaction with the plating substrate during film formation is optimized,
It is presumed to be due to such factors.

In order to obtain particularly excellent corrosion resistance when the component (δ) is contained, a metal component as the component (δ) and a SiO _{2 as the} component (α) in the composite oxide film are required.
The ratio of the particles to the fine particles is determined by the molar ratio [Me / SiO ₂ ] between the metal equivalent Me of the component (δ) and the SiO ₂ equivalent of the component (α).
1/100 to 100/1, more preferably 1/10 to
It is appropriate that the ratio be in the range of 10/1, more preferably 1/2 to 5/1. The reason why particularly excellent corrosion resistance is obtained when the ratio of the component (δ) to the SiO ₂ fine particles is within the above range is not necessarily clear, but the ratio of the metal component as the component (δ) to the SiO ₂ fine particles is not clear. It is presumed that in the above range, the synergistic effect of the corrosion inhibiting action of each of the silicon component and the metal component released from the SiO ₂ fine particles is particularly prominent.

From the same viewpoint, the ratio of phosphoric acid and / or a phosphoric acid compound as the component (β) in the composite oxide film to the metal component as the component (δ) is calculated as P It is appropriate that the molar ratio [P ₂ O ₅ / Me] of the converted amount of ₂ O _{5 to the} converted amount of metal Me of the component (δ) is 1/2 to 2/1. The reason why particularly excellent corrosion resistance can be obtained when the ratio of phosphoric acid and / or the phosphoric acid compound to the metal component (component (δ)) is within the above range is not necessarily clear, but the solubility of the phosphoric acid component is not clear. Since it changes depending on the ratio between phosphoric acid and the metal, it is considered that the film is particularly excellent when the insolubility of the film is in the above range, and the barrier property of the film becomes higher.

In order to obtain the most excellent corrosion resistance,
Metal component and component (δ) in composite oxide film
SiO which is (α)₂The ratio of the fine particles to the component (δ)
Metal conversion amount Me and SiO of component (α)₂Mole with conversion amount
Ratio [Me / SiO₂] From 1/100 to 100/1, more
Preferably 1/10 to 10/1, more preferably 1 /
Components in the range of 2 to 5/1 and in the composite oxide film
(Β) phosphoric acid and / or a phosphoric acid compound and components
The ratio of the metal component (δ) to the metal component ₂O
₅The molar ratio [P of the conversion amount and the metal conversion amount Me of the component (δ) [P
₂O₅/ Me] is preferably 1/2 to 2/1.
You.

The reason why the most excellent corrosion resistance is obtained when the ratio of the metal component, the SiO ₂ fine particles and the phosphoric acid and / or the phosphoric acid compound is within the above range is that the above-mentioned respective components inhibit the corrosion of each component. It is presumed that the synergistic effect of the action is particularly remarkably exhibited, and that the film morphology resulting from the reaction with the plating substrate during film formation is optimized.

In this composite oxide film, the adhesion amount of the above component (α) in terms of SiO ₂ and the P of the above component (β)
_{When the} composition further contains the component (γ) and / or the component (δ), the total amount of the adhered substances in terms of ₂ O ₅ , and the total amount including the adhered amounts in terms of the metals, is 6 to 3600 m.
g / m ² , more preferably 10 to 1000 mg / m ² ,
More preferably, the concentration is 50 to 500 mg / m ² . If the total coating weight is less than 6 mg / m ² , the corrosion resistance is not sufficient, while the total coating weight is 3600 mg / m ^2.
m ² by weight, the conductivity and weldability are degraded to lower.

Next, an organic film formed as a second layer film on the composite oxide film will be described. As the base resin of the organic film, OH groups and / or COO
An organic polymer resin (A) having an H group is used. Among them, a thermosetting resin is preferable, and an epoxy resin or a modified epoxy resin is particularly preferable. Examples of the organic polymer resin having an OH group and / or a COOH group include:
For example, epoxy resin, polyhydroxy polyether resin, acrylic copolymer resin, ethylene-acrylic acid copolymer resin, alkyd resin, polybutadiene resin, phenol resin, polyurethane resin, polyamine resin, polyphenylene resins and the like of these resins Examples thereof include a mixture of two or more kinds or an addition polymer.

(1) Epoxy resin Epoxy resins include bisphenol A, bisphenol F, novolak, and the like, glycidyl etherified epoxy resin, bisphenol A with propylene oxide,
Epoxy resins to which glycidyl ether has been added by adding ethylene oxide or polyalkylene glycol, and furthermore, aliphatic epoxy resins, alicyclic epoxy resins, polyether epoxy resins, and the like can be used. These epoxy resins desirably have a number average molecular weight of 1500 or more, especially when curing at a low temperature is required. The above epoxy resins can be used alone or in combination of different types.

Examples of the modified epoxy resin include resins obtained by reacting various types of modifiers with an epoxy group or a hydroxy group in the above epoxy resin. For example, an epoxy ester resin obtained by reacting a carboxyl group in a drying oil fatty acid,
Epoxy acrylate resin modified with acrylic acid, methacrylic acid, etc., urethane modified epoxy resin obtained by reacting isocyanate compound, amine-added urethane modified epoxy resin obtained by adding alkanolamine to urethane modified epoxy resin obtained by reacting isocyanate compound with epoxy resin, etc. Can be mentioned.

The above polyhydroxy polyether resin is
A polymer obtained by polycondensing mononuclear or dinuclear phenol or a mixture of mononuclear and dinuclear phenols with an approximately equimolar amount of epihalohydrin in the presence of an alkali catalyst. . Representative examples of mononuclear dihydric phenols include resorcin, hydroquinone, and catechol. Representative examples of dinuclear phenols include bisphenol A. These may be used alone or in combination of two or more. You may.

(2) Urethane resin Examples of the urethane resin include an oil-modified polyurethane resin, an alkyd-based polyurethane resin, a polyester-based polyurethane resin, a polyether-based urethane resin, and a polycarbonate-based polyurethane resin. (3) Alkyd resin Examples of the alkyd resin include oil-modified alkyd resin, rosin-modified alkyd resin, phenol-modified alkyd resin,
Styrenated alkyd resin, silicon-modified alkyd resin,
Acrylic-modified alkyd resins, oil-free alkyd resins, high-molecular-weight oil-free alkyd resins and the like can be mentioned.

(4) Acrylic resin Examples of the acrylic resin include polyacrylic acid and its copolymer, polyacrylic ester and its copolymer, polymethacrylic ester and its copolymer, and polymethacrylic ester. And a copolymer thereof, a urethane-acrylic acid copolymer (or urethane-modified acrylic resin), a styrene-acrylic acid copolymer, and the like.
A resin modified with a phenol resin or the like may be used.

(5) Ethylene resin (polyolefin resin) Examples of the ethylene resin include ethylene-based copolymers such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and carboxyl-modified polyolefin resin; Examples thereof include a saturated carboxylic acid copolymer and an ethylene ionomer. Further, a resin obtained by modifying these resins with another alkyd resin, an epoxy resin, a phenol resin, or the like may be used. (6) Acrylic silicone resin As the acrylic silicone resin, for example, a resin containing a hydrolyzable alkoxysilyl group in a side chain or a terminal of an acrylic copolymer as a main component, and a curing agent added thereto is used. When these acrylic silicone resins are used, excellent weather resistance can be expected.

(7) Fluororesins Fluororesins include fluoroolefin copolymers, for example, monomers such as alkyl vinyl ether, synchroalkyl vinyl ether, carboxylic acid-modified vinyl ester, hydroxyalkyl allyl ether, tetrafluoropropyl There is a copolymer obtained by copolymerizing vinyl ether or the like with a fluorine monomer (fluoroolefin). When using these fluororesins,
Excellent weather resistance and excellent hydrophobicity can be expected.

Further, in order to lower the drying temperature of the resin, the core portion and the shell portion of the resin particles have different resin types or cores made of resins having different glass transition temperatures.
A shell-type water-dispersible resin can be used. In addition, by using a water-dispersible resin having self-crosslinking properties, for example, by providing an alkoxysilane group to the resin particles, a silanol group is generated by hydrolysis of the alkoxysilane during heating and drying of the resin, and a silanol group between the resin particles is formed. Cross-linking between particles utilizing a dehydration condensation reaction of the above can be used. Further, as a resin used for the organic film, an organic composite silicate obtained by compounding an organic resin with silica via a silane coupling agent is also suitable.

In the present invention, it is particularly desirable to use a thermosetting resin in order to improve the corrosion resistance and workability of the organic film. In this case, urea resin (butylated urea resin etc.), melamine resin (butylated melamine resin), butylated urea
Amino resins such as melamine resin and benzoguanamine resin,
A curing agent such as a blocked isocyanate, an oxazoline compound, and a phenol resin can be blended.

Among the organic resins described above, epoxy resins and ethylene resins are preferable in consideration of corrosion resistance, workability, and paintability. In particular, thermosetting resins having excellent barrier properties against corrosion factors such as enzymes. Particularly preferred are epoxy resins and modified epoxy resins. As these thermosetting resins, a thermosetting epoxy resin, a thermosetting modified epoxy resin, an acrylic copolymer resin copolymerized with an epoxy group-containing monomer, a polybutadiene resin having an epoxy group,
Examples thereof include polyurethane resins having an epoxy group, and adducts or condensates of these resins. One of these epoxy group-containing resins can be used alone, or two or more can be used in combination.

In the present invention, it is preferable to further add an inorganic rust preventive pigment (a) to the organic film. Examples of the inorganic rust preventive pigments include ion-exchange silica, silica compounds such as fine particle silica, cerium oxide, aluminum oxide, zirconium oxide, antimony oxide, and polyphosphate (for example,
Aluminum polyphosphate: trade name of TAYKA K manufactured by TAYCA Corporation
-WHITE80, Takeka K-WHITE84, Takeka K-WHITE105, Takeka K-WHITE G10
5, Takeka K-WHITE90), phosphate (eg,
Zinc phosphate, aluminum dihydrogen phosphate, zinc phosphite, etc.), molybdate, phosphomolybdate (eg, aluminum phosphomolybdate, etc.) can be used. Among them, particularly, silica compounds such as ion-exchange silica (c) and fine-particle silica (d), phosphates such as zinc phosphate (e) and aluminum phosphate (f), and calcium compounds (g) The corrosion resistance is particularly good when one or two or more of these are blended.

Inorganic rust preventive pigment (a) in organic resin film
Is 1 to 100 parts by weight (solid content), preferably 5 to 80 parts by weight, based on 100 parts by weight (solid content) of the base resin.
It is appropriate that the amount be 10 parts by weight (solid content), more preferably 10 to 50 parts by weight (solid content). If the amount of the inorganic rust preventive pigment (a) is less than 1 part by weight, the effect of improving the corrosion resistance after alkali degreasing is small, while if the amount is more than 100 parts by weight, the corrosion resistance and the like are undesirably reduced.

The ion-exchanged silica (c) used as the inorganic rust preventive pigment (a) is obtained by fixing metal ions such as calcium and magnesium on the surface of a porous silica gel powder, and releases the metal ions in a corrosive environment. To form a precipitate film. In addition, among these ion-exchanged silicas, Ca
Ion exchange silica is most preferred. Any Ca ion exchange silica can be used, but those having an average particle diameter of 6 μm or less, desirably 4 μm or less are preferable. For example, those having an average particle diameter of 2 to 4 μm can be used. The average particle diameter of Ca ion exchange silica is 6
If it exceeds μm, the corrosion resistance decreases and the dispersion stability in the coating composition decreases.

The Ca concentration in the Ca ion exchange silica is 1 w
It is preferably at least t%, preferably 2 to 8 wt%. If the Ca concentration is less than 1% by weight, the rust prevention effect due to the release of Ca cannot be sufficiently obtained. The surface area, pH and oil absorption of Ca ion exchange silica are not particularly limited. As the above Ca ion exchange silica, W.
R. Grace & Co. SHIELDEX C303 (average particle size 2.5 to 3.5 μm, Ca concentration 3 wt%), SH
IELDEX AC3 (average particle diameter of 2.3 to 3.1 µ)
m, Ca concentration 6 wt%), SHIELDEX AC5
(Average particle diameter 3.8-5.2 μm, Ca concentration 6 wt.
%), SHIELDEX manufactured by Fuji Silysia Chemical Ltd.
(Average particle diameter 3 μm, Ca concentration 6 to 8 wt%), SHI
ELDEX SY710 (average particle size 2.2 to 2.5μ)
m, Ca concentration of 6.6 to 7.5 wt%).

The anticorrosion mechanism when the ion exchange silica (c) is added to the organic film is as described above. In particular, in the present invention, the specific organic polymer resin and the ion exchange silica are complexed. An extremely excellent anticorrosion effect is exhibited by combining the barrier function of the specific organic polymer resin film with the corrosion suppression effect of the ion exchange silica in the cathode reaction section.

When the ion-exchanged silica (c) is used as the inorganic rust preventive pigment (a) in the organic film, the compounding amount is as follows:
1 to 100 parts by weight (solid content) of the base resin
It is appropriate that the amount be 5 parts by weight (solid content), preferably 5 to 80 parts by weight (solid content), and more preferably 10 to 50 parts by weight (solid content). If the amount of the ion-exchanged silica (c) is less than 1 part by weight, the effect of improving corrosion resistance after alkali degreasing is small. On the other hand, if the amount exceeds 100 parts by weight, the corrosion resistance is undesirably reduced.

The fine particle silica (d) used as the inorganic rust preventive pigment (a) may be either colloidal silica or fumed silica. When the colloidal silica is based on an aqueous film-forming resin, for example, Snowtex O, Snowtex N, Snowtex 20, Snowtex 30, manufactured by Nissan Chemical Industry Co., Ltd.
Snowtex 40, Snowtex C, Snowtex S, Cataloid S, Cataloid SI-350, Cataloid SI-40, Cataloid S manufactured by Catalysis Chemical Industry Co., Ltd.
A, Cataloid SN, Adelite AT-20-50, Adelite AT-20N, Adelite AT-300, Adelite AT-300S, Adelite AT20Q manufactured by Asahi Denka Kogyo KK can be used.

When the solvent-based film-forming resin is used as a base, for example, organosilica sol MA-ST-M, organosilica sol IPA-ST, and organosilica sol EG-ST manufactured by Nissan Chemical Industries, Ltd. , Organosilica sol E-ST-ZL, organosilica sol NP
C-ST, organosilica sol DMAC-ST, organosilica sol DMAC-ST-ZL, organosilica sol XBA-ST, organosilica sol MIBK-ST,
OSCAL-1132, OSC manufactured by Catalyst Chemical Industry Co., Ltd.
AL-1232, OSCAL-1332, OSCAL-
1432, OSCAL-1532, OSCAL-163
2. OSCAL-1722 or the like can be used.

In particular, the organic solvent-dispersed silica sol is excellent in dispersibility and more excellent in corrosion resistance than fumed silica. Examples of the fumed silica include, for example, AEROSIL R97 manufactured by Nippon Aerosil Co., Ltd.
1, AEROSIL R812, AEROSIL R81
1, AEROSIL R974, AEROSIL R20
2, AEROSILR805, AEROSIL 13
0, AEROSIL 200, AEROSIL 300,
AEROSIL 300CF or the like can be used.

The fine-particle silica contributes to the formation of a dense and stable zinc corrosion product in a corrosive environment, and the corrosion product is formed densely on the plating surface, thereby suppressing the promotion of corrosion. It is considered possible. From the viewpoint of corrosion resistance, the fine particle silica has a particle diameter of 5 to 50 n.
m, preferably 5 to 20 nm, more preferably 5 to 1 nm.
It is preferable to use a 5 nm one.

When the finely divided silica (d) is used as the inorganic rust-preventive pigment (a) in the organic film, the compounding amount is 1 to 100 parts by weight (solid content) based on 100 parts by weight (solid content) of the base resin. Min), preferably 5 to 80 parts by weight (solid content), more preferably 10 to 30 parts by weight (solid content). If the amount of the fine particle silica (d) is less than 1 part by weight, the effect of improving corrosion resistance after alkali degreasing is small. On the other hand, if the amount is more than 100 parts by weight, corrosion resistance and workability are undesirably reduced.

In the present invention, particularly excellent corrosion resistance can be obtained by adding ion exchange silica (c) and fine particle silica (d) as an inorganic rust preventive pigment (a) in an organic film in combination. That is, by adding the ion-exchanged silica (c) and the particulate silica (d) in combination, a particularly excellent anticorrosion effect can be obtained by a composite rust prevention mechanism of both.

When ion-exchanged silica (c) and fine-particle silica (d) are added in combination as the inorganic rust preventive pigment (a) in the organic film, the compounding amount is based on 100 parts by weight (solid content) of the base resin. The total amount of the ion exchange silica (c) and the fine particle silica (d) is 1 to 100 parts by weight (solid content), preferably 5 to 80 parts by weight (solid content); (C) and particulate silica (d)
Weight ratio (c) / (d) of the blending amount (solid content) of
The ratio is suitably from 1/99, preferably from 95/5 to 40/60, more preferably from 90/10 to 60/40.

If the total amount of the ion-exchanged silica (c) and the finely divided silica (d) is less than 1 part by weight, the effect of improving corrosion resistance after alkali degreasing is small. On the other hand, if the total compounding amount exceeds 100 parts by weight, the coatability and workability deteriorate, which is not preferable. If the weight ratio (c) / (d) of the ion-exchanged silica (c) and the particulate silica (d) is less than 1/99, the corrosion resistance is poor, while the weight ratio (c) / (d) is 9
If it exceeds 9/1, the effect of the composite addition of the ion exchange silica (c) and the fine particle silica (d) cannot be sufficiently obtained.

The zinc phosphate (e) and the aluminum phosphate (f) used as the inorganic rust preventive pigment (a) are not particularly limited in the skeleton of the phosphate ion or the degree of condensation, and may be in the form of a regular salt, It may be any of a hydrogen salt, a monohydrogen salt and a phosphite, and the normal salt includes all condensed phosphates such as polyphosphate in addition to orthophosphate. For example, LF Bosei ZP-DL (trade name, manufactured by Kikuchi Color Co., Ltd.) can be applied as zinc phosphate, and Teika K-WHITE (trade name, manufactured by Teika Co., Ltd.) can be applied as aluminum phosphate. These zinc phosphate (e) and aluminum phosphate (f) dissociate into phosphate ions by hydrolysis in a corrosive environment and form a protective film by causing a complexing reaction with the eluted metal.

When zinc phosphate (e) and / or aluminum phosphate (f) is used as the inorganic rust preventive pigment (a) in the organic film, the compounding amount is based on 100 parts by weight (solid content) of the base resin. On the other hand, the amount is suitably 1 to 100 parts by weight (solid content), preferably 5 to 80 parts by weight (solid content), more preferably 10 to 50 parts by weight (solid content). If the amount of zinc phosphate (e) and / or aluminum phosphate (f) is less than 1 part by weight, the effect of improving the corrosion resistance after alkali degreasing is small. On the other hand, when the blending amount is 10
Exceeding 0 parts by weight is not preferred because the corrosion resistance is reduced.

In the present invention, a calcium compound (g) is used together with zinc phosphate (e) and / or aluminum phosphate (f) as an inorganic rust preventive pigment (a) in an organic film.
, A particularly excellent corrosion resistance can be obtained. That is, by adding zinc phosphate (e) and / or aluminum phosphate (f) and calcium compound (g) in combination, a particularly excellent anticorrosion effect can be obtained by a composite rust prevention mechanism of both.

The calcium compound (g) may be any of calcium oxide, calcium hydroxide and calcium salt, and one or more of these can be used. In addition, the type of calcium salt is not particularly limited, and other than a single salt containing only calcium as a cation such as calcium silicate, calcium carbonate, calcium phosphate,
Double salts containing cations other than calcium and calcium, such as calcium / zinc phosphate and calcium / magnesium phosphate, may be used. The calcium compound elutes preferentially over the plating metal in a corrosive environment, causing a complexing reaction with phosphate ions without triggering the elution of the plating metal to form a dense and hardly soluble protective film, It is thought to suppress the corrosion reaction.

When zinc phosphate (e) and / or aluminum phosphate (f) and a calcium compound (g) are added in combination as the inorganic rust preventive pigment (a) in the organic resin film, the compounding amount of 1 to 100 parts by weight (solid content) in total of zinc phosphate (e) and / or aluminum phosphate (f) and calcium compound (g) based on 100 parts by weight (solid content) of resin Is 5 to 80
Parts by weight (solid content) and the weight ratio (e, f) / of the compounding amount (solid content) of zinc (e) and / or aluminum phosphate (f) and the calcium compound (g)
(G) is 99/1 to 1/99, preferably 95/5 to 4
0/60, more preferably 90/10 to 60/40.

When the total amount of zinc phosphate (e) and / or aluminum phosphate (f) and calcium compound (g) is less than 1 part by weight, the effect of improving corrosion resistance after alkali degreasing is small. On the other hand, if the total amount exceeds 100 parts by weight, the corrosion resistance is undesirably reduced. Also,
If the weight ratio (e, f) / (g) of the compounding amount (solid content) of zinc phosphate (e) and / or aluminum phosphate (f) and calcium compound (g) is less than 1/99, the corrosion resistance is poor, On the other hand, when the weight ratio (e, f) / (g) exceeds 99/1, the effect of the complex addition of zinc phosphate and / or aluminum phosphate (e, f) and the calcium compound (g) is sufficiently obtained. Disappears.

In addition to the various inorganic rust preventive pigments described above, organic phosphoric acids and salts thereof (eg, phytic acid, phytate, phosphonic acid, phosphonate, and phosphonate) may be contained in the organic film as corrosion inhibitors. And an organic inhibitor (eg, a hydrazine derivative, a thiol compound, a dithiocarbamate, or the like).

A solid lubricant (b) can be added to the organic film, if necessary, for the purpose of improving the processability of the film. Examples of the solid lubricant applicable to the present invention include the following, and one or more of these can be used. (1) Polyolefin wax, paraffin wax:
For example, polyethylene wax, synthetic paraffin, natural paraffin, micro wax, chlorinated hydrocarbon, etc. (2) Fluororesin fine particles: For example, polyfluoroethylene resin (polytetrafluoroethylene resin, etc.), polyvinyl fluoride resin, polyvinylidene fluoride Resin, etc.

In addition, fatty acid amide compounds (eg, stearic acid amide, palmitic acid amide,
Methylene bisstearamide, ethylenebisstearamide, oleic amide, esylamide, alkylenebisfatty acid amide, etc., metal soaps (eg, calcium stearate, lead stearate, calcium laurate, calcium palmitate, etc.), metals One or more of sulfides (eg, molybdenum disulfide, tungsten disulfide, etc.), graphite, fluorinated graphite, boron nitride, polyalkylene glycol, and alkali metal sulfate may be used.

Among the above solid lubricants, polyethylene wax, fine particles of fluorine resin (particularly, poly 4
Fluorinated ethylene resin fine particles) are preferred. Examples of the polyethylene wax include Sericust 9615A, Seridust 3715, Seridust 3620, Seridust 3910, and Sanyo Kasei Co., Ltd. manufactured by Hoechst Co., Ltd.
Sun wax 131-P, sun wax 161-
P, Chemipearl W-100 manufactured by Mitsui Petrochemical Co., Ltd.
Chemipearl W-200, Chemipearl W-500, Chemipearl W-800, Chemipearl W-950 and the like can be used.

As the fluororesin fine particles, tetrafluoroethylene fine particles are most preferable. For example, Lubron L-2 and Lubron L-5 manufactured by Daikin Industries, Ltd., and MP1100 manufactured by Du Pont-Mitsui Co., Ltd. ,
MP1200, Asahi ICI Fluoropolymers Co., Ltd.
Fullon Dispersion AD1, Fullon Dispersion AD2, Fullon L141J, Fullon L150J, Fullon L155J and the like are suitable.
Among these, a particularly excellent lubricating effect can be expected by using a combination of polyolefin wax and fine particles of tetrafluoroethylene.

The compounding amount of the solid lubricant (b) in the organic film is from 1 to 8 based on 100 parts by weight (solid content) of the base resin.
It is suitably 0 parts by weight (solid content), preferably 3 to 40 parts by weight (solid content). If the amount of the solid lubricant (b) is less than 1 part by weight, the lubricating effect is poor. On the other hand, if the amount is more than 80 parts by weight, the coatability is undesirably reduced.

The organic coating of the organic coated steel sheet of the present invention usually comprises an organic polymer resin (A) as a base resin, and if necessary, an inorganic rust preventive pigment (a) and a solid lubricant (b). ) And a curing agent are added. If necessary, organic color pigments (for example, condensed polycyclic organic pigments and phthalocyanine organic pigments) and coloring dyes (for example, organic solvent-soluble azo Dyes, water-soluble azo metal dyes, etc.), inorganic pigments (eg, titanium oxide), chelating agents (eg, thiol), conductive pigments (eg, metal powder such as zinc, aluminum, nickel, etc.), iron phosphide , Antimony-doped tin oxide, etc.), coupling agents (eg, silane coupling agents, titanium coupling agents, etc.), melamine / cyanuric acid adducts, etc. can be added. .

The coating composition for forming a film containing the above-mentioned base resin and additional components usually contains a solvent (organic solvent and / or water), and if necessary, a neutralizing agent or the like is added. . The organic film as described above is formed on the composite oxide film. The dry thickness of the organic film is 0.1 to 5 μm, preferably 0.3 to 3 μm, and more preferably 0.5 to 2 μm. The thickness of the organic film is 0.
If the thickness is less than 1 μm, the corrosion resistance is insufficient.
If it exceeds μm, conductivity and workability will decrease.

Next, a method for producing the organic coated steel sheet of the present invention will be described. The organic-coated steel sheet of the present invention is obtained by treating the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet with a treatment liquid containing the components of the above-described composite oxide film (applying a treatment liquid), and then drying by heating. In the upper layer,
The above-mentioned organic polymer resin (A) is used as a base resin, and a coating composition to which an inorganic rust preventive pigment (a), a solid lubricant (b) and the like are added as required is applied, and then heated and dried. Manufactured. The surface of the plated steel sheet may be subjected to an alkali degreasing treatment as required before applying the treatment liquid, and may be subjected to a pretreatment such as a surface conditioning treatment to improve adhesion and corrosion resistance.

In order to treat the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet with a treating solution to form a composite oxide film containing the components (α) and (β),
(A) 0.001-3.0 mol / L of oxide fine particles;
(B) It contains 0.001 to 6.0 mol / L of phosphoric acid and / or a phosphoric acid compound in terms of P ₂ O ₅ , and further contains the above-described additional components (organic resin component, iron Treatment with an aqueous solution to which group metal ions, corrosion inhibitors, and other additives have been added, followed by drying by heating.

In order to treat the surface of a galvanized steel sheet or an aluminum-plated steel sheet with a treating solution to form a composite oxide film containing the above components (α), (β) and (γ), Added components (a) and (b)
In addition, (c) each metal ion of Mg, Ca, Sr, and Ba; a water-soluble ion containing at least one of the metals; a compound containing at least one of the metals; One or more selected from composite compounds containing at least one of the above, containing 0.001-3.0 mol / L in total in terms of metal amount of the metal, and if necessary. Treatment with an acidic aqueous solution having a pH of 0.5 to 5 to which each of the above-mentioned additional components (organic resin component, iron group metal ion, corrosion inhibitor, and other additives) is added;
Thereafter, drying by heating is preferred.

In order to treat the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet with a treating solution to form a composite oxide film containing the above components (α), (β) and (δ), Added components (a) and (b)
And (d) Li, Mn, Fe, Co, N
i, each metal ion of Zn, Al, La, and Ce, a water-soluble ion containing at least one of the metals, a compound containing at least one of the metals, and at least one of the metals 1 selected from complex compounds
Species or two or more of them contain 0.001-3.0 mol / L in total in terms of the metal amount of the metal, and each of the above-mentioned additional components (organic resin component, iron group metal ion , Corrosion inhibitors and other additives)
It is preferable to treat with an acidic aqueous solution of 0.5 to 5 and then heat and dry.

Further, the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet is treated with a treating solution to form a composite oxide film containing the components (α), (β), (γ) and (δ). Is the additive component (a) described above,
PH (b) containing (b), (c) and (d) and, if necessary, the above-mentioned additional components (organic resin component, iron group metal ion, corrosion inhibitor, other additives).
It is preferable to treat with an acidic aqueous solution of 5 to 5 and then heat and dry.

Silicon oxide (SiO ₂ fine particles) is most preferable as the oxide fine particles as the additional component (a). This silicon oxide is a water-dispersible SiO ₂ that is stable in an acidic aqueous solution.
Fine particles may be used, and commercially available silica sol or water-dispersible silicate oligomer can be used. However, since fluoride such as hexafluorosilicic acid is highly corrosive and greatly affects the human body, it is desirable not to use it from the viewpoint of affecting the working environment.

The amount of the oxide fine particles added in the processing solution (the amount of SiO _{2 in} the case of silicon oxide) is 0.00
The amount is 1 to 3.0 mol / L, preferably 0.05 to 1.0 mol / L, and more preferably 0.1 to 0.5 mol / L. If the amount of the oxide fine particles is less than 0.001 mol / L, the effect of the addition is not sufficient, and the corrosion resistance is poor. on the other hand,
If the addition amount exceeds 3.0 mol / L, the water resistance of the film becomes poor, and as a result, the corrosion resistance also deteriorates.

The phosphoric acid and / or phosphoric acid compound as the additional component (b) includes orthophosphoric acid, pyrophosphoric acid,
Polyphosphoric acid such as tripolyphosphoric acid, metaphosphoric acid and inorganic salts thereof (for example, aluminum monophosphate), phosphoric acid, phosphorous acid, hypophosphorous acid, hypophosphorous acid, etc. Compounds exist in the form of an anion generated when dissolved in an aqueous solution or as a complex ion with a metal cation, in the form of a free acid, or in the form of an inorganic salt in a water-dispersed state. And the amount of the phosphoric acid component in the present invention is defined as the total of all these forms present in the acidic aqueous solution as P ₂ O ₅ conversion.

The addition amount of phosphoric acid and / or a phosphoric acid compound in the treatment liquid is 0.001 to 6.0 mol / L, preferably 0.02 to 1.0 mol / L in terms of P ₂ O ₅ . More preferably, it is 0.1 to 0.8 mol / L. 0.001 mol / L of phosphoric acid and / or phosphoric acid compound
If less than the above, the effect of the addition is not sufficient, and the corrosion resistance is poor.
On the other hand, if the addition amount exceeds 6.0 mol / L, excessive phosphate ions react with the plating film in a humid environment, and depending on the corrosive environment, promote the corrosion of the plating base material, and cause discoloration and spot-like rust. Become. In addition, as the additional component (b),
Use of an ammonium phosphate salt is also effective because a composite oxide having excellent corrosion resistance can be obtained. As ammonium phosphate, ammonium phosphate monobasic,
It is preferable to use one kind or two or more kinds such as ammonium diphosphate.

The added amount of the above-mentioned additional component (c) in the treatment liquid was 0.001 to 3.0 mol / L in terms of the amount of metal,
Preferably, it is 0.01 to 0.5 mol / L. If the total amount of these additives is less than 0.001 mol / L, the effect of the addition cannot be sufficiently obtained, while the addition amount is 3.0 mol / L.
On the other hand, if it exceeds 3, these components will inhibit the network of the film, and it will be difficult to form a dense film. Further, the metal component is easily eluted from the film, and depending on the environment, a defect such as discoloration of the appearance occurs.

Further, among the above-mentioned additional components (c), Mg
The components most significantly improve corrosion resistance. Also, this Mg
The component may be present in the treatment liquid in a compound containing Mg or a complex compound, but in order to obtain particularly excellent corrosion resistance, a metal ion or a water-soluble ion containing Mg is particularly preferable. In order to supply the ions of the additive component (c) as a metal salt, anions such as chlorine ions, nitrate ions, sulfate ions, acetate ions, and borate ions may be added to the treatment liquid.

The added amount of the above-mentioned additional component (d) in the treatment solution is 0.001-3.0 mol / L in terms of the amount of metal,
Preferably, it is 0.01 to 0.5 mol / L. If the total amount of these additives is less than 0.001 mol / L, the effect of the addition cannot be sufficiently obtained, while the addition amount is 3.0 mol / L.
On the contrary, when these components exceed the above, these components become soluble cations, which hinder the network of the film, making it difficult to form a dense film. Further, among the above-mentioned additional components (d), Ni (nickel component) and / or Mn (manganese component) most significantly improve the corrosion resistance. In order to supply the ion of the additive component (d) as a metal salt,
Anions such as chloride ions, nitrate ions, sulfate ions, acetate ions, and borate ions other than phosphate ions may be added to the treatment liquid.

It is important that the treatment liquid containing the additive component (c) and / or the additive component (d) is an acidic aqueous solution. That is, since the plating component such as zinc is easily dissolved by making the treatment liquid acidic, a phosphate compound layer containing the plating component such as zinc is formed at the interface between the chemical conversion treatment film and the plating, thereby forming an interface between the two. Is presumed to result in a film having excellent corrosion resistance.
The pH of the acidic aqueous solution is 0.5 to 5, preferably 2 to 5.
4 is preferable. If the pH of the treatment liquid is less than 0.5, the reactivity of the treatment liquid becomes too high, so that a fine defect is formed in the film and the corrosion resistance is reduced. On the other hand, when the processing solution is pH
If it exceeds 5, the reactivity of the processing solution becomes low, and the bonding between the plating surface and the interface as described above becomes insufficient. In this case, the corrosion resistance also decreases.

Hereinafter, particularly good performance is provided in the present invention.
Conditions of processing solution for obtaining complex oxide film
Will be described. First, the component (α) described above and
As (β), (α) SiO₂Fine particles of SiO₂Conversion amount
0.01 to 3000 mg / m², (Β) phosphate and
And / or phosphate compound₂O₅0.01-3 in conversion amount
000mg / m²And the components (α) and (β)
Is 6 to 3600 mg / m ²Which is
When forming a composite oxide film, use the above composite oxide film
Additives (a) and (b) in the aqueous solution for formation
And (a) SiO₂Fine particles of SiO₂0.00 in conversion amount
1 to 3.0 mol / L, preferably 0.05 to 1.0 mol
/ L, more preferably 0.1 to 0.5 mol / L (b)
Phosphoric acid and / or phosphate compound₂O₅In conversion amount
0.001 to 6.0 mol / L, preferably 0.02 to
1.0 mol / L, more preferably 0.1 to 0.8 mol
/ L, and further, if necessary,
(Organic resin component, iron group metal ion, corrosion inhibitor,
Treated with an aqueous solution to which other additives have been added, and then heated
Drying is preferred.

In addition to the above components (α) and (β), as the component (γ), one kind selected from the group consisting of (γ) Mg, a compound containing Mg, and a composite compound containing Mg The above is 0.01 to 1000 mg / mg in terms of Mg.
m ² , and when forming a composite oxide film in which the total amount of the components (α), (β) and (γ) is 6 to 3600 mg / m ² , the composite oxide film In the aqueous solution for formation, in addition to the above-mentioned additional components (a) and (b), (iii) Mg ions, water-soluble ions containing Mg, compounds containing Mg, Mg
One or two or more selected from the compound compounds containing 0.001 to 3.0 mol / L, preferably 0.01 to 0.5 mol / L in terms of Mg, more preferably PH at which each of the above-mentioned additives (organic resin component, iron group metal ion, corrosion inhibitor, other additives) is added according to
It is preferable to treat with an acidic aqueous solution of 0.5 to 5 and then heat and dry.

Further, in addition to the above components (α) and (β), (δ) Li, Mn, F
e, Co, Ni, Zn, Al, La, Ce, one or more metals selected from the group consisting of compounds and / or
Or a case where a composite oxide film is contained as a composite compound), and the total amount of the components (α), (β) and (δ) is 6 to 3600 mg / m ^2. In the aqueous solution for forming a composite oxide film, in addition to the additional components (a) and (b), (d) Li, Mn, Fe, C
o, each metal ion of Ni, Zn, Al, La, and Ce, a water-soluble ion containing at least one of the metals, a compound containing at least one of the metals, at least one of the metals One or two or more compounds selected from the composite compounds containing a total of 0.001 to 3.0 mol / L, preferably 0.01
0.5 mol / L, and if necessary, each of the above-mentioned additional components (organic resin component, iron group metal ion, corrosion inhibitor, other additives) and a pH of 0.5 to 5 It is preferable to treat with an acidic aqueous solution and then heat and dry.

Further, in addition to the components (α) and (β), components (γ) and (δ) are contained, and the adhesion amounts of these components (α), (β), (γ) and (δ) In the case of forming a composite oxide film having a total of 6 to 3600 mg / m ² , the above-mentioned additional components (a), (b), (c) and (d) are added to an aqueous solution for forming a composite oxide film. And further treated with an acidic aqueous solution having a pH of 0.5 to 5 to which the above-mentioned additional components (organic resin component, iron group metal ion, corrosion inhibitor, and other additives) are further added, if necessary.
Thereafter, drying by heating is preferred. The reasons for limiting the addition conditions and amounts of the additional components (a), (b), (c) and (d) are as described above.

The ratio of the component (γ) to the component (α) in the composite oxide film was determined by the molar ratio [Mg / Mg) of the component (γ) in terms of Mg and the component (α) in terms of SiO _2. SiO ₂ ]
In order to adjust the ratio between the additive component (c) and the additive component (a) in the acidic aqueous solution for forming the composite oxide film, the ratio of Mg to the additive component (c) is adjusted to fall within the range of 1/100 to 100/1. The molar ratio of the conversion amount and the conversion amount of the additive component (a) to SiO ₂ [Mg /
[SiO ₂ ] in the range of 1/100 to 100/1.

The ratio of the component (γ) to the component (α) in the composite oxide film was determined by the molar ratio of the component (γ) in terms of Mg and the component (α) in terms of SiO ₂ [Mg / SiO ₂ ]
In order to make the range of 1/10 to 10/1 which is a more preferable range and the range of 1/2 to 5/1 which is a still more preferable range,
Additives in acidic aqueous solution for complex oxide film formation (c)
And the ratio of the additive component (a) to the molar ratio [M] of the additive component (c) in terms of Mg and the additive component (a) in terms of SiO _2.
g / SiO ₂ ], and it is appropriate to set the range of 1/10 to 10/1, more preferably 1/2 to 5/1.

Further, the ratio of the component (β) to the component (γ) in the composite oxide film was determined by the molar ratio of the component (β) in terms of P ₂ O ₅ and the component (γ) in terms of Mg [ P ₂ O ₅ / Mg]
In order to make the range of 1/100 to 100/1, the ratio of the additive component (b) to the additive component (c) in the acidic aqueous solution for forming the composite oxide film is determined by adding P _{2 of the} additive component (b). O ₅ equivalent amount to the molar ratio of Mg in terms of additive component (c) _{[P 2 O} 5 /
Mg] in the range of 1/100 to 100/1.

The ratio between the component (β) and the component (γ) in the composite oxide film was determined by the molar ratio of the component (β) in terms of P ₂ O ₅ and the component (γ) in terms of Mg. [P ₂ O ₅ / Mg], it is preferable to add 1/10 to 10/1, which is a more preferable range, and 1/2 to 2/1, which is a still more preferable range, by adding an acidic aqueous solution for forming a complex oxide film. the molar ratio of Mg in terms of the component (b) and _P 2 _{O 5} in terms of weight and additive component the proportion of component (c) added, the additive component (b) (c) _{[P 2 O} 5 /
1] to 10/1, more preferably 1/2.
It is suitably set to ２2/1.

When adjusting the ratio of the additional component (b) and the additional component (c) in the acidic aqueous solution for forming the composite oxide film,
It is preferable to use an aqueous solution of magnesium monophosphate, which is obtained by defining the molar ratio of the magnesium component and the phosphoric acid component in advance, since other anion components do not mix in the treatment liquid. However, when an aqueous solution of magnesium monophosphate is used, if the value of the molar ratio [P ₂ O ₅ / Mg] decreases, the stability of the compound in the aqueous solution decreases.
₂ O ₅ / Mg] is preferably 1/2 or more.

On the other hand, when the molar ratio [P ₂ O ₅ / Mg] of the aqueous solution of monobasic magnesium phosphate is increased, the pH of the processing solution is increased.
, The reactivity with the plating substrate is increased, and as a result, uneven formation of the film due to uneven reaction occurs, which affects the corrosion resistance. Therefore, when using an aqueous solution of magnesium monophosphate, which is obtained by defining the molar ratio of the magnesium component and the phosphoric acid component, the molar ratio [P ₂ O ₅
/ Mg] is preferably 2/1 or less.

In order to obtain the most excellent corrosion resistance, the ratio of the component (γ) to the component (α) in the composite oxide film was determined as follows:
The molar ratio [Mg / SiO ₂ ] of the amount of component (γ) in terms of Mg and the amount of component (α) in terms of SiO _{2 is} 1/100 to 100 /.
1, more preferably 1/10 to 10/1, still more preferably 1/2 to 5/1, and the ratio of component (β) to component (γ) in the composite oxide film is adjusted to component (β) P ₂ O ₅
The molar ratio [P ₂ O ₅ ] between the conversion amount and the Mg conversion amount of the component (γ).
/ Mg] is 1/100 to 100/1, more preferably 1/100/1.
/ 10 to 10/1, and more preferably 1/2 to 2/1, the ratio of the additive component (c) and the additive component (a) in the acidic aqueous solution for forming the composite oxide film is The molar ratio [Mg / SiO ₂ ] of the amount of the added component (c) in terms of Mg and the amount of the added component (a) in terms of SiO _{2 is} 1/100 to 100 /.
1, preferably in the range of 1/10 to 10/1, more preferably in the range of 1/2 to 5/1, and the ratio of the additional component (b) to the additional component (c) is determined by the P of the additional component (b). the molar ratio of Mg in terms of ₂ O ₅ in terms of weight and additive component (c) _[P 2 _{O 5}
/ Mg], from 1/100 to 100/1, preferably 1/1.
It is suitable to set it to 0 to 10/1, more preferably 1/2 to 2/1.

The ratio of the component (δ) to the component (α) in the composite oxide film was determined by the molar ratio [Me] of the component (δ) in terms of metal and the component (α) in terms of SiO _2. / Si
O ₂ ] in the range of 1/100 to 100/1, the ratio of the additive component (d) to the additive component (a) in the acidic aqueous solution for forming the composite oxide film is adjusted to the additive component (d). ) May be in the range of 1/100 to 100/1 in terms of the molar ratio [Me / SiO ₂ ] of the metal conversion amount Me of the additive component (a) to the SiO ₂ conversion amount.

The ratio of the component (δ) to the component (α) in the composite oxide film was determined by the molar ratio [Me] of the component (δ) in terms of metal and the component (α) in terms of SiO _2. / Si
O ₂ ] in a more preferred range of 1/10 to 10/1,
In order to set the ratio of the additional component (d) and the additional component (a) in the acidic aqueous solution for forming a composite oxide film to a more preferable range of 1/2 to 5/1, the ratio of the additional component (d) )) And the molar ratio [Me / SiO ₂ ] of the added component (a) in terms of SiO ₂ is in the range of 1/10 to 10/1, more preferably 1/2 to 5/1. Is appropriate.

Further, the ratio between the component (β) and the component (δ) in the composite oxide film was determined by the molar ratio of the component (β) in terms of P ₂ O ₅ and the component (δ) in terms of the metal equivalent Me. [P ₂ O ₅ / M
In order to set the ratio of the additive component (b) to the additive component (d) in the acidic aqueous solution for forming the composite oxide film, the ratio of the additive component (b) to the range of 1/2 to 2/1 in e]. The molar ratio [P ₂ O ₅ ] between the P ₂ O ₅ conversion amount and the metal conversion amount Me of the additive component (d).
/ Me] in the range of 1/2 to 2/1.

In order to obtain the most excellent corrosion resistance, the ratio of component (δ) to component (α) in the composite oxide film is
The molar ratio [Me / SiO ₂ ] of the metal conversion amount Me of the component (δ) to the SiO ₂ conversion amount of the component (α) is 1/100 to 10
0/1, more preferably 1/10 to 10/1, still more preferably 1/2 to 5/1, and the ratio of the component (β) to the component (δ) in the composite oxide film is determined by the component ( β) P ₂
In order to make the molar ratio [P ₂ O ₅ / Me] between the O ₅ conversion amount and the metal conversion amount Me of the component (δ) 1/2 to 2/1,
Additives in acidic aqueous solution for complex oxide film formation (d)
Of the additive component (a) in terms of the molar ratio [Me / SiO ₂ ] of the additive component (a) in terms of metal and the additive component (a) in terms of SiO _{2, from} 1/100 to 100/1. , Preferably 1/10 to 10/1, more preferably 1/2 to 5
/ 1 and the additional component (b) and the additional component (d)
Is the molar ratio [P ₂ O ₅ / M] between the P ₂ O ₅ equivalent of the additive component (b) and the metal equivalent Me of the additive component (d).
It is appropriate that e] is set to 1/2 to 2/1.

The treatment liquid further contains any of metal ions of Ni, Fe, and Co as additional components (e),
One or more selected from among water-soluble ions containing at least one of the above metals can be added in an appropriate amount, and the addition of such an iron group metal results when no iron group metal is added. Further, the blackening phenomenon caused by the corrosion of the plating surface layer in a humid environment can be avoided. In addition, among these iron group metals, the effect of Ni is particularly high, and an excellent effect is recognized even in a trace amount. However, excessive addition of iron group metals such as Ni and Co leads to deterioration of corrosion resistance, so that an appropriate amount is required.

The addition amount of the above-mentioned additive component (e) is 1/1000 to 1 mol, in terms of metal amount, per 1 mol of the addition component (c) or 1 mol of the addition component (d) in terms of metal amount. Desirably, the range is 1/1000 to 1/100 mol. The amount of the additive component (e) is 1 to 1 mol of the additive component (c) or 1 mol of the additive component (d).
If the amount is less than / 10,000 mol, the effect of the addition is not sufficient, while if the amount exceeds 1 mol, the corrosion resistance deteriorates as described above.

An organic resin (f) can be further added to the processing solution for forming the composite oxide film for the purpose of improving the workability and corrosion resistance of the film. Examples of the organic resin include a water-soluble resin such as an epoxy resin, a urethane resin, an acrylic resin, an acryl-ethylene copolymer, an acryl-styrene copolymer, an alkyd resin, a polyester resin, and an ethylene resin, and / or a water dispersion. Resin. Furthermore, in addition to these aqueous resins,
A water-soluble epoxy resin, a water-soluble phenol resin, a water-soluble butadiene rubber (SBR, NBR, MBR), a melamine resin, a blocked isocyanate, an oxazoline compound, or the like can be added as a crosslinking agent. In the treatment liquid, in addition to the above-mentioned additional components (a) to (f), an appropriate amount of the above-mentioned additional components to be added to the film may be added.

The method of coating the surface of the plated steel sheet with the treatment liquid may be any of a coating method, a dipping method and a spraying method. Or any other coating means. In addition, coating treatment using a squeeze coater, dipping treatment,
After the spray treatment, it is also possible to adjust the amount of application, make the appearance uniform, and make the film thickness uniform by an air knife method or a roll drawing method. There is no special restriction on the temperature of the processing solution,
A normal temperature to about 60 ° C. is appropriate. If the temperature is lower than room temperature, equipment for cooling is required, which is uneconomical.
If the temperature is higher than 0 ° C., the water tends to evaporate, so that the management of the processing liquid becomes difficult.

After the treatment liquid is coated as described above, heating and drying are usually performed without washing with water. However, since the treatment liquid used in the present invention forms a hardly soluble salt by reaction with the base plated steel sheet, It may be washed later. The method of heating and drying the coated processing solution is optional, for example, a dryer, a hot air oven, a high-frequency induction heating oven,
Means such as an infrared furnace can be used. This heating and drying treatment is performed at an ultimate plate temperature of 50 to 300 ° C, preferably 80 to 300 ° C.
It is preferable to carry out the reaction at a temperature of 200 ° C, more preferably 80 to 160 ° C. If the heating and drying temperature is lower than 50 ° C., a large amount of water remains in the film, and the corrosion resistance becomes insufficient. on the other hand,
When the heating and drying temperature exceeds 300 ° C., not only is it uneconomical, but also the coating tends to have defects and the corrosion resistance is reduced.

After a composite oxide film is formed on the surface of a zinc-based steel sheet or an aluminum-based steel sheet as described above, the above-mentioned coating composition for forming an organic film is applied to the upper layer. As a method of applying the coating composition, any method such as an application method, an immersion method, and a spray method can be adopted. As a coating method, any method such as a roll coater (three-roll system, two-roll system, etc.), a squeeze coater, a die coater and the like may be used. In addition, after the coating, dipping, or spraying with a squeeze coater or the like, it is also possible to adjust the coating amount, uniform the appearance, and uniform the film thickness by an air knife method or a roll drawing method.

After application of the coating composition, heating and drying are usually performed without washing with water, but a washing step may be performed after application of the coating composition. For the heating and drying treatment, a drier, a hot air oven, a high-frequency induction heating oven, an infrared oven, or the like can be used. The heat treatment is performed at a plate temperature of 50 to 350.
C., preferably in the range of 80.degree. C. to 250.degree. If the heating temperature is lower than 50 ° C., a large amount of water in the film remains, and the corrosion resistance becomes insufficient. When the heating temperature is 35
If it exceeds 0 ° C., it is not only uneconomical, but also there is a possibility that a defect occurs in the film and the corrosion resistance is reduced.

The present invention includes a steel sheet having the above-mentioned organic film on both sides or one side. Therefore, examples of the form of the steel sheet of the present invention include the following. (1) One side: plating film-composite oxide film-organic film,
One side: Plating film (2) One side: Plating film-Composite oxide film-Organic film,
One side: plating film-known phosphate treatment film, etc. (3) Both surfaces: plating film-composite oxide film-organic film (4) One surface: plating film-composite oxide film-organic film,
One side: Plating film-Composite oxide film (5) One surface: Plating film-Composite oxide film-Organic film,
One side: plating film-organic film

[0171]

EXAMPLES Example 1 Treatment liquids (coating compositions) for forming the first layer film shown in Tables 2 to 17 and resin compositions for forming the second layer film shown in Table 18 were prepared. The resin composition shown in Table 18 is appropriately mixed with ion-exchanged silica, fine-particle silica shown in Table 19, and a solid lubricant shown in Table 20, and dispersed using a paint dispersing machine (sand grinder) for a required time to obtain the desired composition. A coating composition was obtained. The ion-exchanged silica is a Ca-exchanged silica such as SHIE manufactured by WRGrace & Co.
LDEX C303 (average particle size 2.5 to 3.5 μm,
(Ca concentration 3 wt%) was used.

In order to obtain an organically coated steel sheet for home appliances, building materials and automobile parts, the sheet thickness: 0.8 mm and the surface roughness Ra: 1.0
Using a plated steel sheet shown in Table 1 in which various zinc-based or aluminum-based plating was applied to a cold-rolled steel sheet of μm as a processing base plate, the surface of this plated steel sheet was subjected to alkali degreasing treatment, washed with water, and dried. The treatment liquid (coating composition) shown was applied with a roll coater and dried by heating to form a first layer coating. The thickness of the first layer film is determined by the solid content of the treatment liquid (residual residue after heating) or the coating conditions (rolling force,
Rotation speed). Next, a composition prepared by blending various additives with the coating compositions shown in Table 18 was applied by a roll coater and dried by heating to form a second layer film, thereby producing organic-coated steel sheets of the present invention and comparative examples. The thickness of the second layer film was adjusted according to the solid content of the coating composition (residual residue after heating) or the application conditions (roll rolling force, rotation speed, etc.).

The obtained organic coated steel sheets were evaluated for quality performance (coating appearance, white rust resistance, white rust resistance after alkali degreasing, paint adhesion, workability). The results are shown in Tables 21 to 21 together with the film configurations of the first layer film and the second layer film.
It is shown in Table 81. The evaluation of the quality performance of the organic coated steel sheet was performed as follows. (1) Appearance of Film For each sample, the uniformity of the film appearance (with or without unevenness) was visually evaluated. The evaluation criteria are as follows. ：: uniform appearance without any unevenness △: appearance with some unevenness ×: appearance with unevenness

(2) White Rust Resistance For each sample, a salt spray test (JIS-Z-23)
71) was carried out, and evaluated by the area ratio of white rust occurrence after a predetermined time. The evaluation criteria are as follows. ◎: No white rust generated ○ +: White rust generation area ratio less than 5% ○: White rust generation area ratio 5% or more and less than 10% ○-: White rust generation area ratio 10% or more and less than 25% △: White rust Generated area rate 25% or more, less than 50% ×: White rust generated area rate 50% or more

(3) White rust resistance after alkali degreasing For each sample, an alkali treatment liquid CLN-364S manufactured by Nippon Parkerizing Co., Ltd. (60 ° C., spray 2
Min), and then a salt spray test (JIS)
-Z-2371), and evaluated by a white rust area ratio after a predetermined time. The evaluation criteria are as follows. ◎: No white rust generated ○ +: White rust generation area ratio less than 5% ○: White rust generation area ratio 5% or more and less than 10% ○-: White rust generation area ratio 10% or more and less than 25% △: White rust Generated area rate 25% or more, less than 50% ×: White rust generated area rate 50% or more

(4) Adhesiveness of paint For each sample, a melamine-based baking paint (film thickness 30
μm), immersed in boiling water for 2 hours, immediately cut in a grid (10 × 10 grids at 1 mm intervals), adhered and peeled with an adhesive tape, and peeled area of the coating film Rate was evaluated. The evaluation criteria are as follows. ：: No peeling ○: Peeling area rate less than 5% △: Peeling area rate 5% or more, less than 20% ×: Peeling area rate 20% or more

(5) Workability Deep drawing was performed with a blank diameter of φ120 mm and a die diameter of φ50 mm (under no oiling conditions), and evaluated by the molding height until cracks occurred. The evaluation criteria are as follows. ◎: Draw-out ○: Molding height 30 mm or more △: Molding height 20 mm or more, less than 30 mm ×: Molding height less than 20 mm

[0178]

[Table 1]

[0179]

[Table 2]

[0180]

[Table 3]

[0181]

[Table 4]

[0182]

[Table 5]

[0183]

[Table 6]

[0184]

[Table 7]

[0185]

[Table 8]

[0186]

[Table 9]

[0187]

[Table 10]

[0188]

[Table 11]

[0189]

[Table 12]

[0190]

[Table 13]

[0191]

[Table 14]

[0192]

[Table 15]

[0193]

[Table 16]

[0194]

[Table 17]

[0195]

[Table 18]

[0196]

[Table 19]

[0197]

[Table 20]

In the following Tables 21 to 81, * 1 to * 13 described in the tables indicate the following contents. * 1: No. described in Table 1. * 2: No. described in Tables 2 to 17 * 3: No. described in Table 18 * 4: SiO ₂ fine particles (α) = SiO ₂ of SiO ₂ fine particles
Adhesion amount in conversion: Mg component (γ) = Mg, one or more types of M selected from the group consisting of Mg-containing compounds, and Mg-containing composite compounds.
Adhesion amount in terms of g: P ₂ O ₅ component (β) = adhesion amount of phosphoric acid and / or phosphate compound in terms of P ₂ O ₅ * 5: Mg component (γ) in terms of Mg and SiO ₂ equivalent S at
iO ₂ fine particles (alpha) and the molar ratio of _{* 6: P 2 O 5 P} 2 O 5 component (beta) and Mg component in terms of Mg in terms of (gamma) (provided that the alkaline earth metal component is Ca
In the case of the component, Sr component or Ba component, the molar ratio with the Ca component, Sr component or Ba component in terms of each metal) * 7: ion-exchanged silica (c) based on 100 parts by weight of the solid content of the resin composition * 8: No. listed in Table 19 * 9: The solid content (parts by weight) of the fine particle silica (d) based on 100 parts by weight of the solid content of the resin composition * 10: The ion-exchange silica (c) and the fine particle silica (100 parts by weight) relative to the solid content of 100 parts by weight of the resin composition d) Total solid content (parts by weight) * 11: Ratio of solid content by weight of ion-exchanged silica (c) and particulate silica (d) * 12: No. listed in Table 20 * 13: The solid content of the solid lubricant (b) per 100 parts by weight of the solid content of the resin composition (parts by weight)

[0199]

[Table 21]

[0200]

[Table 22]

[0201]

[Table 23]

[0202]

[Table 24]

[0203]

[Table 25]

[0204]

[Table 26]

[0205]

[Table 27]

[0206]

[Table 28]

[0207]

[Table 29]

[0208]

[Table 30]

[0209]

[Table 31]

[0210]

[Table 32]

[0211]

[Table 33]

[0212]

[Table 34]

[0213]

[Table 35]

[0214]

[Table 36]

[0215]

[Table 37]

[0216]

[Table 38]

[0219]

[Table 39]

[0218]

[Table 40]

[0219]

[Table 41]

[0220]

[Table 42]

[0221]

[Table 43]

[0222]

[Table 44]

[0223]

[Table 45]

[0224]

[Table 46]

[0225]

[Table 47]

[0226]

[Table 48]

[0227]

[Table 49]

[0228]

[Table 50]

[0229]

[Table 51]

[0230]

[Table 52]

[0231]

[Table 53]

[0232]

[Table 54]

[0233]

[Table 55]

[0234]

[Table 56]

[0235]

[Table 57]

[0236]

[Table 58]

[0237]

[Table 59]

[0238]

[Table 60]

[0239]

[Table 61]

[0240]

[Table 62]

[0241]

[Table 63]

[0242]

[Table 64]

[0243]

[Table 65]

[0244]

[Table 66]

[0245]

[Table 67]

[0246]

[Table 68]

[0247]

[Table 69]

[0248]

[Table 70]

[0249]

[Table 71]

[0250]

[Table 72]

[0251]

[Table 73]

[0252]

[Table 74]

[0253]

[Table 75]

[0254]

[Table 76]

[0255]

[Table 77]

[0256]

[Table 78]

[0257]

[Table 79]

[0258]

[Table 80]

[0259]

[Table 81]

As a conventional reactive type chromate treated steel sheet,
Chromic anhydride: 30 g / l, phosphoric acid: 10 g / l, Na
F: 0.5 g / l, K ₂ TiF ₆ : 4 g / l, spray treatment at a bath temperature of 40 ° C., followed by washing and drying to obtain the amount of chromium deposited (in terms of chromium metal). Manufactured a chromate-treated steel sheet of 20 mg / m ² . When this was subjected to a salt spray test under the same conditions as in this example, white rust was generated in about 24 hours. Therefore,
From these results and the results of this example, it can be seen that the organic-coated steel sheet of the present invention can provide much better corrosion resistance than the conventional chromate-treated steel sheet.

Example 2 Nos. Shown in Tables 2 to 5 were used as treatment liquids (coating compositions) for forming the first layer coating. 1 to N
o. 15 was used. In addition, as the resin composition (coating composition) for forming the second layer film, Table 18 which is the same as in Example 1 was used.
The following was used. These coating compositions include zinc phosphate and / or aluminum phosphate as shown in Table 82;
The calcium compound shown in Table 3 and the solid lubricant shown in Table 20 were appropriately blended and dispersed using a paint disperser (sand grinder) for a required time to obtain a desired paint composition.

In order to obtain an organically coated steel sheet for home appliances, building materials and automobile parts, the sheet thickness: 0.8 mm and the surface roughness Ra: 1.0
Using a galvanized steel sheet shown in Table 1 obtained by applying various zinc-based or aluminum-based plating to a cold-rolled steel sheet having a thickness of μm as a processing base plate, the surface of the plated steel sheet is subjected to alkali degreasing treatment, washed with water, and dried. The treatment liquid No. 1 to N
o. 15 (coating composition) was applied by a roll coater and dried by heating to form a first layer coating. The thickness of the first layer film was adjusted by the solid content of the treatment liquid (residual residue of heating) or the application conditions (roll rolling force, rotation speed, etc.). Next, a composition prepared by blending various additives with the coating compositions shown in Table 18 was applied by a roll coater and dried by heating to form a second layer film, thereby producing organic-coated steel sheets of the present invention and comparative examples. The thickness of the second layer film was adjusted according to the solid content of the coating composition (residual residue after heating) or application conditions (roll rolling force, rotation speed, etc.).

The obtained organic coated steel sheets were evaluated for quality performance (coating appearance, white rust resistance, white rust resistance after alkali degreasing, paint adhesion, workability). The results are shown in Tables 84 to 84 together with the film configurations of the first and second layer films.
It is shown in Table 106. In each of Examples in Tables 84 to 106, the amount of the first layer coating, the amounts of the components (α), (β) and (γ), the molar ratio (γ) / (α), and the molar ratio ( β)
Since / (γ) is the same as that of the first-layer film having the same film thickness to which the same treatment composition is applied in [Example 1], the description in the table is omitted. Evaluation of the quality performance of the organic coated steel sheet was performed in the same manner as in [Example 1].

[0264]

[Table 82]

[0265]

[Table 83]

In the following Tables 84 to 106, * 1 to * 11 described in the tables indicate the following contents. * 1: No. described in Table 1. * 2: No. described in Tables 2 to 5 * 3: No. described in Table 18 * 4: No. described in Table 82. * 5: The solid content (parts by weight) of zinc phosphate (e) and / or aluminum phosphate (f) based on 100 parts by weight of the solid content of the resin composition. * 7: Solid content of calcium compound (g) based on 100 parts by weight of solids of resin composition * 8: Zinc phosphate (e) and / or aluminum phosphate (f) based on 100 parts by weight of solids of resin composition ) And calcium compound (g) in total solid content (parts by weight) * 9: Zinc phosphate (e) and / or solid content weight ratio of aluminum phosphate (f) and calcium compound (g) * 10: Table No. 20 described in No. 20 * 11: The solid content (parts by weight) of the solid lubricant (b) based on 100 parts by weight of the solid content of the resin composition

[0267]

[Table 84]

[0268]

[Table 85]

[0269]

[Table 86]

[0270]

[Table 87]

[0271]

[Table 88]

[0272]

[Table 89]

[0273]

[Table 90]

[0274]

[Table 91]

[0275]

[Table 92]

[0276]

[Table 93]

[0277]

[Table 94]

[0278]

[Table 95]

[0279]

[Table 96]

[0280]

[Table 97]

[0281]

[Table 98]

[0282]

[Table 99]

[0283]

[Table 100]

[0284]

[Table 101]

[0285]

[Table 102]

[0286]

[Table 103]

[0287]

[Table 104]

[0288]

[Table 105]

[0289]

[Table 106]

As a conventional reactive type chromate treated steel sheet,
Chromic anhydride: 30 g / l, phosphoric acid: 10 g / l, Na
F: 0.5 g / l, K ₂ TiF ₆ : 4 g / l, spray treatment at a bath temperature of 40 ° C., followed by washing and drying to obtain the amount of chromium deposited (in terms of chromium metal). Manufactured a chromate-treated steel sheet of 20 mg / m ² . When this was subjected to a salt spray test under the same conditions as in this example, white rust was generated in about 24 hours. Therefore,
From these results and the results of this example, it can be seen that the organic-coated steel sheet of the present invention can provide much better corrosion resistance than the conventional chromate-treated steel sheet.

Example 3 The treatment liquids (film compositions) for forming the first layer film shown in Tables 107 to 112 were prepared. As the resin composition (coating composition) for forming the second layer film, the same one shown in Table 18 as in [Example 1] was used.
These coating compositions are appropriately blended with the inorganic rust preventive pigments shown in Tables 113 to 115 and the solid lubricant shown in Table 20, and dispersed using a paint dispersing machine (sand grinder) for a required time to obtain a desired coating composition. The composition was used.

In order to obtain an organically coated steel sheet for home appliances, building materials and automobile parts, the sheet thickness: 0.8 mm and the surface roughness Ra: 1.0
Using a coated steel sheet shown in Table 1 in which various zinc-based plating or aluminum-based plating was applied to a μm cold-rolled steel sheet as a processing base plate, the surface of the plated steel sheet was subjected to alkali degreasing treatment, washed with water, and dried. The treatment liquid (coating composition) shown was applied with a roll coater and dried by heating to form a first layer coating. The thickness of the first layer film was adjusted by the solid content of the treatment liquid (residual residue of heating) or the application conditions (roll rolling force, rotation speed, etc.). Next, a composition prepared by blending various additives with the coating compositions shown in Table 18 was applied by a roll coater and dried by heating to form a second layer film, thereby producing organic-coated steel sheets of the present invention and comparative examples.
The thickness of the second layer film is determined by the solid content of the coating composition (residual residue after heating).
Alternatively, it was adjusted according to the coating conditions (roll rolling force, rotation speed, etc.).

The obtained organic coated steel sheets were evaluated for quality performance (coating appearance, white rust resistance, white rust resistance after alkali degreasing, paint adhesion, workability). The results are shown in Table 116 together with the film configurations of the first layer film and the second layer film.
To Table 154. Evaluation of the quality performance of the organic coated steel sheet was performed in the same manner as in [Example 1].

[0294]

[Table 107]

[0295]

[Table 108]

[0296]

[Table 109]

[0297]

[Table 110]

[0298]

[Table 111]

[0299]

[Table 112]

[0300]

[Table 113]

[0301]

[Table 114]

[0302]

[Table 115]

In the following Tables 116 to 154, * 1 to * 13 described in the tables indicate the following contents. * 1: No. described in Table 1. * 2: No. described in Tables 107 to 112. * 3: No. described in Table 18 * 4: SiO ₂ fine particles (α) = SiO ₂ of SiO ₂ fine particles
Adhesion amount in conversion (mg / m ² ) and weight ratio (wt%) to total adhesion amount of film: P ₂ O ₅ component (β) = adhesion of phosphoric acid and / or phosphate compound in P ₂ O ₅ conversion Amount: metal component (δ) = Li, Mn, Fe, Co, Ni, Z
Attachment amount in terms of metal of one or more metals selected from n, Al, La and Ce (including cases where they are included as compounds and / or composite compounds) * 5: In metal equivalent Component (δ) and SiO _{2 in} terms of SiO _2
2 fine particles (alpha) and the molar ratio of _{* 6: P 2 O 5 P} 2 O 5 component in terms of (beta) and components in terms of metal ([delta]) and the molar ratio of * 7: described in Table 113 to Table 115 No. * 8: Solid content of inorganic rust preventive pigment (a) based on 100 parts by weight of solids of resin composition (parts by weight) * 9: Total of pigment 1 and pigment 2 based on 100 parts by weight of solids of resin composition Solids content (parts by weight) * 10: Weight ratio of solids of Pigment 1 and Pigment 2 * 11: No. in Table 20 * 12: Solid content of solid lubricant (b) per 100 parts by weight of solid content of resin composition (parts by weight)

[0304]

[Table 116]

[0305]

[Table 117]

[0306]

[Table 118]

[0307]

[Table 119]

[0308]

[Table 120]

[0309]

[Table 121]

[0310]

[Table 122]

[0311]

[Table 123]

[0312]

[Table 124]

[0313]

[Table 125]

[0314]

[Table 126]

[0315]

[Table 127]

[0316]

[Table 128]

[0317]

[Table 129]

[0318]

[Table 130]

[0319]

[Table 131]

[0320]

[Table 132]

[0321]

[Table 133]

[0322]

[Table 134]

[0323]

[Table 135]

[0324]

[Table 136]

[0325]

[Table 137]

[0326]

[Table 138]

[0327]

[Table 139]

[0328]

[Table 140]

[0329]

[Table 141]

[0330]

[Table 142]

[0331]

[Table 143]

[0332]

[Table 144]

[0333]

[Table 145]

[0334]

[Table 146]

[0335]

[Table 147]

[0336]

[Table 148]

[0337]

[Table 149]

[0338]

[Table 150]

[0339]

[Table 151]

[0340]

[Table 152]

[0341]

[Table 153]

[0342]

[Table 154]

As a conventional reactive chromate treated steel sheet,
Chromic anhydride: 30 g / l, phosphoric acid: 10 g / l, Na
F: 0.5 g / l, K ₂ TiF ₆ : 4 g / l, spray treatment at a bath temperature of 40 ° C., followed by washing and drying to obtain the amount of chromium deposited (in terms of chromium metal). Manufactured a chromate-treated steel sheet of 20 mg / m ² . When this was subjected to a salt spray test under the same conditions as in this example, white rust was generated in about 24 hours. Therefore,
From these results and the results of this example, it can be seen that the organic-coated steel sheet of the present invention can provide much better corrosion resistance than the conventional chromate-treated steel sheet.

[0344]

As described above, the organically coated steel sheet of the present invention contains no hexavalent chromium in the processing solution during production or in the film component of the product, and furthermore, the organic coated steel sheet for use in building materials, home appliances, automobiles, etc. It has high corrosion resistance as a steel sheet,
Excellent paint adhesion.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C23C 28/00 C23C 28/00 A (72) Inventor Akihiko Furuta 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Inside Nippon Kokan Co., Ltd. (72) Akira Matsuzaki, Inventor 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Japan Inside Nippon Kokan Co., Ltd. (72) Takafumi Yamachi 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Japan Inside the Kokan Co., Ltd. (72) Tatsuya Miyoshi, 1-2-1, Marunouchi, Chiyoda-ku, Tokyo, Japan Inside Nihon Kokan Co., Ltd. (72) Takahiro Kubota 1-2-1, Marunouchi, Chiyoda-ku, Tokyo, Japan Inside the company (72) Inventor Masaru Sagiyama 1-2-1 Marunouchi, Chiyoda-ku, Tokyo Inside Nihon Kokan Co., Ltd. (72) Masaaki Yamashita Maru, Chiyoda-ku, Tokyo 1-2-1 Uchi terminus in Nippon Kokan Co., Ltd. F-term (reference) 4D075 CA33 DA06 DB01 DB05 DB07 EB01 EB02 EB43 EC01 EC10 EC15 4F100 AA03H AA04C AA04H AA17C AA18C AA19C AA20C AA23C AA24C AA25C AAB AB01ABD BA04 BA07 CA15D CA19D DE01C DE01H EA061 EH112 EH462 EH71B EJ642 EJ862 GB07 GB32 GB48 JB02 JB05D JB13D JB20H JL00 JM02C JM02D 4K026 AA02 AA07 AA09 AA12 AA13 CA04 BB02CA02 BA02 BA02 BA08 BA08 AA02 AB02 BA10 BA12 BA17 BA21 BB04 BC01 BC02 BC04 BC05 BC09 CA11 CA16 CA18 CA53

Claims (45)

[Claims] Claims: 1. A film containing (α) oxide fine particles and (β) phosphoric acid and / or a phosphoric acid compound as a first layer film on a surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. A composite oxide film having a thickness of 0.005 to 3 μm or a total adhesion amount of the component (α) and the component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ^2; OH group and / or C
An organic-coated steel sheet having excellent corrosion resistance, comprising an organic film having a thickness of 0.1 to 5 [mu] m using an organic polymer resin (A) having an OOH group as a base resin. 2. A film containing (α) oxide fine particles and (β) phosphoric acid and / or a phosphoric acid compound as a first layer film on a surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. A composite oxide film having a thickness of 0.005 to 3 μm or a total adhesion amount of the component (α) and the component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ^2; OH group and / or C
A film containing an organic polymer resin (A) having an OOH group as a base resin and containing 1 to 100 parts by weight (solid content) of an inorganic rust preventive pigment (a) based on 100 parts by weight (solid content) of the base resin. An organic-coated steel sheet having excellent corrosion resistance, comprising an organic film having a thickness of 0.1 to 5 μm. 3. A film containing (α) oxide fine particles and (β) phosphoric acid and / or a phosphoric acid compound as a first layer film on a surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. A composite oxide film having a thickness of 0.005 to 3 μm or a total adhesion amount of the component (α) and the component (β) in terms of P ₂ O ₅ of 6 to 3600 mg / m ^2; OH group and / or C
An organic polymer resin having an OOH group (A) is used as a base resin, and a film thickness containing 1 to 80 parts by weight (solid content) of a solid lubricant (b) with respect to 100 parts by weight (solid content) of the base resin is obtained. An organic coated steel sheet having excellent corrosion resistance, having an organic coating of 0.1 to 5 μm. 4. A film containing (α) oxide fine particles and (β) phosphoric acid and / or a phosphate compound as a first layer film on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. The thickness is 0.005 to 3 μm or the total amount of the component (α) and the component (β) in terms of P ₂ O ₅ is 6 to 3
It has a composite oxide film of 600 mg / m ² , and a OH group and / or C
An organic polymer resin (A) having an OOH group is used as a base resin, and 1 to 100 parts by weight (solid content) of an inorganic rust preventive pigment (a) is used with respect to 100 parts by weight (solid content) of the base resin. An organically coated steel sheet having excellent corrosion resistance, comprising an organic film having a thickness of 0.1 to 5 μm containing 1 to 80 parts by weight (solid content) of the agent (b). 5. The inorganic rust preventive pigment (a) in the organic film is one or more selected from a silica compound, a phosphate and a calcium compound. 5. The organic coated steel sheet having excellent corrosion resistance described in 3 or 4. 6. The organic coated steel sheet having excellent corrosion resistance according to claim 5, wherein the inorganic rust preventive pigment (a) in the organic film is ion-exchanged silica. 7. The organic coated steel sheet having excellent corrosion resistance according to claim 5, wherein the inorganic rust preventive pigment (a) in the organic film is fine-particle silica. 8. The inorganic rust preventive pigment (a) in the organic film comprises ion exchange silica (c) and fine particle silica (d),
And the weight ratio (c) / (d) of the content (solid content) of the ion-exchanged silica (c) and the fine particle silica (d) is from 1/99 to 9
The organic-coated steel sheet having excellent corrosion resistance according to claim 5, wherein the ratio is 9/1. 9. An excellent corrosion resistance according to claim 5, wherein the inorganic rust preventive pigment (a) in the organic film is zinc phosphate (e) and / or aluminum phosphate (f). Organic coated steel sheet. 10. The inorganic rust preventive pigment (a) in the organic film comprises zinc phosphate (e) and / or aluminum phosphate (f) and a calcium compound (g), and zinc phosphate (e) and And / or the weight ratio (e, f) / (g) of the total content (solid content) of aluminum phosphate (f) to the content (solid content) of calcium compound (g) is 1/99.
The organic-coated steel sheet having excellent corrosion resistance according to claim 5, wherein the thickness is from 99/1 to 99/1. 11. An ion exchange silica (c) in an organic film.
Is a Ca ion exchange silica, The organic coated steel sheet excellent in corrosion resistance according to claim 5, 6, or 8. 12. The organic coated steel sheet having excellent corrosion resistance according to claim 11, wherein the Ca ion-exchanged silica has an average particle size of 4 μm or less. 13. The Ca ion exchange silica having a Ca concentration of 2
11. The composition according to claim 11, wherein the content is about 8 wt%.
3. The organic coated steel sheet having excellent corrosion resistance according to 2. 14. The organic polymer resin (A) having an OH group and / or a COOH group is a thermosetting resin, wherein the organic polymer resin (A) is a thermosetting resin. 8,
The organic-coated steel sheet having excellent corrosion resistance according to 9, 10, 11, 12 or 13. 15. The organic polymer resin (A) having an OH group and / or a COOH group is an epoxy resin and / or a modified epoxy resin. 6, 7, 8, 9, 10, 11, 1
The organic-coated steel sheet excellent in corrosion resistance according to 2, 13, or 14. 16. The composition according to claim 1, wherein the component (α) contained in the composite oxide film is silicon oxide.
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
The organic-coated steel sheet excellent in corrosion resistance according to 13, 14, or 15. 17. The organic coated steel sheet having excellent corrosion resistance according to claim 16, wherein the primary particle diameter of silicon oxide is 8 nm or less. 18. The amount of silicon oxide contained as component (α) in the composite oxide film in terms of SiO ₂ is from 5 to 95% by weight based on the total adhesion amount of the composite oxide film. An organically coated steel sheet having excellent corrosion resistance according to claim 16. 19. The composite oxide film comprises the component (α) and
As (β), (α) SiO₂Fine particles of SiO₂0.01-3 in conversion amount
000mg / m²(Β) phosphoric acid and / or phosphate compound₂O₅Exchange
0.01 to 3000 mg / m by calculation², Containing and ingredients
(Α) and (β) have a total of 6 to 3600
mg / m ²18. The method according to claim 16, wherein
Or an organically coated steel sheet excellent in corrosion resistance according to 18. 20. The composite oxide film further comprises (γ) one or more metals selected from Mg, Ca, Sr, and Ba (provided that they are contained as compounds and / or composite compounds) And a film thickness of 0.005 to 3 μm or a total adhesion amount of the component (α), the component (β) in terms of P ₂ O ₅ and the component (γ) in terms of metal of 6 to 3600 mg. / M ² , wherein the ratio is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1.
The organic coated steel sheet excellent in corrosion resistance according to 1, 12, 13, 14, 15, 16, 17, 18 or 19. 21. The composite oxide film further comprises: (δ) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, one or more metals selected from Ce (including the case where they are included as a compound and / or a composite compound), and the film thickness is 0.005 to 3 μm
Alternatively, the total adhesion amount of the component (α), the component (β) in terms of P ₂ O ₅ , and the component (δ) in terms of metal is 6 to 3600 m.
g / m ² , wherein g / m ² .
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 1
The organic-coated steel sheet excellent in corrosion resistance according to 4, 15, 16, 17, 18 or 19. 22. The composite oxide film further comprises (γ) one or more metals selected from Mg, Ca, Sr, and Ba (provided that they are contained as a compound and / or a composite compound. (Δ) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, one or two or more metals selected from Ce (provided that they are included as compounds and / or composite compounds), and have a thickness of 0.005 to 3 μm.
m or the total amount of the component (α), the component (β) in terms of P ₂ O ₅ , the component (γ) in terms of metal, and the component (δ) in terms of metal is 6 to 3600 mg / m ² . Claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
19. The organic coated steel sheet having excellent corrosion resistance according to 17, 18, or 19. 23. The method according to claim 20, wherein the component (γ) contained in the composite oxide film is Mg (including the case where it is contained as a compound and / or a composite compound). Organic coated steel sheet with excellent corrosion resistance. 24. The component (δ) contained in the composite oxide film is one or two selected from Ni and Mn (both of which are included as compounds and / or composite compounds). 3. The method according to claim 2, wherein
The organic coated steel sheet having excellent corrosion resistance according to 1 or 22. 25. A composite oxide film comprising the components (α) and (β)
And (γ): (α) 0.01 to 3 SiO ₂ fine particles in terms of SiO ₂
000 mg / m ² , (β) phosphoric acid and / or a phosphate compound in an amount of 0.01 to 3000 mg / m ^{2 in} terms of P ₂ O ₅ , (γ) Mg (provided that they are contained as a compound and / or a complex compound ) In terms of Mg in an amount of 0.01 to 1
000 mg / m ² , and the total amount of the components (α), (β) and (γ) is 6 to 3600 mg / m ^2.
The organic-coated steel sheet excellent in corrosion resistance according to claim 20, characterized in that: 26. A composite oxide film comprising the components (α) and (β)
And (δ): (α) 0.01 to 3 SiO ₂ fine particles in terms of SiO ₂
000 mg / m ² , (β) phosphoric acid and / or a phosphate compound in an amount of 0.01 to 3000 mg / m ^{2 in} terms of P ₂ O ₅ , (δ) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, one or two or more metals selected from Ce (including those contained as compounds and / or composite compounds) in an amount of 0.01 to 1000 mg in terms of metal.
/ ^{M 2,} containing the component (alpha), the corrosion resistance of claim 21 or 24 total of the deposition amount is equal to or is 6~3600mg / ^{m 2} of (beta) and ([delta]) Excellent organic coated steel sheet. 27. A composite oxide film comprising component (α),
As (β), (γ) and (δ), (α) SiO ₂ fine particles are used in an amount of 0.01 to 3 in terms of SiO _2.
000 mg / m ² , (β) phosphoric acid and / or a phosphate compound in an amount of 0.01 to 3000 mg / m ^{2 in} terms of P ₂ O ₅ , (γ) Mg (provided that they are contained as a compound and / or a complex compound ) In terms of Mg in an amount of 0.01 to 1
000 mg / m ² , (δ) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, one or two or more metals selected from Ce (including those contained as compounds and / or composite compounds) in an amount of 0.01 to 1000 mg in terms of metal.
/ ^{M 2,} containing the component (α), (β), (γ) and the sum of the adhesion amount ([delta]) is in claim 22 or 24, characterized in that a 6~3600mg / ^{m 2} An organic coated steel sheet having excellent corrosion resistance as described. 28. The composition according to claim 28, wherein the component (γ) in the composite oxide film is Mg.
(Including the case where the component (γ)) and the component (α) are contained as a compound and / or a complex compound, and the ratio of the component (γ) to the component (α) is determined by the conversion of the component (γ) to Mg and the Si of the component (α).
1/100 in molar ratio [Mg / SiO ₂ ] with O ₂ conversion amount
3. The range of 100-1.
The organic coated steel sheet excellent in corrosion resistance according to 0, 22, 24, 25, 26 or 27. 29. The component (γ) in the composite oxide film is Mg
(Provided that the component (β) is contained as a compound and / or a complex compound), and the ratio of the component (β) to the component (γ) is the P ₂ O ₅ equivalent of the component (β) and the component (γ) 1/100 in molar ratio [P ₂ O ₅ / Mg]
3. The range of 100-1.
The organic-coated steel sheet excellent in corrosion resistance according to 0, 22, 24, 25, 26, 27 or 28. 30. The ratio of the component (δ) to the component (α) in the composite oxide film is the metal conversion amount Me of the component (δ) (however, when two or more metals are contained, the total amount thereof). And the molar ratio of the component (α) to the amount converted to SiO ₂ [Me / SiO ₂ ]
The organic-coated steel sheet having excellent corrosion resistance according to claim 21, wherein the ratio is in the range of 1/100 to 100/1. 31. The ratio of the component (β) to the component (δ) in the composite oxide film is determined by the P ₂ O ₅ conversion amount of the component (β) and the metal conversion amount Me (2 (In the case of containing more than one kind of metal, the total amount thereof) and the molar ratio [P ₂ O ₅ / Me] is 1
3. The range of / 2 to 2/1.
The organic-coated steel sheet excellent in corrosion resistance according to 1, 22, 23, 24, 26, 27, 28, 29 or 30. 32. The composite oxide film according to claim 1, further comprising an organic resin.
6, 7, 8, 9, 10, 11, 12, 13, 14, 1
5, 16, 17, 18, 19, 20, 21, 22, 2,
The organic-coated steel sheet excellent in corrosion resistance according to 3, 24, 25, 26, 27, 28, 29, 30 or 31. 33. The surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet is coated with at least (a) 0.001 to 3.0 mol / L of oxide fine particles, and (b) phosphoric acid and / or a phosphate compound. It is treated with an aqueous solution containing 0.001 to 6.0 mol / L in terms of P ₂ O ₅ , and then heated and dried to form a first layer film on the surface of the plated steel sheet. Fine particles, (β) phosphoric acid and / or a phosphoric acid compound, having a film thickness of 0.005 to 3 μm or the total adhesion of the above component (α) and the above component (β) in terms of P ₂ O ₅ 6 to 3
Forming a composite oxide film having a thickness of 600 mg / m ² and then forming a composite oxide film thereon,
A coating composition for forming an organic film containing the organic film constituent component described in 8, 9, 10, 11, 12, 13, 14 or 15 is applied, and the film is heated and dried to have a film thickness of 0.1 to 0.1.
A method for producing an organic-coated steel sheet having excellent corrosion resistance, comprising forming an organic film having a thickness of 5 μm. 34. A method for coating a surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet with at least (a) 0.001 to 3.0 mol / L of oxide fine particles, and (b) phosphoric acid and / or a phosphate compound. from 0.001 to 6.0 mol / L in terms _of P ₂ O ₅ content, (iii) Mg, Ca, Sr, each metal ion Ba, water-soluble ions comprising at least one of the metal, the metal A compound containing at least one of the above, and one or more selected from a composite compound containing at least one of the above metals in a total of 0.001 to 3.0 in terms of the metal amount of the above metal. Mol / L, containing pH 0.5 to
5 and then dried by heating to form a first layer film on the surface of the plated steel sheet, (α) oxide fine particles, (β) phosphoric acid and / or a phosphate compound, and (γ) ) Containing one or more metals selected from Mg, Ca, Sr, and Ba (including the case where they are included as compounds and / or composite compounds), and having a film thickness of 0.005 to 0.005. 3 μm or the above component (α) and P ₂ O ₅
The above component (β) in conversion and the above component (γ) in metal conversion
Forming a composite oxide film having a total adhesion amount of 6 to 3600 mg / m ² , and then forming a composite oxide film thereon.
3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 1
An organic film having a thickness of 0.1 to 5 μm is formed by applying a coating composition for forming an organic film containing the organic film constituents described in 3, 14, or 15, and drying by heating. For producing organic-coated steel sheets with excellent corrosion resistance. 35. A method for coating a surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet with at least (a) 0.001 to 3.0 mol / L of oxide fine particles, and (b) phosphoric acid and / or a phosphate compound. 0.001 to 6.0 mol / L in terms of P ₂ O ₅ (d) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, each metal ion of Ce, a water-soluble ion containing at least one of the above metals, a compound containing at least one of the above metals, and a composite compound containing at least one of the above metals. One or two or more of these metals in a total of 0.001-3.0 in terms of the metal amount of the metal.
Mol / L, and then treated with an acidic aqueous solution having a pH of 0.5 to 5 and then dried by heating to form a first layer film on the surface of the plated steel sheet. (Δ) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, one or two or more metals selected from Ce (provided that they are included as compounds and / or composite compounds), and have a thickness of 0.005 to 3 μm.
m or the total adhesion amount of the component (α), the component (β) in terms of P ₂ O ₅ and the component (δ) in terms of metal is 6
~ 3600 mg / m ² to form a composite oxide film,
Then, claim 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14, or 15
The coating composition for forming an organic film containing the organic film constituents described in 1) is applied, and dried by heating to obtain a film thickness of 0.1.
A method for producing an organically coated steel sheet having excellent corrosion resistance, comprising forming an organic film having a thickness of 1 to 5 μm. 36. The surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet, at least (a) 0.001-3.0 mol / L of oxide fine particles, and (b) phosphoric acid and / or a phosphoric acid compound. from 0.001 to 6.0 mol / L in terms _of P ₂ O ₅ content, (iii) Mg, Ca, Sr, each metal ion Ba, water-soluble ions comprising at least one of the metal, the metal A compound containing at least one of the above, and one or more selected from a composite compound containing at least one of the above metals in a total of 0.001 to 3.0 in terms of the metal amount of the above metal. Mol / L, (d) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, each metal ion of Ce, a water-soluble ion containing at least one of the above metals, a compound containing at least one of the above metals, and a composite compound containing at least one of the above metals. One or two or more of these metals in a total of 0.001-3.0 in terms of the metal amount of the metal.
Mol / L, and then treated with an acidic aqueous solution having a pH of 0.5 to 5 and then dried by heating to form a first layer film on the surface of the plated steel sheet. An acid and / or phosphoric acid compound, and (γ) one or more metals selected from Mg, Ca, Sr, and Ba (including the case where they are included as a compound and / or a composite compound), (Δ) Li, Mn, Fe, Co, Ni, Zn, Al, L
a, one or two or more metals selected from Ce (provided that they are included as compounds and / or composite compounds), and have a thickness of 0.005 to 3 μm.
m or the total amount of the component (α), the component (β) in terms of P ₂ O ₅ , the component (γ) in terms of metal, and the component (δ) in terms of metal, is 6 to 3600 mg / m. ^2. forming a composite oxide film, and then forming a composite oxide film on top of the composite oxide film.
Applying a coating composition for forming an organic film containing the organic film constituents described in 12, 13, 14, or 15, and drying by heating to form an organic film having a thickness of 0.1 to 5 μm. Manufacturing method of organic coated steel sheet with excellent corrosion resistance. 37. The organic-coated steel sheet excellent in corrosion resistance according to claim 33, wherein the additional component (a) in the aqueous solution for forming a composite oxide film is silicon oxide. Production method. 38. The organic material having excellent corrosion resistance according to claim 33, wherein the additional component (b) in the aqueous solution for forming a composite oxide film is ammonium phosphate. Manufacturing method of coated steel sheet. 39. The additive component (c) in the acidic aqueous solution for forming a composite oxide film is one selected from Mg ions, water-soluble ions containing Mg, compounds containing Mg, and composite compounds containing Mg. 39. The method for producing an organically coated steel sheet having excellent corrosion resistance according to claim 34, wherein the number is two or more. 40. The additive component (d) in the acidic aqueous solution for forming a complex oxide film contains Ni ions, Mn ions, water-soluble ions containing Ni, water-soluble ions containing Mn, compounds containing Ni, and Mn. Compound, compound compound containing Ni, M
36. A compound selected from the group consisting of compound compounds containing n and at least two of them.
40. The method for producing an organically coated steel sheet having excellent corrosion resistance according to 8 or 39. 41. An additive component (c) in an acidic aqueous solution for forming a composite oxide film, wherein at least one selected from the group consisting of Mg ions, water-soluble ions containing Mg, compounds containing Mg, and composite compounds containing Mg. The ratio of the additive component (c) to the additive component (a) is _two or more, and the molar ratio of the additive component (c) in terms of Mg and the additive component (a) in terms of SiO ₂ [Mg / 39, wherein the ratio of SiO ₂ ] is in the range of 1/100 to 100/1.
40. The method for producing an organic-coated steel sheet having excellent corrosion resistance according to 40. 42. The additive component (c) in the acidic aqueous solution for forming a composite oxide film is one selected from the group consisting of Mg ions, water-soluble ions containing Mg, compounds containing Mg, and composite compounds containing Mg. The ratio of the additive component (b) to the additive component (c) is two or more, and the molar ratio of the additive component (b) in terms of P ₂ O ₅ and the additive component (c) in terms of Mg is [ claim, characterized in that in P ₂ O ₅ / Mg] is in the range of 1/100 to 100/1 34,36,37,3
The method for producing an organically coated steel sheet having excellent corrosion resistance according to 8, 40 or 41. 43. The ratio of the additional component (d) to the additional component (a) in the acidic aqueous solution for forming the composite oxide film is such that the metal equivalent Me of the additional component (d) and the SiO 2 of the additional component (a) ₂
1/100 to 1 in molar ratio [Me / SiO ₂ ]
35. The range of 00/1.
6. The method for producing an organic-coated steel sheet having excellent corrosion resistance according to 6, 37, 38, 39, 40, 41 or 42. 44. A P ₂ O ₅ equivalent amount and additive component ratio of the additive component in an acidic aqueous solution for composite oxide film formation (b) and additive component (D) is added component (B) (D) In a molar ratio [P ₂ O ₅ / Me] with the metal conversion amount Me of 1/2 to 2/1
35. The apparatus according to claim 35, wherein
7. The method for producing an organic-coated steel sheet having excellent corrosion resistance according to 7, 38, 39, 40, 41, 42 or 43. 45. The aqueous solution for forming a composite oxide film further comprises an organic resin.
34, 35, 36, 37, 38, 39, 40, 41, 4
45. The method for producing an organically coated steel sheet having excellent corrosion resistance according to 2, 43 or 44.