JP2002030460A - Metallic surface treating agent, metallic surface treating method and surface treated metallic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chromium-free metallic surface treating agent used for imparting excellent corrosion resistance and alkali resistance to a metallic material and to provide a metallic surface treating method and a surface treated metallic material using the same. SOLUTION: This metallic surface treating agent contains at least one kind of vanadium compound (A) and a metallic compound (B) containing at least one kind of metal selected from the groups consisting of zirconium, titanium, molybdenum, tungsten, manganese and cerium. For further improving the physical properties thereof, the prescription of the ratio of pentavalent vanadium ions to the whole vanadium and the incorporation of an organic compound having a specific functional group, an etching agent, a water soluble high polymer or/and a water-based emulsion resin are possible. The metallic surface treating method and the surface treated metallic material use the same treating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal surface treating agent which can impart excellent corrosion resistance and alkali resistance to the surface of a sheet coil or a molded product made of a metal, and is used for forming a chromium-free film. , Metal surface treatment method,
It relates to a surface-treated metal material. More specifically, the present invention relates to a galvanized steel sheet, a steel sheet, an automobile body made of an aluminum-based metal material, an automobile part, a building material,
A surface treatment agent, a surface treatment method, and a surface-treated metal used to form a chromium-free coating that imparts excellent corrosion resistance and alkali resistance to molded products such as home appliance parts, cast products, sheet coils, and the like. About the material.

[0002]

2. Description of the Related Art Metal materials such as galvanized steel sheets, steel sheets, and aluminum metal materials are oxidized and corroded by oxygen, moisture, ions contained in moisture, and the like in the atmosphere. As a method of preventing such corrosion, there has been a method of forming a chromate film by bringing the surface of a metal material into contact with a treatment solution containing chromium such as chromate chromate and phosphoric acid chromate. Films formed by using these chromate treatments have excellent corrosion resistance and coating adhesion, but contain harmful hexavalent chromium in the treatment liquid, and wastewater treatment takes time and cost. In addition, since hexavalent chromium is also contained in the film formed by the treatment, it tends to be avoided from environmental and safety aspects.

[0003] Japanese Patent Application Laid-Open No. 7-278410 discloses a method for using a chromium-free non-chromate treatment solution, which is disclosed in Japanese Patent Application Laid-Open No. 7-278410. And a surface treatment method disclosed in Japanese Patent Application Laid-Open No. H8-73775, which includes two or more kinds of silane coupling agents having different types of reactive functional groups having specific structures capable of reacting with each other and having excellent fingerprint resistance and the like. Surface treatment agent and treatment method, JP-A-9-24
No. 1576 discloses a metal surface treating agent containing a silane coupling agent having a specific structure and a phenolic resin-based polymer having a specific structure and a processing method. Japanese Patent Application Laid-Open No. 10-1789 discloses a method having at least one nitrogen atom. Epoxy resin,
Acrylic resin, metal surface treatment agent containing an organic polymer such as urethane resin and a specific polyvalent anion, a treatment method and a treated metal material, JP-A-10-60233,
(1) a rust inhibitor containing a bisphenol A epoxy resin having a specific structure; (2) a solid content ratio of a phenolic resin and another specific resin such as polyester when mixed is 4:
Disclosed are a rust preventive contained in a ratio of 1 to 1: 4, a treatment method using (1) and (2), and a treated metal material. However, the metal surface treatments without chromium disclosed in these patent publications have the advantage that the treatment solution does not contain hexavalent chromium, but the formed film has insufficient corrosion resistance as compared with chromate, It has the disadvantage that the fingerprint and lubricity are insufficient.

[0004] Also, JP-A-10-1789 discloses that
Vanadic acid is described in the specified polyvalent anions, but vanadic acid, which is an oxygen acid of pentavalent vanadium, is inferior in water resistance and alkali resistance. Therefore, the treated metal material is washed particularly with alkali. When this was done, there was a problem that the coating dropped off from the film and the corrosion resistance was extremely reduced. In addition, it describes that after treatment, washing and drying are performed, and there is no problem of chromium wastewater, but there is a problem of wastewater such as COD due to organic substances.

In addition, as an invention using a vanadium compound as a rust inhibitor, Japanese Patent Application Laid-Open No. 1-9229 discloses a phosphate ion source which releases phosphate ions in an environment where water and oxygen are present, and a vanadate ion. Patent No. 2795710 discloses a vanadate ion source containing a vanadate ion source and a film-forming resin, and discloses (A) a specific concentration of vanadate ion in a dispersion dispersed in water. There is disclosed a rust preventive composition in which a vanadate ion source and (B) a specific compound such as an organic phosphonic acid having a specific concentration of solubility in a water dispersion are mixed at a specific ratio. The vanadate ion source is added to act as a rust-preventive pigment for the rust-preventive paint, and when the vanadate ion source is fired at a high temperature of 600 ° C. or more, a pigment having an average particle size of several μm is obtained. The pigment particles exhibit an anticorrosion effect in a coating film having a certain thickness (several times the particle size of the pigment),
No anticorrosion effect can be exhibited at all in a thin film (several μm or less) in the field of surface treatment. Further, when the treating agent is left, there is a problem that these particles are aggregated and settle therein.

Therefore, at present, a non-chromate metal surface treating agent capable of forming a film capable of simultaneously imparting excellent corrosion resistance, alkali resistance and fingerprint resistance to the surface of a metal material has not been obtained.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and
It is an object of the present invention to provide a chromium-free metal surface treatment agent, a metal surface treatment method, and a surface treated metal material used for imparting excellent corrosion resistance and alkali resistance to a metal material.

[0008]

Means for Solving the Problems The present inventors have solved the above problem by treating the surface of a metal material with a surface treatment agent containing a vanadium compound and a specific metal compound as essential components. The inventors have found that a film having excellent corrosion resistance and alkali resistance can be obtained, and have completed the present invention. That is, the present invention includes at least one vanadium compound (A) and a metal compound (B) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium. A metal surface treatment agent characterized by the following:

In the above-mentioned vanadium compound (A), the ratio V ⁵⁺ / V of vanadium ions having a valence of 5 to the total vanadium is in the range of 0 to 0.6, which means that the stability of the vanadium compound in the treating agent is high. It is preferable from the viewpoints of improving properties, corrosion resistance of the formed film, and alkali resistance. Further, the metal surface treating agent further has at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group and a phosphonic acid group. Including the organic compound (C)
When a pentavalent vanadium compound is used, the pentavalent
It is preferable to reduce to divalent and / or to improve the stability of the vanadium compound in the treatment liquid of the present invention.

[0010] Further, the metal surface treating agent may further contain at least one etching agent (D) selected from inorganic acids, organic acids and fluorine compounds in order to improve the adhesion of the film to be formed. preferable. Further, the metal surface treating agent may further contain a water-soluble polymer and / or an aqueous emulsion resin (E) to improve the corrosion resistance, fingerprint resistance, solvent resistance and surface lubricity of the film to be formed. Preferred.

The present invention is further characterized in that after treating the surface of a metal material with any one of the above-mentioned metal surface treating agents, the material is heated and dried so that the temperature of the material is 50 to 250 ° C. The present invention relates to a method for surface treatment of a material. The present invention further relates to a surface-treated metal material having a film formed by using the surface treatment method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The vanadium compound (A) contained in the metal surface treating agent of the present invention has a pentavalent, tetravalent, trivalent or divalent vanadium compound, such as vanadium pentoxide (Vanadium pentoxide). V ₂ O ₅ ), metavanadic acid (HV
O ₃ ), ammonium metavanadate, sodium metavanadate, vanadium compounds having a valence of 5, such as vanadium oxytrichloride (VOCl ₃ ), vanadium trioxide (V ₂ O ₃ ), vanadium dioxide (VO ₂ ), vanadium oxysulfate (VOSO ₄ ), vanadium oxyacetylacetonate [VO (OC (CH ₃ ) = CHCOC]
H ₃ )) ₂ ], vanadium acetylacetonate [V (O
C (CH ₃ ) = CHCOCH ₃ )) ₃ ], vanadium trichloride (VCl ₃ ), rimvanadomolybdate {H ₁₅ -X
[PV ₁₂ -xMoxO ₄₀ ] · nH ₂ O (6 <x <12,
n <30)}, vanadium sulfate _{(VSO 4 · 7H 2 O)} ,
Vanadium dichloride (VCl ₂ ), vanadium oxide (V
At least one selected from vanadium compounds having an oxidation number of 4 to 2 such as O).

It is preferable that the treating agent contains a vanadium compound having an oxidation number of 4 or less (usually 4 to 2) as the vanadium compound (A). That is, the ratio V ⁵⁺ / V of vanadium ions having a valence of 5 to all vanadium ions
(Wherein, V ⁵⁺ and V respectively represent the mass of vanadium having a valence of 5 and the total mass of vanadium), preferably in the range of 0 to 0.6, and more preferably in the range of 0 to 0.4. More preferably, it is more preferably in the range of 0 to 0.2, and most preferably in the range of 0 to 0.1. When the above ratio exceeds 0.6, the stability of the vanadium compound in the treating agent generally deteriorates, and the corrosion resistance and alkali resistance of the formed film decrease.

As a method of including a 4- to 2-valent vanadium compound in the present treating agent, a 4- to 2-valent vanadium compound as described above may be used. Those reduced to divalent can be used. The reducing agent to be used may be either an inorganic type or an organic type, but is preferably an organic type, and particularly preferably uses the organic compound (C).

The metal surface treating agent of the present invention contains
The metal compound (B) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium is an oxide, hydroxide, complex compound, inorganic acid, or organic acid of the metal. And the like. Examples of the metal compound (B) include zirconyl nitrate (ZrO (NO ₃ ) ₂ ), zirconyl acetate, zirconyl sulfate, zirconyl ammonium carbonate {(NH ₄ ) ₂ [Zr (CO ₃ ) ₂ (OH) ₂ }, Zirconium acetate, titanyl sulfate (TiOSO ₄ ), titanium lactate, diisopropoxytitanium bisacetylacetone {(C ₅ H ₇ O ₂ ) ₂ Ti [OCH (CH ₃ ) ₂ ]
₂ ｝, reaction product of lactic acid and titanium alkoxide, molybdic acid (H ₂ MoO ₄ ), ammonium molybdate,
Sodium molybdate, molybdophosphate compound (for example, ammonium molybdophosphate @ (NH ₄ ) ₃ [PO _{4
Mo 1 2 O 36] · 3H} 2 O}, sodium molybdophosphate _{{Na 3 [PO 4 · 12MoO} 3] · nH 2 O}), metatungstate _{{H 6 [H 2 W 12} O 40]}, metatungstate Ammonium salt {(NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ]}, sodium metatungstate, paratungstate {H
₁₀ [W ₁₂ O ₄₆ H ₁₀ ]｝, ammonium paratungstate, sodium paratungstate, permancanoic acid (H
MnO ₄ ), potassium permanganate, sodium permanganate, manganese dihydrogen phosphate [Mn (H ₂ P
O ₄ ) ₂ ], manganese nitrate [Mn (NO ₃ ) ₂ ], manganese sulfate, manganese fluoride, manganese carbonate (MnCO ₃ ),
Manganese acetate, cerium acetate [Ce (CH ₃ C
O ₂ ) ₃ ], cerium nitrate, cerium chloride and the like.

The organic compound (C) to be contained in the metal surface treating agent of the present invention, if necessary, includes a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group,
It is an organic compound having at least one functional group selected from the group consisting of a phosphate group and a phosphonic acid group. Such organic compounds (C) include methanol, ethanol,
Alcohols such as isopropanol and ethylene glycol, formaldehyde, acetaldehyde, furfural, acetylacetone, ethyl acetoacetate, dipivaloylmethane, carbonyl compounds such as 3-methylpentanedione, formic acid, acetic acid, propionic acid, tartaric acid, ascorbic acid, glucone Acids, organic acids such as citric acid and malic acid, amine compounds such as triethylamine, triethanolamine, ethylenediamine, pyridine, imidazole, pyrrole, morpholine and piperazine, acid amides such as formamide, acetamide, propionamide and N-methylpropionamide Compounds, amino acids such as glycine, alanine, proline, glutamic acid, aminotri (methylene phosphonic acid), 1-hydroxyethylidene-1,1 ′
Organic phosphoric acid such as diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), phytic acid, glucose,
Mannose, monosaccharides such as galactose, maltose, oligosaccharides such as sucrose, starch, natural polysaccharides such as cellulose, tannic acid, humic acid, ligninsulfonic acid, aromatic compounds such as polyphenols, polyvinyl alcohol,
Examples include synthetic polymers such as polyethylene glycol, polyacrylic acid, polyacrylamide, polyethyleneimine, and water-soluble nylon. Among these organic compounds,
At least one selected from the above functional groups in one molecule
Preferably, the organic compound contains at least two functional groups selected from a hydroxyl group, a carbonyl group, a carboxyl group, a phosphoric acid group and a phosphonic acid group in one molecule.

The use of these organic compounds (C) is achieved by reducing the pentavalent vanadium compound to tetravalent, trivalent or divalent when it is used, and / or reducing the vanadium compound in the treatment solution of the present invention. It is preferable to improve the stability of the compound.

The organic compound (C) is mixed with a vanadium compound in advance and heated (for example, at 40 to 100 ° C. for 5 to 120
The mixture can be mixed with the surface treatment agent as a mixture that has undergone sufficient reduction and stabilization reactions, for example, by applying it to the metal surface as a mixed surface treatment agent. Can be advanced.

The etching agent (D) to be contained in the metal surface treating agent of the present invention, if necessary, is at least one compound selected from inorganic acids, organic acids and fluorine compounds. The etching agent (D) to be contained in the surface treatment agent of the present invention, if necessary, may be an inorganic acid, an organic acid, or a salt of an inorganic acid or an organic acid (particularly, an alkali metal such as an ammonium salt, a sodium salt, or a potassium salt). Salt) and at least one compound selected from fluorine compounds. The compound is used for etching a material metal at the time of applying a treating agent or drying by heating. As the etching agent (D), phosphoric acid,
Inorganic acids such as nitric acid and sulfuric acid or salts thereof (especially ammonium salts, sodium salts and potassium salts), organic acids such as formic acid and acetic acid or salts thereof (especially ammonium salts, sodium salts and potassium salts), hydrofluoric acid , Hydrofluoric acid (HBF ₄ ), hydrosilicic acid (H ₂ SiF ₆ ), zirconium hydrofluoric acid (H ₂ ZrF ₆ ), titanium hydrofluoric acid (H ₂ TiF ₆ ), tin (I) (SnF ₂ ),
Fluorine compounds such as tin (II) fluoride (SnF ₄ ), ferrous fluoride, and ferric fluoride can be used. Use of the etching agent (D) is preferable for improving the adhesion of the film to be formed.

The amount of each component in the treating agent of the present invention is preferably from 1 to 200 g / L, more preferably from 2 to 100 g / L, in terms of vanadium compound (A). The metal compound (B) is 1 to 200 g in terms of metal.
/ L is preferable, and 2 to 100 g / L is more preferable. Further, the mass ratio of the vanadium compound (A) / the metal compound (B) is preferably 1/9 to 9/1 in terms of metal, and is preferably 2/8 to 8/1.
/ 2 is more preferred. The organic compound (C) is preferably 0.05 to 10, and more preferably 0.1 to 5, assuming that the mass of pentavalent vanadium in the vanadium compound is 1. The addition in excess of the amount required for reduction is more preferable in order to improve the stability of the reduced form in the treatment solution.
The etching agent (D) is preferably 1 to 200 g / L,
-100 g / L is more preferred.

In the treating agent of the present invention, a water-soluble polymer and / or an aqueous emulsion resin (E) such as polyacrylic acid and polyacrylamide are used for the purpose of improving corrosion resistance, fingerprint resistance, solvent resistance and surface lubricity. , Polyvinyl alcohol, water-soluble polymers such as polyethylene glycol,
Aqueous emulsion resins such as acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin, polyolefin resin, ethylene-acrylic acid copolymer resin, polyacetal resin, and polybutyral resin dispersed in water can be added. . These can be used alone or in combination of two or more. The resin in the aqueous emulsion resin (E) may be dispersed in a liquid state or in a solid state. The addition amount of the water-soluble polymer and / or the aqueous emulsion resin (E) is preferably from 5 to 95% by mass, more preferably from 10 to 90% by mass of the total nonvolatile components.

In the treating agent of the present invention, a silica sol dispersed in water and / or a metal sol such as an alumina sol or a zirconia sol can be added. By adding these, corrosion resistance, water resistance and fingerprint resistance are improved. In this case, the amount to be added is 2 to 80% by mass of the total nonvolatile components.
Is preferable, and 5 to 60 mass% is more preferable. Further, in the treating agent of the present invention, a silane coupling agent such as aminosilane, epoxysilane, mercaptosilane and the like can be added. By adding these, adhesion and corrosion resistance are improved. In this case, the amount to be added is preferably 5 to 40% by mass, more preferably 10 to 30% by mass of the total nonvolatile components.

Further, in the treating agent of the present invention, a lubricant such as polyethylene wax, polypropylene wax, microcrystalline wax, carnauba wax and polytetrafluoroethylene can be added. By adding these, slip properties, moldability, and scratch resistance can be imparted. In this case, the amount to be added is preferably from 1 to 40% by mass, more preferably from 5 to 30% by mass of the total nonvolatile components. In the present invention, the term “all non-volatile components” refers to components remaining after the surface treatment agent is dried by heating at 110 ° C. for 2 hours.

The solvent used in the surface treatment agent of the present invention is mainly water, but does not prevent the combined use of alcohol, ketone, and cellosolve-based water-soluble organic solvents as required, such as improvement of the drying property of the film. In addition, a surfactant, an antifoaming agent, a leveling agent, a bactericidal / antibacterial agent, a coloring agent, and the like can be added as long as the purpose of the present invention and the film performance are not impaired.

Next, the surface treatment method of the present invention will be described. Although there is no particular limitation on the pre-process of this treatment, usually, before performing this treatment, the material is washed with an alkaline degreaser or an acidic degreaser to remove oil and dirt attached to the material, or is washed with hot water or a solvent. Perform cleaning, etc. Thereafter, if necessary, the surface is adjusted with an acid, an alkali, or the like. In the cleaning of the material surface, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the material surface as much as possible.

In the present treatment method, it is sufficient that the surface treatment agent of the present invention can be dried by heating at 50 to 250 ° C. after being applied to the surface of the metal material, and there are no particular restrictions on the application method and drying method. Usually, a roll coating method in which the treatment agent is transferred to the material surface by roll transfer, or a method in which the treatment agent is squeezed with a roll after pouring with a shower ringer, a method in which the material is immersed in the treatment liquid, and a method in which the treatment agent is sprayed on the material Used. The temperature of the treatment liquid is not particularly limited, but since the solvent of the treatment agent is mainly water,
The treatment temperature is preferably from 0 to 60C, more preferably from 5 to 40C.

The drying step does not necessarily require heat, and may be air drying or physical removal such as air blow. However, drying may be performed by heating to improve the film forming property and adhesion. In that case, the temperature is preferably from 50 to 250C, more preferably from 60 to 220C.

The coating amount of the formed film is 0.
005 to 1.5 μm, preferably 0.01 to 1.0 μm
Is more preferred. If the thickness is less than 0.005 μm, sufficient corrosion resistance and adhesion to the top coat cannot be obtained, and if the thickness exceeds 1.5 μm, cracks or the like may occur in the coating and the adhesion of the coating itself may be reduced.

By providing an organic polymer film on the film formed from the surface treating agent of the present invention so that the dry film thickness becomes 0.3 to 3.0 μm, the corrosion resistance and alkali resistance of the metal material to be treated are improved. , As well as fingerprint resistance, solvent resistance and surface lubricity.

As a method for providing such an organic polymer film, an overcoating agent (Z) containing a water-soluble or water-dispersible organic polymer as a main component is applied, and the temperature of the material reaches 50%.
A method of heating and drying at ~ 250 ° C is desirable. The water-soluble or water-dispersible organic polymer used for the overcoat treatment agent (Z) is
An acrylic resin obtained by polymerizing an addition polymerizable unsaturated monomer, a polyolefin resin, an epoxy resin obtained by a condensation reaction, a urethane resin, a polyester resin, a polyamide resin, a phenol resin, and the like.
The glass transition point of the organic polymer is preferably from 0 to 120 ° C, more preferably from 10 to 100 ° C. If the temperature is lower than 0 ° C, the strength and hardness of the film are poor, and the temperature is 120 ° C.
If it exceeds 3, film-forming properties are inferior and adhesion is inferior.

It is preferable that the above-mentioned overcoating agent contains at least one selected from these organic polymers, and further contains water-dispersible silica in order to improve the toughness and fingerprint resistance of the film. In order to further improve lubricity, it is desirable to add a water-based wax. The content of these components is, assuming that the total nonvolatile content is 100 parts by mass, the organic polymer is 50 to 100 parts by mass in the nonvolatile content,
0 to 40 parts by mass of water-dispersible silica, 0 to
30 parts by weight are preferred. Further, a crosslinking agent capable of crosslinking an organic polymer can be contained.

[0032]

The surface treating agent of the present invention is applied to a base metal,
Reacts with the material metal surface when heated and dried. Form a dense passive film. The film formed by the surface treatment agent of the present invention exhibits excellent corrosion resistance because of the barrier effect of blocking the transmission of oxygen, moisture and ions of the film, as well as the effect of delocalizing corroded electrons (smoothing potential). ). Vanadium compound (A) specified in the present invention
In the above, the pentavalent vanadium compound is present as a polyvalent anion bonded to oxygen and has poor water resistance and alkali resistance, so that sufficient performance cannot be obtained, but a reduced tetravalent vanadium compound and a trivalent vanadium compound It is considered that a film formed using a treatment agent containing at least one of a vanadium compound and a divalent vanadium compound has improved water resistance and alkali resistance. Further, the organic compound (C) used is at least one of tetravalent, trivalent and divalent reduced in the aqueous solution at the same time as the reduction of the pentavalent vanadium compound.
It is considered that vanadium having various valences has an effect of chelating and stabilizing in an aqueous solution. When a top coat mainly composed of an organic polymer is applied on the film of the present invention, the corrosion resistance is further increased due to a synergistic effect with the barrier effect of the top coat.

[0033]

Next, the present invention will be described with reference to examples and comparative examples. However, the present examples are merely examples, and do not limit the present invention. The evaluation method for the processed plate samples produced in the examples and comparative examples is as follows. 1. Material a: Electro-galvanized steel sheet (sheet thickness: 0.8 mm) b: Hot-dip galvanized steel sheet (sheet thickness: 0.8 mm) c: 55% aluminum galvanized steel sheet (sheet thickness: 0.5 mm)

2. Treatment liquid of the present invention (1) Components of treatment liquid The vanadium compound (A) used is described below. A1: Ammonium metavanadate A2: Vanadium pentoxide A3: Vanadium trioxide A4: Vanadium oxyacetylacetonate The metal compound (B) used is described below. B1: ammonium molybdate B2: ammonium metatungstate B3: ammonium zirconium carbonate B4: fluorotitanic acid B5: manganese carbonate

The organic compound (C) used is described below. C1: L-ascorbic acid C2: D-glucose C3: glyoxal C4: citric acid The etching agent (D) used is described below. D1: HF D2: H ₂ ZrF ₆ D3: CH ₃ COOH D 4: H ₂ SiF ₆ D5: (NH ₄ ) ₂ HPO ₄

The used water-soluble polymer and / or aqueous emulsion resin (E) is shown below. E1: Water-based polyurethane resin (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Superflex 100) E2: Water-based ethylene-acrylic acid copolymer resin (ethylene / acrylic acid = 80/20 *, average molecular weight about 20,000) E3: Water-based epoxy resin (Adeka Resin EPEA-0434 manufactured by Asahi Denka Kogyo KK) E4) water-based acrylic resin (butyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid / glycidyl methacrylate / styrene =
50/20/5/8/2/15) * * The figures are mol%

(2) Preparation of treatment liquid In the case of Examples 1 to 7 and Comparative Examples 1 and 2, a vanadium compound (A), a metal compound (B), an etching agent (D) and deionized water were mixed. Heated at 0 ° C. for 1 hour. In the case of Examples 8 to 16 and Comparative Example 3 After mixing the vanadium compound (A) with a 5% aqueous solution of the organic compound (C), the mixture was heated at 80 to 100 ° C for 30 minutes,
After cooling to room temperature, the metal compound (B) and the etching agent (D) were added, and finally, deionized water was added to adjust the concentration to a predetermined value. In the case of Examples 17 to 21 and Comparative Example 4 After mixing the vanadium compound (A) with a 5% aqueous solution of the organic compound (C), the mixture was heated at 80 to 100 ° C for 30 minutes,
After cooling to room temperature, the metal compound (B), the etching agent (D), the water-soluble polymer and / or the aqueous emulsion resin (E) were added, and finally, deionized water was added to adjust to a predetermined concentration.

3. Topcoat treatment liquid The topcoat treatment agent (Z) used and the treatment method are described below. Z1: 100 parts by mass of water-based polyurethane (Superflex 100, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 20 parts by mass of water-based silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) in terms of silica, water-based wax (Mitsui Chemicals, Inc.
Aqueous treatment liquid having a solid content of 10 parts by mass and having a nonvolatile content of 10%. Z2: 100 parts by mass of an ammonia-neutralized water-based polymer of an ethylene-acrylic acid copolymer (ethylene / acrylic acid = 80/20, average molecular weight: about 20,000) in terms of solid content, and water-dispersible silica being 10 in terms of silica. A water-based treatment liquid having a nonvolatile content of 20% by mass.

4. Treatment method (1) Degreasing The material was degreased with an alkali degreasing agent PALCLEAN 364S (manufactured by Nippon Parkerizing Co., Ltd., 20 g / L bath, 60 ° C, 10 seconds spray, spray pressure 50 kPa), and then spray-washed for 10 seconds. . (2) Application and Drying of the Treatment Liquid of the Present Invention I: The treatment liquid was applied using a bar coater # 3 and dried at a plate temperature of 80 ° C. using a hot air circulation oven. II: The treatment liquid was applied with a bar coater # 3, and dried at a plate temperature of 120 ° C. using a hot air circulation type oven.

(3) Coating and Drying of the Topcoat Treatment Solution The topcoat treatment solution is applied by bar coating onto a film formed by using the treatment solution and the treatment method of the present invention so that the dry film thickness becomes about 1 μm. And dried by heating at a plate temperature of 100 ° C.

5. Evaluation method (1) Corrosion resistance Based on the salt spray test method JIS-Z-2371, the area of white rust occurrence after 72 hours and 120 hours after salt spray was determined and evaluated. Evaluation criteria: White rust generation area ◎ Less than 10%, ○ 10% or more and less than 30%, Δ30% or more and less than 60%, × 60% or more (2) Alkali resistance Alkaline degreasing agent manufactured by Nippon Parkerizing Co., Ltd. Palclean 364S was bathed at 20 g / L, sprayed with a degreasing agent aqueous solution adjusted to 60 ° C for 30 seconds, washed with water, and then dried at 80 ° C. This plate was evaluated for corrosion resistance under the conditions and evaluation method described in (1) above.

(3) Fingerprint Resistance A finger was pressed against the surface of the treated plate, and the trace of the fingerprint was visually observed and evaluated. Evaluation criteria: ◎ No trace at all, ○ Very slight trace,
△ There is a trace, × a clear trace remains. (4) Solvent resistance A gauze impregnated with ethanol is wound around a silicone rubber cube (1 cm square), and the test surface is 50,000 kP.
Rubbing was performed 10 times in a. Evaluation criteria: ◎ Almost no film peeling, ○ Slight film peeling, Δ Partial film peeling, × Film peeled over the entire surface and the substrate was visible

Tables 1, 2 and 3 show the treatment liquid contents and treatment methods of Examples and Comparative Examples, and Tables 4 and 5 show the evaluation results of the treated plates. As shown in Table 4, the coating formed from the treating agent of the present invention (Examples 1 to 16) containing the specific vanadium compound (A) and the specific metal compound (B) shows excellent corrosion resistance and alkali resistance. I understand. In comparison, Comparative Examples 1 to 3 containing no vanadium compound (A) or metal compound (B) were inferior in corrosion resistance and alkali resistance. From Table 5, Examples 17 to 21 and Example 1
(Examples 22 to 32) obtained by applying a top coat resin film (Z1 or Z2) on the films Nos. 11 to 11 are excellent in corrosion resistance and alkali resistance, and also excellent in fingerprint resistance and solvent resistance. . In comparison, Comparative Examples 4 to 7, which did not contain the vanadium compound (A) or the metal compound (B), were inferior in corrosion resistance and alkali resistance, and inferior in solvent resistance.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

Example 22 The film formed in Example 1 was treated with an overcoating agent Z1. Example 23 The film formed in Example 2 was treated with an overcoat treatment agent Z1. Example 24 The film formed in Example 3 was treated with an overcoat treatment agent Z1. Example 25 The film formed in Example 4 was treated with an overcoat treatment agent Z2. Example 26 The film formed in Example 5 was treated with the overcoat treatment agent Z1. Example 27 The film formed in Example 6 was treated with an overcoat treatment agent Z2. Example 28 The film formed in Example 7 was treated with the overcoat treatment agent Z1. Example 29 The film formed in Example 8 was treated with an overcoat treatment agent Z2. Example 30 The film formed in Example 9 was treated with the overcoat treatment agent Z1. Example 31 The film formed in Example 10 was treated with the overcoat treatment agent Z2. Example 32 The film formed in Example 11 was treated with the overcoat treatment agent Z2.

Comparative Example 5 The film formed in Comparative Example 1 was treated with the overcoating agent Z1. Comparative Example 6 Overcoating agent Z was applied on the film formed in Comparative Example 2.
1 was performed. Comparative Example 7 Finishing agent Z on the film formed in Comparative Example 3
2 was performed.

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

The treating agent of the present invention is a non-chromate type containing no harmful chromium compound, and the film formed from the surface treating agent has corrosion resistance equal to or higher than that of a conventional chromate film. And the surface treatment agent of the present invention,
The surface treatment method and the surface treated metal material have extremely high industrial utility value.

 ────────────────────────────────────────────────── ─── Continued on front page (72) Inventor Mayumi Yamamoto 1-15-1 Nihonbashi, Chuo-ku, Tokyo Japan F-term in Parkerizing Co., Ltd. (reference) 4K026 AA02 AA07 AA09 AA12 AA13 AA22 BA01 BA08 BA12 BB04 BB08 BB09 BB10 CA16 CA18 CA24 CA26 CA28 CA29 CA30 CA31 CA32 CA33 CA36 CA37 CA38 CA39 CA41 DA11 EA08 EB08

Claims (7)

[Claims] 1. A composition comprising at least one vanadium compound (A) and a metal compound (B) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese and cerium. A metal surface treatment agent characterized by the following. 2. The metal surface treating agent according to claim 1, wherein in the vanadium compound (A), the ratio V ⁵⁺ / V of vanadium ions having a valence of 5 to all vanadium is in the range of 0 to 0.6. 3. An organic compound (C) having at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group and a phosphonic acid group. The metal surface treating agent according to claim 1 or 2, which comprises: 4. The metal surface treating agent according to claim 1, further comprising at least one etching agent (D) selected from an inorganic acid, an organic acid and a fluorine compound. 5. The metal surface treating agent according to claim 1, further comprising a water-soluble polymer and / or an aqueous emulsion resin (E). 6. After treating the surface of a metal material with the metal surface treating agent according to any one of claims 1 to 5, heating and drying the material to a temperature of 50 to 250 ° C. Characteristic surface treatment method for metal materials. 7. A surface-treated metal material having a film formed by using the surface treatment method according to claim 6.