JP4521010B2 - Metal surface treatment agent, metal surface treatment method and surface treatment metal material - Google Patents

Description

The present invention provides a sheet coil made of metal as a raw material, imparts excellent corrosion resistance and alkali resistance to the surface of a molded product, and further has excellent interlayer adhesion between a resin layer and a metal material formed by painting or lamination, and chromium. The present invention relates to a metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material that are used for forming a film that does not contain a metal.
More specifically, the present invention relates to a steel body such as steel, zinc-based plated steel, and aluminum-based plated steel, as well as a non-ferrous metal material such as aluminum, magnesium, copper, and alloys thereof. , Surface treatment agents used for forming molded products such as home appliance parts, cast products, sheet coils and the like, which are excellent in corrosion resistance and alkali resistance, and further excellent in interlayer adhesion and forming a chromium-free film, The present invention relates to a surface treatment method and a surface-treated metal material.

Steel, zinc-plated steel, aluminum-plated steel, and other non-ferrous metal materials such as aluminum, magnesium, copper, and alloys thereof are oxidized by oxygen, moisture, ions contained in moisture, etc. Corrosion. As a method for preventing such corrosion, conventionally, there is a method of forming a chromate film by bringing a metal material surface into contact with a treatment liquid containing chromium such as chromate chromate and phosphate chromate.
Films formed using these chromate treatments have excellent corrosion resistance and paint adhesion, but contain harmful hexavalent chromium in the treatment liquid, which requires labor and cost for wastewater treatment. In addition, since the film formed by the treatment contains hexavalent chromium, it tends to be avoided from the environmental and safety aspects.

  As a method of using a non-chromate treatment liquid not containing chromium, Patent Document 1 discloses a metal containing an organic polymer such as an epoxy resin, an acrylic resin, or a urethane resin having at least one nitrogen atom and a specific polyvalent anion. A surface treatment agent is disclosed. Here, vanadic acid is described in the specified polyvalent anion, but vanadic acid, which is an oxygen acid of pentavalent vanadium, is inferior in water resistance and alkali resistance. When washed with, etc., there was a problem that the corrosion resistance dropped drastically from the film. Moreover, although it describes that it wash | cleans and dries after a process and there is no problem of chromium wastewater, it has the problem of wastewater, such as COD by an organic substance.

Patent Document 2 includes a metal surface treatment agent containing a vanadium compound and a metal compound containing at least one metal selected from zirconium, titanium, molybdenum, tungsten, manganese, and cerium.
The metal surface treatment described in Patent Document 2 has an advantage that the treatment liquid does not contain hexavalent chromium, and the formed film is considerably improved in corrosion resistance and alkali resistance.
JP-A-10-1789 (Claims 1 to 3) JP 2002-30460 A (Claim 1)

The metal surface treatment described in Patent Document 2 can provide a film having good corrosion resistance and alkali resistance, but it is still not sufficient as compared with the chromate film, and further improvement of these performances has been demanded.
The present invention was made in order to solve the problems of the prior art, and provides excellent corrosion resistance and alkali resistance to a metal material, and also provides excellent interlayer adhesion, and does not contain chromium. An object is to provide a metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material.

As a result of intensive research on the means for solving the above problems, the present inventor treated the surface of a metal material using a surface treatment agent having a specific composition, thereby providing excellent corrosion resistance, alkali resistance and interlayer adhesion. The present inventors have found that a film having the above can be obtained, and have completed the present invention.
That is, the present invention provides at least one vanadium compound (A) and a metal compound (B) containing at least one metal selected from the group consisting of cobalt, nickel, zinc, magnesium, aluminum, calcium, strontium, barium and lithium. And a metal surface treatment agent.

In the present invention, interlayer adhesion refers to adhesion between a film obtained by using a metal surface treatment agent such as the metal surface treatment agent of the present invention and a resin film usually applied thereon, and the film. It means both adhesion to the metal surface. However, in practice, the film obtained by using the metal surface treatment agent such as the metal surface treatment agent of the present invention is a chemical conversion film that has good adhesion to the metal surface. Adhesion usually means adhesion to a resin film. However, a resin component can be contained in the coating itself, and in this case, interlayer adhesion means adhesion to the metal surface.

In the present invention, the surface treatment agent may further contain a metal compound (C) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese and cerium. It is preferable in order to improve alkalinity and adhesion between tree layers.
In the vanadium compound (A), the ratio V ⁵⁺ / V of the pentavalent oxide vanadium ion to the total vanadium is in the range of 0 to 0.6, the stability of the vanadium compound in the treatment agent, From the viewpoint of improving the corrosion resistance, alkali resistance and interlayer adhesion of the formed film.
The metal surface treatment 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. When the pentavalent vanadium compound is used, the inclusion of the organic compound (D) reduces the tetravalent to divalent and / or improves the stability of the vanadium compound in the treatment liquid of the present invention. Therefore, it is preferable.

Moreover, the metal surface treatment agent further contains at least one etching agent (E) selected from an inorganic acid, an organic acid, a salt of an inorganic acid or an organic acid, and a fluorine compound, and a film to be formed. This is preferable for improving the adhesion to the metal surface.
Further, when the metal surface treatment agent further contains a water-soluble polymer or / and an aqueous emulsion resin (F), the corrosion resistance, fingerprint resistance, solvent resistance and surface lubricity of the film to be formed are improved. Therefore, it is preferable.

  In the present invention, the surface of the metal material is brought into contact with any of the above-described metal surface treatment agents, and then dried by heating so that the temperature of the material becomes 30 to 250 ° C., so that at least one side of the surface of the metal material Furthermore, the present invention relates to a surface treatment method for a metal material characterized by forming a dry film having a thickness of 0.001 to 2 μm, and a surface-treated metal material having a film formed by using the surface treatment method. Furthermore, the metal material is preferably selected from the group consisting of zinc-based plated steel, aluminum-based plated steel, aluminum / zinc-based alloy plated steel, aluminum, aluminum alloy, magnesium alloy and copper alloy.

  The metal surface treatment agent of the present invention is a non-chromate type that does not contain harmful chromium compounds, and the film formed from this surface treatment agent has a corrosion resistance equal to or higher than that of a conventional chromate film. The surface treatment agent, the surface treatment method and the surface-treated metal material of the invention have extremely high industrial utility value. The metal material treated with the surface treatment agent has excellent corrosion resistance, excellent alkali resistance, and excellent interlayer adhesion.

The vanadium compound (A) contained in the metal surface treatment agent of the present invention has a vanadium oxidation number of pentavalent, tetravalent, trivalent or divalent vanadium compounds such as vanadium pentoxide (V ₂ O ₅ ), metavanadium. Acid (HVO ₃ ), ammonium metavanadate, sodium metavanadate, vanadium trioxide oxide such as vanadium oxytrichloride (VOCl ₃ ), vanadium trioxide (V ₂ O ₃ ), vanadium dioxide (VO ₂ ), oxy Vanadium sulfate (VOSO ₄ ), vanadium oxyacetylacetonate [VO (OC (CH ₃ ) ═CHCOCH ₃ ) ₂ ], vanadium acetylacetonate [V (OC (CH ₃ ) ═CHCOCH ₃ ) ₃ ], vanadium trichloride ( VCl _3), phosphovanadomolybdic acid _{{H 15 -X [PV 12 -xMoxO} 40] · nH 2 O (6 x <12, n <30) }, at least selected from vanadium sulfate _{(VSO 4 · 7H 2 O)} , vanadium dichloride (VCl _2), an oxidation number of 4 to 2 valent vanadium compounds such as vanadium oxide (VO), etc. One type.

The treatment agent preferably 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 with an oxidation number of 5 to the total vanadium (where V ⁵⁺ and V represent the mass of vanadium with an oxidation number of 5 and the total vanadium mass, respectively) is in the range of 0 to 0.6. Preferably in the range of 0 to 0.4, more preferably in the range of 0 to 0.2, and most preferably in the range of 0 to 0.1.
When the ratio exceeds 0.6, the stability of the vanadium compound in the treatment agent is generally deteriorated, and the corrosion resistance, alkali resistance, and interlayer adhesion of the formed film are lowered.

  As a method for incorporating a tetravalent or divalent vanadium compound into the present treating agent, a tetravalent or bivalent vanadium compound as described above is used, or a pentavalent vanadium compound is previously converted into a tetravalent or bivalent value using a reducing agent. What was reduced to can be used. The reducing agent used may be either inorganic or organic, but is preferably organic, and particularly preferably the organic compound (D).

The metal compound (B) containing at least one metal selected from the group consisting of cobalt, nickel, zinc, magnesium, aluminum, calcium, strontium, barium and lithium, contained in the metal surface treatment agent of the present invention, Metal oxides, hydroxides, complex compounds, salts with inorganic acids or organic acids, and the like. Examples of the metal compound (B) include cobalt (II) acetylacetonate [Co (OC (CH ₃ ) ═CHCOCH ₃ ) ₂ ], cobalt (III) acetylacetylacetonate [Co (OC (CH ₃ ) = CHCOCH ₃ ) ₃ ], cobalt nitrate (II), cobalt sulfate (II), cobalt acetate (II), cobalt oxalate (II), cobalt oxalate (III), cobalt oxide (II), cobalt oxide (III), Cobalt (IV) oxide, nickel (II) nitrate, nickel (II) acetate, nickel (III) acetate, nickel (II) oxalate, nickel (II) oxide, nickel (II) acetylacetonate [Ni (OC (CH _{3) = CHCOCH 3) 2]} , amide nickel sulfate, basic nickel carbonate _[NiCO 3 · 2Ni (O ) _3], nickel hydroxide (II), zinc fluoride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxide, zinc (II) acetylacetonate _{[Zn (OC (CH 3)} = CHCOCH 3) 2], bases Zinc carbonate [2ZnCO ₃ .3Zn (OH) ₂ ], magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium fluoride, magnesium hydroxide, magnesium oxalate, magnesium oxide, basic magnesium carbonate [(MgCO ₃ ) ₄ .Mg (OH) ₂ ], aluminum nitrate, aluminum sulfate, aluminum oxide, aluminum hydroxide, aluminum fluoride, aluminum acetate, calcium acetate, calcium fluoride, calcium phosphinate [Ca (PH ₂ O ₂ ) ₂ ], calcium nitrate, Calcium hydroxide, calcium oxalate, Calcium oxide, calcium acetate, strontium nitrate, strontium acetate, strontium carbonate, barium nitrate, barium carbonate, barium oxide, lithium nitrate, lithium phosphate, lithium fluoride, lithium hydroxide, lithium sulfate, lithium carbonate, dilithium oxalate, Examples thereof include lithium oxide.
Of these metal compounds (B), metal compounds containing at least one metal selected from the group consisting of cobalt, nickel, zinc and magnesium are preferred.

The metal compound (C) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese and cerium, contained as an optional component in the metal surface treatment agent of the present invention, Oxides, hydroxides, complex compounds, salts with inorganic acids or organic acids, and the like. Examples of the metal compound (C) 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 }, a reaction product of lactic acid and titanium alkoxide, Molybdic acid (H ₂ MoO ₄ ), ammonium molybdate, sodium molybdate, molybdophosphoric acid compounds (for example, ammonium molybdophosphate {(NH ₄ ) ₃ [PO ₄ Mo ₁₂ O ₃₆ ] · 3H ₂ O}, sodium molybdophosphate { Na ₃ [PO ₄ · 12MoO ₃ ] · nH ₂ O}), metatungstic acid {H ₆ [H ₂ W ₁₂ O ₄₀ ]}, ammonium metatungstate {(NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ]}, sodium metatungstate, paratungstic acid {H ₁₀ [W ₁₂ O ₄₆ H ₁₀ ]}, ammonium paratungstate, sodium paratungstate, permanganic acid (HMnO ₄ ), potassium permanganate, sodium permanganate, manganese dihydrogen phosphate [Mn (H ₂ PO ₄ ) ₂ ], manganese nitrate [Mn (NO ₃ ) ₂ ], manganese sulfate, manganese fluoride, manganese carbonate (MnCO ₃ ), manganese acetate, cerium acetate [Ce (CH ₃ CO ₂ ) ₃ ], cerium nitrate, cerium chloride and the like.
Of these metal compounds (C), metal compounds containing zirconium and / or titanium are preferred.

  Suitable combinations of the metal compounds (A), (B) and (C) include a vanadium compound (A) and a metal compound containing cobalt and / or nickel as the metal compound (B) and a metal compound (C). The combination with the metal compound containing zirconium gives the most excellent corrosion resistance, alkali resistance and interlayer adhesion to all the metal materials used in the present invention. A combination of a vanadium compound (A), a metal compound containing zinc and / or magnesium as the metal compound (B), and a metal compound containing titanium as the metal compound (C) Similar to the combination, it provides excellent corrosion resistance, alkali resistance and interlayer adhesion.

The organic compound (D) to be included in the metal surface treatment agent of the present invention, if necessary, comprises 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. An organic compound having at least one functional group selected from the group.
Examples of the organic compound (D) include alcohols such as methanol, ethanol, isopropanol, and ethylene glycol, carbonyls such as formaldehyde, acetaldehyde, furfural, acetylacetone, ethyl acetoacetate, glyoxal, dipivaloylmethane, and 3-methylpentanedione. Compounds, formic acid, acetic acid, propionic acid, tartaric acid, ascorbic acid, gluconic acid, citric acid, malic acid, glyoxylic acid and other organic acids, triethylamine, triethanolamine, ethylenediamine, pyridine, imidazole, pyrrole, morpholine, piperazine and other amines Compounds, acid amide compounds such as formamide, acetamide, propionamide, N-methylpropionamide, amino acids such as glycine, alanine, proline, glutamic acid Aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1'-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), organic phosphates such as phytic acid, monosaccharides such as glucose, mannose, galactose, maltose, sucrose Oligosaccharides such as starch, natural polysaccharides such as cellulose, tannic acid, humic acid, lignin sulfonic acid, aromatic compounds such as polyphenol, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, polyethyleneimine, water-soluble nylon And synthetic polymers such as

  Among these organic compounds (D), an organic compound containing two or more of at least one selected from the above functional groups in one molecule is preferable. Further, as the above functional group, a hydroxyl group, a carbonyl group, a carboxyl group, phosphorus An organic compound containing at least one selected from an acid group and a phosphonic acid group in one molecule is more preferable.

  These organic compounds (D) are reduced to tetravalent, trivalent or divalent when a pentavalent vanadium compound is used, and / or improve the stability of the vanadium compound in the treatment liquid of the present invention. This is preferable.

  These organic compounds (D) are mixed with a vanadium compound in advance and heated (for example, at 40 to 100 ° C. for 5 to 120 minutes) or the like to sufficiently reduce and stabilize the surface treatment agent. However, it is also possible to allow reduction to proceed at the time of heat-drying after simply applying to the metal surface as a mixed surface treatment agent.

The etching agent (E) to be included in the metal surface treatment agent of the present invention as required is at least one compound selected from inorganic acids, organic acids, inorganic acids or salts of organic acids, and fluorine compounds. . The etching agent (E) to be included in the surface treatment agent of the present invention, if necessary, is an inorganic acid, an organic acid, an inorganic acid or a salt of an organic acid (in particular, 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, and is used for etching a material metal at the time of applying a treatment agent or heat drying. Examples of the etching agent (E) include inorganic acids such as phosphoric acid, 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 (particularly ammonium salts). , Sodium salt, potassium salt), hydrofluoric acid, borohydrofluoric acid (HBF ₄ ), silicohydrofluoric acid (H ₂ SiF ₆ ), zirconium hydrofluoric acid (H ₂ ZrF ₆ ), titanium hydrofluoric acid ( Fluorine compounds such as H ₂ TiF ₆ ), tin (I) fluoride (SnF ₂ ), tin (II) fluoride (SnF ₄ ), ferrous fluoride, and ferric fluoride can be used.
The use of the etching agent (E) is preferable in order to increase the reactivity to the metal material and improve the adhesion between the film to be formed and the metal material.

About the quantity of each structural component in the processing agent of this invention, 0.1-100 g / L is preferable in vanadium conversion, and 1-70 g / L is more preferable. The metal compound (B) is preferably 0.01 to 50 g / L, more preferably 0.1 to 20 g / L in terms of metal. The metal compound (C) is preferably 0.1 to 100 g / L, more preferably 1.0 to 70 g / L in terms of metal.
The mass ratio of the vanadium compound (A), the metal compound (B), and the metal compound (C) is, in terms of metal, V / metal compound mass in the metal compound (C) = 1/200 to 9/1, and metal Metal equivalent mass in compound (B) / (V + metal equivalent mass in metal compound (C)) = 1/1000 to 1/5, preferably V / metal equivalent mass in metal compound (C) = More preferably, it is 1/100 to 8/2, and the metal equivalent mass in the metal compound (B) / (V + metal equivalent mass in the metal compound (C)) = 1/200 to 1/10.
The organic compound (D) is preferably 0.05 to 10, more preferably 0.1 to 5, when the mass of pentavalent vanadium in the vanadium compound is 1. It is more preferable to add in excess than the amount necessary for the reduction because the stability of the reductant in the treatment liquid is improved.
The etching agent (E) is preferably from 0.01 to 100 g / L, more preferably from 0.1 to 70 g / L.

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

In the treatment agent of the present invention, silica sol dispersed in water and / or metal sol such as alumina sol and zirconia sol can be added. By adding these, the corrosion resistance, water resistance, and fingerprint resistance are improved. In this case, the amount to be added is preferably 2 to 80% by mass, more preferably 5 to 60%, based on the total nonvolatile components.
In the treatment agent of the present invention, a silane coupling agent such as amino silane, epoxy silane, or mercapto silane can be added. By adding these, interlayer adhesion and corrosion resistance are improved. In this case, the amount to be added is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass of the total nonvolatile components.

In the treatment agent of the present invention, a lubricant such as polyethylene wax, polypropylene wax, microcrystalline wax, carnauba wax, polytetrafluoroethylene and the like can be added. By adding these, slipperiness, moldability, and scratch resistance can be imparted. In this case, the amount to be added is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass of the total nonvolatile components.
In the present invention, the total non-volatile component means a component remaining after the surface treatment agent is heated and dried at 110 ° C. for 2 hours.

Although the solvent used in the surface treating agent of the present invention is mainly water, it does not hinder the combined use of alcohol, ketone and cellosolve-based water-soluble organic solvents as necessary, such as improvement of the drying property of the film.
In addition, surfactants, antifoaming agents, leveling agents, antibacterial and antifungal agents, coloring agents, and the like can be added within a range that does not impair the gist and film performance of the present invention.

Next, the surface treatment method of the present invention will be described.
There are no particular restrictions on the pre-treatment of this treatment, but usually the oil or dirt adhering to the material is removed before the treatment by washing with an alkaline or acidic degreasing agent, hot water washing, solvent Perform cleaning. Thereafter, surface adjustment with acid, alkali or the like is performed as necessary. In cleaning the surface of the material, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the surface of the material as much as possible.

About this processing method, after apply | coating the surface treating agent of this invention to the surface of a metal raw material, it should just be heat-dried and there is no restriction | limiting in particular about an application method, a drying method, etc.
Usually, a roll coat method in which a treatment agent is roll-transferred and applied to the surface of the material, or a method of squeezing with a roll after pouring by a shower ringer, a method of immersing the material in the treatment agent, or a method of spraying the treatment agent on the material is used. It is done. Although the temperature of a process liquid is not specifically limited, Since the solvent of this processing agent is mainly water, process temperature is preferable 0-60 degreeC, and 5-40 degreeC is more preferable.

  The drying step does not necessarily require heat and may be air-dried or physically removed by air blow or the like, but may be heat-dried in order to improve film forming properties and interlayer adhesion. In that case, the temperature is preferably 30 to 250 ° C, more preferably 60 to 220 ° C.

  The amount of the film formed is preferably 0.001 to 2 [mu] m, more preferably 0.005 to 1 [mu] m in terms of dry film amount. If it is less than 0.001 μm, sufficient corrosion resistance, alkali resistance and interlayer adhesion cannot be obtained, and if it exceeds 2 μm, the coating itself may crack, and the adhesion to the metal material may be reduced.

  By providing a resin layer on the film formed from the surface treatment agent of the present invention so that the dry film thickness is 0.3 to 50 μm, the corrosion resistance and alkali resistance of the metal material to be processed are improved, and fingerprint resistance is also improved. , Solvent resistance and surface lubricity can be imparted.

As a method for providing such a resin layer, a solvent-based paint or water-based paint in which a resin is dissolved or dispersed in advance is applied onto a film formed from the surface treatment agent of the present invention and dried at 0 to 200 ° C. And a method of laminating a film-like resin on the film. Examples of the resin having interlaminar adhesion with the film include polyester resin, vinyl chloride resin, acrylic resin, epoxy resin, polyimide resin, polyolefin resin, polyamide resin, phenol resin, and the like.
In particular, as a method of providing a resin layer so as to impart fingerprint resistance, solvent resistance and surface lubricity, a water-based paint (Z) containing a water-soluble or water-dispersible resin as a main component is used in the present invention. A method of coating on a film formed from a surface treatment agent and drying by heating at a material reaching temperature of 50 to 250 ° C. is desirable. Water-soluble or water-dispersible resins used in the water-based paint (Z) are acrylic resins obtained by polymerizing addition polymerizable unsaturated monomers, polyolefin resins, epoxy resins obtained by condensation reactions, urethane resins, Examples thereof include polyester resins, polyamide resins, phenol resins, and the like. The glass transition point of the resins is preferably 0 to 120 ° C, and more preferably 10 to 100 ° C. When the glass transition point is less than 0 ° C., the strength and hardness of the film are poor, and when it exceeds 120 ° C., the film forming property is poor and the adhesion is poor.

  The water-based paint (Z) contains at least one selected from these resins. In addition, in order to improve the toughness and fingerprint resistance of the film, it is desirable to contain water-dispersible silica, and further lubrication. In order to improve the properties, it is desirable to add an aqueous wax. The content of these components is 50 to 100 parts by mass of resin, 0 to 40 parts by mass of water-dispersible silica, and 0 to 30 parts by mass of water-based wax when the total nonvolatile content is 100 parts by mass. Is preferred. Moreover, the crosslinking agent which can bridge | crosslink resin can be contained.

The surface treatment agent of the present invention reacts with the surface of the material metal when it is applied to the material metal and dried by heating to form a dense passive film.
The film formed by the surface treating agent of the present invention exhibits excellent corrosion resistance because of the barrier effect that blocks the permeation of oxygen, moisture, and ions of the film, as well as the effect of delocalizing corrosion electrons (potential smoothing). It is thought to be due to In the vanadium compound (A) specified in the present invention, the pentavalent vanadium compound exists as a polyvalent anion bonded to oxygen and has poor water resistance and alkali resistance, so that sufficient performance cannot be obtained, but it is reduced. It is considered that a film formed using a treatment agent containing at least one of a tetravalent vanadium compound, a trivalent vanadium compound and a divalent vanadium compound has improved water resistance, alkali resistance and interlayer adhesion. . In addition, the metal compound (B) to be used exhibits a sacrificial anticorrosive action on the surface of the metal material, promotes the localization of the corrosion electrons, or gradually forms ions and sparingly soluble salts that diffuse in the metal material film. This action is considered to have the effect of insolubilizing the coating itself and further inactivating the metal material. Moreover, it is thought that the metal compound (C) to be used immobilizes the vanadium compound (A) present in the film to be formed and further enhances the barrier effect.
In addition, the organic compound (D) to be used acts to reduce the pentavalent vanadium compound and at the same time to chelate-stabilize the tetravalent, trivalent and divalent vanadium reduced in the aqueous solution in the aqueous solution. It is thought that there is.
When a layer mainly composed of a resin is further formed on the film of the present invention by coating or laminating, the corrosion resistance is further enhanced by a synergistic effect with the barrier effect of the resin layer.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention, a present Example is only a mere example and does not limit this invention. The evaluation method for the treated plate samples produced in the examples and comparative examples is as follows.
1. Material a: Electrogalvanized steel sheet (thickness: 0.8mm)
b: Hot-dip galvanized steel sheet (thickness: 0.8 mm)
c: 55% aluminum galvanized steel sheet (thickness: 0.5 mm)
d: Magnesium alloy aluminum plate, A5182 (plate thickness: 0.3 mm)

2. Process liquid of the present invention (1) Process liquid component 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: Basic nickel carbonate B2: Cobalt nitrate B3: Magnesium nitrate B4: Zinc oxide B5: Lithium hydroxide

The metal compound (C) used is described below.
C1: ammonium molybdate C2: ammonium metatungstate C3: ammonium zirconium carbonate C4: fluorotitanic acid C5: manganese carbonate

The organic compound (D) used is described below.
D1: L-ascorbic acid D2: D-glucose D3: Glyoxal The etching agent (E) used is described below.
E1: HF
E2: H ₂ ZrF ₆
E3: CH ₃ COOH
E4: H ₂ SiF ₆
E5: (HH ₄ ) ₂ HPO ₄

The water-soluble polymer and / or aqueous emulsion resin (F) used is shown below.
F1: Water-based polyurethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 100)
F2: Water-based ethylene-acrylic acid copolymer resin (ethylene / acrylic acid = 80/20 *, average molecular weight of about 20,000)
F3: Water-based epoxy resin (Asahi Denka Kogyo Co., Ltd., Adeka Resin EPEA-0434)
F4: Water-based acrylic resin (butyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid / glycidyl methacrylate / styrene = 50/20/5/8/2/15) *
* Figures are mol%

(2) Preparation of treatment liquid Examples 1 to 11 and Comparative Examples 1 to 3 Vanadium compound (A), metal compound (B), metal compound (C), etching agent (E) and deionized water were mixed. And heated at 50 ° C. for 1 hour.
Examples 12 to 21 and Comparative Example 4 After mixing the vanadium compound (A) in a 5% aqueous solution of the organic compound (D), the mixture was heated at 80 to 100 ° C. for 30 minutes, cooled to room temperature, and the metal compound ( B) and the metal compound (C) were added, followed by the etching agent (E), and finally deionized water was added to adjust to a predetermined concentration.

3. Paint and film for forming resin layer The top coat (X) used for forming the resin layer is described below.
X: Solvent-based paint (Delicon 700, manufactured by Dainippon Paint Co., Ltd.)
The laminate film (Y) used for forming the resin layer is described.
Y: Polyester film (Lumirror S10, TORAY Industries. Inc.)
The water-based paint (Z) used for forming the resin layer and the treatment method will be described. As the water-based paint (Z), Z1 or Z2 shown below was used.
Z1: 100 parts by mass of solid polyurethane (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Superflex 100), 20 parts by mass of water-based silica (Nissan Chemical Co., Ltd., Snowtex C) in terms of silica, water-based wax An aqueous processing solution having a nonvolatile content of 10% (made by Mitsui Chemicals, Chemipearl W900) having a solid content of 10 parts by mass.
Z2: 100 parts by mass of ammonia-neutralized water-based polymer of ethylene-acrylic acid copolymer (ethylene / acrylic acid = 80/20, average molecular weight of about 20,000) in terms of solid content, and 10 in terms of silica for water-dispersible silica An aqueous treatment liquid having a non-volatile content of 20% consisting of parts by mass.

4). Treatment Method (1) Degreasing Alkali degreasing agent Pulclean 364S manufactured by Nippon Parkerizing Co., Ltd.
The material was degreased with (20 g / L building bath, 60 ° C., 10 seconds spray, spray pressure 50 kPa), and then washed with spray water for 10 seconds.
(2) Application and Drying of the Treatment Solution of the Present Invention I: The treatment solution was applied with a bar coater # 3 and dried at a plate temperature of 80 ° C. using a hot air circulating oven.
II: The treatment liquid was applied with a bar coater # 3 and dried at a plate temperature of 150 ° C. using a hot-air circulating oven.

(3) Formation conditions of resin layer The resin layer was formed with the following method on the film | membrane of the surface treatment metal material formed using the processing agent of this invention, and the processing method.
X: Solvent-based paint The solvent-based paint (X) was bar-coated so that the dry film thickness was about 25 μm, placed in a commercially available batch-type drying oven, and dried by heating at 140 ° C. for 30 minutes.
Y: Polyester film The surface-treated metal material of the present invention was heated in a heating furnace until the ultimate plate temperature reached 240 ° C, and the polyester film (Y) heated in advance to 100 ° C was pressure-laminated and bonded together. .
Z: Water-based paint The water-based paint (Z) is applied to the film formed by using the treatment liquid and treatment method of the present invention with a bar coat so that the dry film thickness is about 1 μm, and heated at a plate temperature of 100 ° C. Dried.

5). Evaluation Method (1) Corrosion Resistance Based on the salt spray test method JIS-Z-2371, the white rust generation area after 120 hours and 240 hours after salt spray was determined and evaluated.
Evaluation criteria: White rust occurrence area ◎ <10%, ○ 10% or more and less than 30%,
△ 30% or more and less than 60%, x60% or more (2) Alkali resistance A degreasing agent aqueous solution prepared by bathing 20g / L of alkaline degreasing agent Parklein 364S manufactured by Nihon Parkerizing Co., Ltd. and adjusted to 60 ° C. After spraying for 30 seconds, washing with water, and drying at 80 ° C. About this board, corrosion resistance was evaluated by the conditions and evaluation method described in said (1).

(3) Interlayer adhesion After a resin layer is formed using a solvent-based paint (X) or polyester film (Y), a cross-cut test of 1 mm and 100 squares is performed, and further, the part is subjected to Erichsen processing by extruding 7 mm. gave. After processing, it was immersed in boiling water for 5 hours, and the treated plate was taken out and naturally dried for 30 minutes in a room temperature atmosphere. Subsequently, a tape peeling test was carried out, and the number of remaining resin layers was determined and determined according to the following evaluation criteria.
Evaluation criteria: Number of remaining coating films ◎: 100
○: 98 or more and less than 100
Δ: 50 or more and less than 98
×: Less than 50

(4) Fingerprint resistance A finger was pressed against the surface of the treated plate, and the trace state of the fingerprint was observed and evaluated with the naked eye.
Evaluation criteria: ◎ no trace, ○ very slight trace,
Δ There is a trace, and a trace remains clearly. (5) Solvent resistance A gauze impregnated with ethanol was wound around a cube made of silicon rubber (1 cm square), and the test surface was rubbed 30 times at 50,000 kPa.
Evaluation criteria: ◎ almost no film peeling, ○ slightly film peeling,
△ There is some peeling of the film.

The treatment liquid contents and treatment methods of Examples and Comparative Examples are shown in Tables 1, 2 and 3, and the evaluation results of the treatment plates are shown in Tables 4 and 5.
The film formed from the processing agent (Examples 1-21) of this invention containing specific vanadium compound (A) and specific metal compound (B) from Table 4 is corrosion resistance, alkali resistance, and also a resin layer. It turns out that the result which was excellent comprehensively in the interlayer adhesiveness with (X or Y) and various metal materials is shown. In comparison with this, none of Comparative Examples 1 to 4 containing no vanadium compound (A) or metal compound (B) satisfied all the performances of corrosion resistance, alkali resistance, and interlayer adhesion.
From Table 5, although Examples 22-27 containing water-soluble polymer or water-based emulsion resin (F) are a single-layer treatment in which a resin layer is not provided on the upper layer, they are excellent in corrosion resistance and alkali resistance. In addition, it can be seen that fingerprint resistance and solvent resistance are also excellent. Although Examples 28-42 do not contain water-soluble polymer or water-based emulsion resin (F) in the treatment agent of the present invention, a resin layer (Z1 or Z2) is further formed on the film of Examples 1-15. It is a two-layer process. It can be seen that these Examples 28 to 42 are also excellent in corrosion resistance and alkali resistance, and also excellent in fingerprint resistance and solvent resistance. In comparison, Comparative Example 5 (in which the coating itself contains a resin component) and Comparative Examples 6 to 9 (resin on the coatings of Comparative Examples 1 to 4) do not contain the vanadium compound (A) or the metal compound (B). None of the layers (Z)) satisfied all the performances of corrosion resistance, alkali resistance and solvent resistance.

Example 28 The topcoat treatment agent Z1 was treated on the film formed in Example 1.
Example 29 The topcoat treatment agent Z2 was treated on the film formed in Example 2.
Example 30 The film formed in Example 3 was treated with the topcoat treatment agent Z1.
Example 31 The film formed in Example 4 was treated with the topcoat treatment agent Z2.
Example 32 The film formed in Example 5 was treated with the topcoat treatment agent Z2.
Example 33 The film formed in Example 6 was treated with the topcoat treatment agent Z2.
Example 34 The film formed in Example 7 was treated with the top coat treating agent Z1.
Example 35 The film formed in Example 8 was treated with the topcoat treatment agent Z2.

Example 36 The topcoat treatment agent Z2 was treated on the film formed in Example 9.
Example 37 The film formed in Example 10 was treated with the topcoat treatment agent Z2.
Example 38 The topcoat treatment agent Z1 was treated on the film formed in Example 11.
Example 39 The topcoat treatment agent Z2 was treated on the film formed in Example 12.
Example 40 The film formed in Example 13 was treated with the topcoat treatment agent Z2.
Example 41 The film formed in Example 14 was treated with the topcoat treatment agent Z2.
Example 42 The film formed in Example 15 was treated with the top coat treatment Z2.

Comparative Example 6 The film formed in Comparative Example 1 was treated with the topcoat treatment agent Z2. Comparative Example 7 On the film formed in Comparative Example 2, the treatment with the topcoat treatment agent Z2 was performed. Comparative Example 8 The film formed in Comparative Example 3 was treated with the topcoat treatment agent Z2.
Comparative Example 9 The film formed in Comparative Example 4 was treated with the topcoat treatment agent Z2.

Claims (8)

  Containing at least one vanadium compound (A), a metal compound (B) containing zinc and / or magnesium, and a metal compound (C) containing titanium, the vanadium compound (A), the metal compound (B) and The amount of the metal compound (C) is 1 to 70 g / L in terms of vanadium, 0.1 to 20 g / L in terms of zinc and / or magnesium, and 1.0 to 70 g / L in terms of titanium, and , Vanadium compound (A), metal compound (B), and metal compound (C) have a mass ratio of V / Ti = 1/100 to 8/2 in terms of metal, and equivalent to metal in metal compound (B) Mass / (V + Ti) = 1/200 to 1/10 Surface treatment agent for aluminum-containing metal material The surface treating agent according to claim 1, wherein in the vanadium compound (A), the ratio V ⁵⁺ / V of the vanadium ions having an oxidation number of 5 to the total vanadium is in the range of 0 to 0.6.   Furthermore, it contains an organic compound (D) 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. Item 3. The surface treating agent according to Item 1 or 2.   Furthermore, at least 1 sort (s) of etching agents (E) chosen from the group which consists of an inorganic acid, an organic acid, a salt of an inorganic acid or an organic acid, and a fluorine compound are described in any one of Claims 1-3. Surface treatment agent.   Furthermore, the surface treating agent of any one of Claims 1-4 containing water-soluble polymer or / and water-system emulsion resin (F).   After bringing the surface of the aluminum-containing metal material into contact with the surface treatment agent according to any one of claims 1 to 5, the material is heated and dried so that the temperature of the material becomes 30 to 250 ° C, and at least the A surface treatment method for an aluminum-containing metal material, wherein a dry film having a thickness of 0.001 to 2 μm is formed on one side of the surface of the metal material.   An aluminum-containing metal material having a film formed by the surface treatment according to claim 6. The metal material according to claim 7, wherein the aluminum-containing metal material is selected from the group consisting of an aluminum-based plated steel material, an aluminum / zinc-based alloy plated steel material, an aluminum material, and an aluminum alloy material.