JP2009174050A - Composition for metal surface treatment, and surface treated metallic material having metal surface treatment layer obtained from the composition for metal surface treatment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-pollution type composition for metal surface treatment having rust prevention force equal to that of the conventional chromatizing agent and phosphatizing agent, and also having storage stability, workability, top coat applicability or the like, and to provide a surface treated metallic material using the composition for metal surface treatment. <P>SOLUTION: Disclosed is a composition for metal surface treatment comprising: (A) peroxo vanadic acid; (B) organic phosphonic acid; and, if required, (C) a water soluble or water dispersible organic resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a metal surface treatment composition and a surface-treated metal material having a metal surface treatment layer obtained from the metal surface treatment composition.

  Conventionally, chromate treatment and phosphate treatment are generally performed to improve the corrosion resistance of metal surfaces. However, in recent years, the toxicity of chromium has become a social problem. The surface treatment method using chromate is the problem of scattering of chromate fume in the treatment process, the wastewater treatment equipment is expensive, and the problem of elution of chromic acid from the chemical conversion treatment film, etc. There is. Hexavalent chromium compounds are extremely harmful substances as many public institutions, including IARC (International Agency for Research on Cancer Review), have designated as carcinogenic substances for the human body.

  In the phosphate treatment, zinc phosphate-based and iron phosphate-based surface treatment is usually performed. After phosphating, rinsing with chromic acid is usually performed for the purpose of imparting corrosion resistance. For this reason, there are problems such as slag treatment due to effluent treatment of reaction accelerators and metal ions in the phosphate treatment agent and elution of metal ions from the metal to be treated, along with the problem of chromium treatment.

  Zirconium-based and titanium-based surface treatment agents are well known as treatment methods other than chromate treatment and phosphate treatment (see Patent Document 1, etc.), and have been put to practical use mainly in aluminum-based materials. Yes. However, there is a problem that the corrosion resistance of zinc-based materials is inferior to that of conventional chromate treatment.

  In addition to zirconium-based and titanium-based, vanadium-based treating agents have been studied, and Patent Document 2 discloses an electrolysis for metal surface treatment containing a vanadium salt and / or a vanadium salt of an inorganic acid and an organic acid having a reducing power. A chemical conversion solution is disclosed. This can form a film excellent in corrosion resistance even in a zinc material by performing a cathodic conversion treatment. However, there is a limit to the treatment method called electrolytic conversion treatment, and the cost is higher than the treatment of simply immersing or coating the material in the treatment liquid, so that it is limited to a specific application.

  Since vanadium is excellent in corrosion resistance, it is used as a rust inhibitor as a vanadate such as ammonium metavanadate. However, since the vanadium compound is inferior in stability in water, a method of dispersing in a specific aqueous organic resin and dispersing in water is employed. However, even in such a method, a large amount of vanadium compound cannot be put in the surface treatment agent, and a reduction in corrosion resistance of the metal surface having a layer made of the surface treatment agent is inevitable. . Therefore, it has been studied to use a vanadium compound as a peroxovanadate by reacting with hydrogen peroxide.

Patent Document 3 discloses a surface treatment agent using a peroxo metal oxyacid salt, and vanadium is exemplified as the metal. However, although peroxovanadic acid has better stability in water than the above-described vanadate, it easily precipitates and has a problem in terms of storage stability. In addition, none of the patent documents describes examples using peroxovanadate, so that sufficient studies have not been made. This is presumably because the storage stability of the treatment agent has not reached a practically satisfactory level.
Japanese Patent Publication No. 48-24618 JP-A-9-95796 JP 54-147141 A

  An object of the present invention is to provide a pollution-free metal surface treatment composition having a rust preventive power comparable to that of a chromate treatment agent and a phosphate treatment agent and having excellent storage stability.

  As a result of intensive studies to solve the above-mentioned object, the present inventors have found that a metal surface treatment composition containing peroxovanadate and organic phosphonic acid is a conventional chromate treatment agent and phosphate treatment. It has been found that it has a rust preventive power comparable to that of the agent and is excellent in storage stability, and has completed the present invention.

That is, the present invention provides the following metal surface treatment composition and a surface treatment metal material having a metal surface treatment layer obtained from the metal surface treatment composition.
1. A metal surface treatment composition comprising (A) peroxovanadate and (B) an organic phosphonic acid.
2. Item 2. The metal surface treatment composition according to Item 1, wherein the organic phosphonic acid (B) has a hydroxyl group-containing organic group.
3. The organic phosphonic acid (B) is at least one selected from 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and 1-hydroxypropane-1,1-diphosphonic acid. Item 3. The metal surface treatment composition according to Item 1 or 2, which is contained.
4). Item 4. The metal surface treatment composition according to any one of Items 1 to 3, wherein the organic phosphonic acid (B) is contained within a range of 1 to 250 parts by mass with respect to 100 parts by mass of the peroxovanadate acid (A). object.
5. Item 5. The metal surface treatment composition according to any one of Items 1 to 4, further comprising a water-soluble or water-dispersible organic resin (C).
6). 6. The metal surface treatment according to item 5, wherein the water-soluble or water-dispersible organic resin (C) is contained within a range of 1 to 20,000 parts by mass with respect to 100 parts by mass of peroxovanadate (A). Composition.
7). Item 7. The metal surface treatment composition according to any one of Items 1 to 6, wherein the metal surface treatment composition is for a steel material plated with zinc or a zinc alloy.
8). A surface-treated metal material having a metal surface-treated layer obtained from the composition for metal surface treatment according to any one of Items 1 to 6 on a steel material plated with zinc or a zinc alloy.
9. A surface-treated steel sheet having a metal surface treatment layer obtained from the metal surface treatment composition according to any one of Items 1 to 6 on a steel sheet plated with zinc or a zinc alloy.
10. The manufacturing method of the surface treatment metal material which forms the metal surface treatment layer obtained from the composition for metal surface treatment in any one of said item | item 1-6 on the raw material plated with zinc or zinc alloy.
11. The manufacturing method of the surface treatment steel plate which forms the metal surface treatment layer obtained from the composition for metal surface treatment in any one of said claim | item 1-6 on the steel plate plated with zinc or zinc alloy.

  The metal surface treatment composition of the present invention contains peroxovanadate acid and organic phosphonic acid. Peroxovanadic acid is excellent in corrosion resistance, but it is difficult to put it to practical use because it alone has poor stability in water and easily precipitates. However, by combining this with organic phosphonic acid, the storage stability of the treatment liquid is remarkably improved, and the combination with aqueous organic resin can be widely used, so that the performance of the treated membrane can be improved. Since it is easy to achieve a balance (for example, a balance between corrosion resistance and workability, material adhesion, etc.) and performance comparable to chromate and phosphate treatment agents is obtained, non-chromium instead of these treatment agents It is extremely useful as a mold surface treatment agent for surface treatment of metals.

  The surface-treated metal material of the present invention is excellent in workability, corrosion resistance, top coatability, and the like.

  The metal surface treatment composition of the present invention comprises peroxovanadic acid (A) and organic phosphonic acid (B). This will be described in detail below.

Peroxovanadate (A)
The peroxovanadate which is the component (A) of the present invention can be easily produced, for example, by reacting a vanadium compound with hydrogen peroxide.

  Examples of the vanadium compounds include vanadium oxides such as vanadium trioxide and vanadium pentoxide; vanadium oxyhalides such as vanadium oxydichloride and vanadium trichloride; vanadium halides such as vanadium trichloride; ammonium metavanadate and metavanadate Examples thereof include sodium, sodium orthovanadate, vanadyl sulfate, sodium pyrovanadate, and the like. Among these, vanadium pentoxide and ammonium metavanadate are particularly preferable from the viewpoint of ease of production.

  It is preferable that the addition amount of hydrogen peroxide with respect to a vanadium compound is about 10-5000 mass parts with respect to 100 mass parts of vanadium compounds.

  Peroxovanadic acid can be usually produced by adding a vanadium compound to an aqueous hydrogen peroxide solution and heating at 20 to 100 ° C. for about 15 to 120 minutes.

  The concentration of peroxovanadic acid (A) in the metal surface treatment composition is not particularly limited, and can be used by appropriately changing the dilution rate depending on the form of use. For example, in the metal surface treatment composition It is preferable that it is 0.01-100 g / L, and it is more preferable that it is 0.1-30 g / L. If the concentration of peroxovanadic acid (A) is less than the above range, sufficient corrosion resistance tends to be not obtained, and if it exceeds the above range, the storage stability of the liquid tends to be poor.

Organic phosphonic acid (B)
Examples of the organic phosphonic acid as the component (B) of the present invention include 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1- Phosphonic acids having a hydroxyl group-containing organic group such as diphosphonic acid; phosphonic acids having a carboxyl group-containing organic group such as 2-hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof It is mentioned as a suitable thing.

  The organic phosphonic acid is excellent in the effect of improving the storage stability of the peroxovanadic acid (A) aqueous solution, and among these, a phosphonic acid having a hydroxyl group-containing organic group is preferable from the viewpoint of storage stability. Methane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid are more preferable, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable. .

  Since peroxovanadic acid (A) has poor stability in water, it is preferable to add organic phosphonic acid (B) immediately after the production of peroxovanadate.

  Since the metal surface treatment composition of the present invention contains peroxovanadate (A) and organic phosphonic acid (B), it has excellent storage stability.

  The addition amount of the organic phosphonic acid (B) is preferably 1 to 250 parts by mass with respect to 100 parts by mass of the solid content of peroxovanadic acid (A) from the viewpoint of storage stability. More preferably, it is more preferably 25 to 160 parts by mass.

Water-soluble or water-dispersible organic resin (C)
In the metal surface treatment composition of the present invention, addition of a water-soluble or water-dispersible organic resin (C) can result in adhesion when a paint is applied on the layer made of the metal surface treatment composition. From the viewpoint of improvement in workability and workability.

  The water-soluble or water-dispersible organic resin (C) is an organic resin that can be dissolved or dispersed in water. As a method for water-solubilizing or dispersing the organic resin in water, a conventionally known method can be used.

  Specifically, as an organic resin that can be dissolved or dispersed in water, specifically, a functional group (for example, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, an amino (imino) group, a sulfide group) that can be dissolved in water or dispersed in water alone. , A phosphine group, etc.) and, if necessary, those in which part or all of the functional groups are neutralized. As a resin in which a part or all of the functional groups are neutralized, when the resin is an acidic resin (carboxyl group-containing resin or the like), an amine compound such as ethanolamine or triethylamine; ammonia water; lithium hydroxide, water What neutralized with alkali metal hydroxides, such as sodium oxide and potassium hydroxide, can be mentioned. When the resin is a basic resin (such as an amino group-containing resin), fatty acids such as acetic acid and lactic acid; those neutralized with a mineral acid such as phosphoric acid, and the like can be given.

  Examples of organic resin base resins that can be dissolved or dispersed in water include epoxy resins, phenol resins, acrylic resins, polyurethane resins, olefin-carboxylic acid resins, nylon resins, resins having a polyoxyalkylene chain, and polyvinyl resins. Examples include alcohol, polyglycerin, carboxymethylcellulose, hydroxymethylcellulose, and hydroxyethylcellulose. The above resins can be used alone or in combination of two or more. Of these, at least one resin selected from the group consisting of water-soluble or water-dispersible acrylic resins, polyurethane resins, and epoxy resins is preferably used from the viewpoint of storage stability of the metal surface treatment composition.

i) Acrylic resin A water-soluble or water-dispersible acrylic resin is prepared by a conventionally known method, for example, an emulsion polymerization method, a suspension polymerization method, or a polymer having a hydrophilic group by solution polymerization, and if necessary, a medium. It can be obtained by, for example, a method of adding water to water.

  The polymer having a hydrophilic group includes, for example, unsaturated monomers having a hydrophilic group such as a carboxyl group, an amino group, a hydroxyl group, a polyoxyalkylene group, and derivatives thereof and, if necessary, other impurities. It can be obtained by polymerizing with a saturated monomer.

  Examples of the carboxyl group-containing unsaturated monomers and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid, itaconic acid, and the like.

  Examples of the amino group-containing unsaturated monomer and derivatives thereof include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and Nt-butylaminoethyl (meth). Nitrogen-containing alkyl (meth) acrylates such as acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N -Polymerizable amides such as butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; To mention That.

  Nitrogen-containing monomers such as 2-vinylpyridine, 1-vinyl-2-pyrrolidone, and 4-vinylpyridine can also be used as unsaturated monomers having a hydrophilic group.

  Examples of hydroxyl-containing unsaturated monomers include hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. (Meth) acrylate and the like can be mentioned.

  Examples of the polyoxyalkylene group-containing unsaturated monomer include monoesterified products of polyhydric alcohols such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid. Can do.

  In addition, a compound obtained by ring-opening polymerization of ε-caprolactone to the monoesterified product of the above hydroxyalkyl (meth) acrylate or polyhydric alcohol and acrylic acid or methacrylic acid can also be used.

  Other unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert -C1-C1 such as butyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, etc. 24 alkyl (meth) acrylates; vinyl acetate and the like. These compounds can be used alone or in combination of two or more. In the present invention, “(meth) acrylate” means acrylate or methacrylate.

  The content of the unsaturated monomer having a hydrophilic group is preferably 100% by mass or less, more preferably 80% by mass or less in the total monomer.

  Further, the water-soluble or water-dispersible acrylic resin is preferably obtained by copolymerizing styrene from the viewpoint of corrosion resistance and the like. The amount of styrene in the total unsaturated monomer is preferably 60% by mass or less, more preferably 10 to 60% by mass, and further preferably 15 to 50% by mass.

  The Tg (glass transition point) of the acrylic resin obtained by polymerization is preferably 30 to 80 ° C., and preferably within the range of 40 to 70 ° C., from the viewpoint of the toughness of the resulting film. More preferred.

  As a commercial item of the acrylic resin, Aquabrid CC234 (manufactured by Daicel Chemical Industries, Ltd.) can be exemplified.

ii) Polyurethane resin As the water-soluble or water-dispersible polyurethane resin, a polyurethane composed of a polyol and a diisocyanate such as a polyester polyol or a polyether polyol and, if necessary, two or more active hydrogens such as a diol and a diamine are added. Those having a low molecular weight compound, which is chain-extended in the presence of a chain extender and stably dispersed or dissolved in water, can be suitably used, and known ones can be used widely (for example, Japanese Patent Publication No. 42-24192, (See JP-B-42-24194, JP-B-42-5118, JP-B-49-986, JP-B-49-33104, JP-B-50-15027, and JP-B-53-29175).

As a method for producing a water-soluble or water-dispersible polyurethane resin, for example, the following method can be used.
(1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, an amino group, or a carboxyl group into the side chain or terminal of a polyurethane polymer, and dispersing or dissolving in water by self-emulsification.
(2) A method in which a polyurethane polymer or a polyurethane polymer in which a terminal isocyanate group is blocked with a blocking agent such as oxime, alcohol, phenol, mercaptan, amine or sodium bisulfite is forcibly dispersed in water using an emulsifier and mechanical shearing force. . Furthermore, a urethane polymer having a terminal isocyanate group is mixed with water, an emulsifier and a chain extender, and dispersion and high molecular weight are simultaneously performed using mechanical shearing force.
(3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol as a main polyurethane raw material and is dispersed or dissolved in water as a water-soluble polyurethane.

  The above-mentioned polyurethane resin is not limited to a single method with respect to the dispersion or dissolution method described above, and a mixture obtained by each method can also be used.

  Examples of the diisocyanate that can be used in the synthesis of the polyurethane resin include alicyclic, aliphatic, and aromatic diisocyanates. Specifically, hexamethylene diisocyanate, tetramethylene diisocyanate; 1,3- (diisocyanatomethyl) cyclohexanone. 1,4- (diisocyanatomethyl) cyclohexanone, 4,4′-diisocyanatocyclohexanone, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate; 3,3′-dimethoxy-4,4′-biphenylene Diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diiso Aneto, m- phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, and the like. Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred.

  Examples of commercially available polyurethane resins include Adekabon titer UX206 (manufactured by ADEKA), Hydran HW-330, HW-340, HW-350 (all manufactured by Dainippon Ink and Chemicals), Superflex 100 150, E-2500, and F-3438D (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

iii) Epoxy resin Examples of the water-soluble or water-dispersible epoxy resin include cationic epoxy resins obtained by adding amines to epoxy resins; modified epoxy resins such as acrylic-modified epoxy resins and urethane-modified epoxy resins. be able to.

  Examples of cationic epoxy resins include adducts of epoxy compounds with primary mono- or polyamines, secondary mono- or polyamines, and primary and secondary mixed polyamines (see, for example, US Pat. No. 3,984,299). An adduct of an epoxy compound with a secondary mono- or polyamine having a ketiminated primary amino group (see, for example, US Pat. No. 4,017,438); having an epoxy compound and a primary amino group ketiminated Examples include etherification reaction products with hydroxyl compounds (see, for example, JP-A-59-43013).

  Examples of the modified epoxy resin include an acrylic modified epoxy resin and a urethane modified epoxy resin.

  Examples of the acrylic-modified epoxy resin include a resin obtained by a reaction between an epoxy compound and a carboxyl group-containing acrylic resin, and a resin obtained by graft polymerization or copolymerization of a polymerizable unsaturated monomer mixture containing a carboxyl group-containing monomer on an epoxy compound. Etc.

  Examples of urethane-modified epoxy resins include resins obtained by reacting polyisocyanate compounds or monoisocyanate compounds with amine-added epoxy resins obtained by reacting amines with epoxy compounds, and polyisocyanate compounds with epoxy compounds and polyalkylene glycols. Reaction of bisphenol A to a mixture of epoxy compound such as bisphenol A type epoxy resin and polyalkylene glycol diglycidyl ether, resin with alkanolamine or other amines added to the epoxy group of urethane-modified epoxy resin obtained by reaction if necessary Further, a resin in which an amine such as alkanolamine is added to the epoxy group of a urethane-modified epoxy resin obtained by further reacting with an isocyanate compound, if necessary, can be exemplified.

  The urethane-modified epoxy resin is dissolved or dispersed in water by neutralizing part or all of the anionic group or cationic group with a neutralizing agent as necessary.

  The number average molecular weight of the epoxy compound is preferably 400 to 4,000, and more preferably 800 to 2,000. Moreover, it is preferable that epoxy equivalent is 190-2,000, and it is more preferable that it is 400-1,000.

  Such an epoxy compound can be obtained, for example, by a reaction between a polyphenol compound and epichlorohydrin.

  Examples of the polyphenol compound include bis (4-hydroxyphenyl) -2,2-propane, 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl)- 1,1-isobutane, bis (4-hydroxy-tert-butylphenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane , Tetra (4-hydroxyphenyl) -1,1,2,2-ethane, 4,4-dihydroxydiphenylsulfone, phenol novolak, cresol novolak and the like.

  As a commercial item of the said epoxy resin, Adeka Resin EM-0718 (made by ADEKA) etc. can be mentioned.

  The addition amount of the water-soluble or water-dispersible organic resin (C) is preferably 20,000 parts by mass or less with respect to 100 parts by mass of peroxovanadate (A) from the viewpoint of paint adhesion and the like. It is more preferably ˜20,000 parts by mass, further preferably 5 to 10,000 parts by mass, and particularly preferably 20 to 5,000 parts by mass. If the addition amount of the water-soluble or water-dispersible organic resin (C) is less than the above range, there is a tendency to be inferior in terms of adhesion to the top coating and processability of the treated film, and if it exceeds the above range, corrosion resistance Tend to be inferior.

Other components The metal surface treatment composition of the present invention contains a metal compound such as a vanadate compound other than peroxovanadate, a zirconium fluoride compound, a zirconium carbonate compound, a titanium fluoride compound, if necessary. Can do.

  Examples of the vanadic acid compound include lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, and anhydrous vanadic acid. Among these, ammonium metavanadate is particularly preferable from the viewpoint of corrosion resistance and the like.

  Examples of the zirconium fluoride compound include zirconium hydrofluoric acid and salts of zirconium hydrofluoric acid such as sodium, potassium, lithium, and ammonium. Among these, zirconium ammonium fluoride and zirconium hydrofluoric acid are preferable from the viewpoint of corrosion resistance and the like.

  Examples of the zirconium carbonate compound include salts of zirconium carbonate such as sodium, potassium, lithium, and ammonium. Among these, ammonium zirconium carbonate is preferable from the viewpoint of corrosion resistance and the like.

  Examples of the titanium fluoride compound include salts of titanium hydrofluoric acid such as sodium, potassium, lithium, and ammonium. Among these, ammonium titanium fluoride is preferable from the viewpoint of corrosion resistance and the like.

  The addition amount of these metal compounds is preferably 2,000 parts by mass or less, for example, from 1 to 2,000 parts by mass with respect to 100 parts by mass of peroxovanadic acid (A) from the viewpoint of corrosion resistance and the like. More preferably, it is more preferably 10 to 1,500 parts by mass, still more preferably 20 to 800 parts by mass, and particularly preferably 50 to 300 parts by mass.

  If necessary, a silane coupling agent can be added to the metal surface treatment composition of the present invention. Examples of the silane coupling agent include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N -Β (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrimethoxy Silane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, octadecyldimethyl [3- (trimethoxy Silyl) propyl] ammonium chloride, trimethylchlorosilane, and the like.

  The addition amount of the silane coupling agent is typically 400 parts by mass or less with respect to 100 parts by mass of peroxovanadic acid (A) from the viewpoint of corrosion resistance after the film is alkali degreased, and 1 to 400 parts. A range of 10 parts by mass and 10 parts by mass is preferred.

  If necessary, organic fine particles and / or inorganic fine particles can be further added to the metal surface treatment composition of the present invention. By adding the fine particles, the transparency of the coating film is lowered, and nitrile (interference color) that tends to occur in the thin film can be suppressed, which is suitable for applications in which appearance is important.

  The average particle diameter of the fine particles is preferably 3 to 1000 nm, particularly 3 to 500 nm, from the viewpoint of sedimentation stability and corrosion resistance.

  Examples of the organic fine particles include resin fine particles such as acrylic, polyurethane, nylon, and polyethylene glycol. Examples of the inorganic fine particles include silica, titanium dioxide, barium sulfate, and calcium carbonate. Silica, titanium dioxide, barium sulfate and the like are preferable from the viewpoint of cost.

  The addition amount of the organic fine particles and / or inorganic fine particles is typically 30% by mass or less, 1-30% by mass, 1-20% by mass in the solid content of the metal surface treatment composition from the viewpoint of corrosion resistance and the like. % Range is preferred.

  In the metal surface treatment composition of the present invention, in addition to the above-described components as necessary, for example, etching agents such as inorganic phosphoric acid compounds and hydrofluoric acid, heavy metal compounds other than the components of the present invention, thickening Agents, surfactants, lubricity-imparting agents (polyethylene wax, fluorine-based wax, carnauba wax, etc.), rust preventives, color pigments, extender pigments, rust preventive pigments, dyes and the like.

  Examples of the inorganic phosphoric acid compound include orthophosphoric acid, metaphosphoric acid, phosphoric acid, metaphosphoric acid, hypophosphoric acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, hexaphosphoric acid, trimetaphosphoric acid, pyro Examples include phosphoric acid and phosphoric acid derivatives. These compounds can be used alone or in combination of two or more. Moreover, these phosphoric acid compounds may form a salt with an alkali compound. Examples of the alkali compound include organic or inorganic alkali compounds containing lithium, sodium, potassium, ammonium and the like. It is preferable to use an inorganic phosphate compound that is soluble in water.

  Examples of heavy metal compounds include metal salts such as Co, Fe, Ni, and In; molybdic acid, tungstic acid, and salts thereof.

  Other examples of rust preventives include polyhydric phenol compounds such as tannic acid; sulfur atom-containing compounds such as thiols and thiocarbonyls; nitrogen atom-containing compounds such as triazoles; thiazoles, thiadiazoles, and thiurams. Sulfur and nitrogen atom-containing compounds; calcium atom-containing compounds such as calcium ion-exchanged silica; boric acid and metaboric acid.

  The metal surface treatment composition of the present invention may be used as diluted with a hydrophilic organic solvent such as methanol, ethanol, isopropyl alcohol, ethylene glycol solvent, propylene glycol solvent, etc., if necessary. it can. Although the dilution rate of the hydrophilic organic solvent can be appropriately changed depending on the use form, for example, the amount of the hydrophilic organic solvent used is preferably 90% by mass or less in the metal surface treatment composition.

  The method for producing the metal surface treatment composition of the present invention is not particularly limited, and peroxovanadate (A), organic phosphonic acid (B), and other components are blended as necessary. It can be manufactured by diluting with water to adjust the solid content to 0.1 to 50% by mass (preferably 0.5 to 40% by mass).

Surface-treated metal material The surface-treated metal material of the present invention is a surface-treated metal material having a metal surface-treated layer obtained from the metal surface treatment composition of the present invention on a metal material. Specifically, a surface-treated metal material can be obtained by applying and baking the metal surface treatment composition of the present invention on a substrate.

  The substrate to which the metal surface treatment composition is applied is not limited as long as it is a metal substrate. Examples thereof include iron, copper, aluminum, tin, zinc, and alloys containing these metals, steel materials plated with these metals, or products deposited with the metals. Among these, when used for steel materials plated with zinc or zinc alloys, particularly galvanized steel sheets and zinc alloy plated steel sheets, the effect of improving corrosion resistance and the like is remarkable.

  Here, the steel material includes a lump or molded product of iron (including an alloy), a plate shape, and a rod shape, and the steel plate is a plate of iron (including an alloy).

  The method for applying the metal surface treatment composition of the present invention onto the substrate is not particularly limited, and can be performed by a known application method.

  Examples of the application method include dip coating, spray coating, roll coating, and the like. As for the baking (drying) conditions for the surface treatment film, it is usually preferable to dry the material for about 2 seconds to about 30 seconds under the condition that the maximum material arrival temperature is about 60 to about 250 ° C.

Moreover, as a process film thickness of the composition for metal surface treatment, it is preferable that it is 0.001-10 g / m < ² > by a dry film thickness normally, and it is more preferable that it is 0.05-3 g / m < ² >. If the treatment film thickness is made too thin, performances such as corrosion resistance and water resistance tend to be lowered. On the other hand, if the treatment film thickness is made too thick, the surface treatment film tends to be broken or the workability is lowered.

  The use of the surface-treated steel sheet of the present invention can be used without particular limitation for applications using conventional surface-treated steel sheets such as for building materials, home appliances, automobiles, cans, and precoated steel sheets. Moreover, undercoat paint, topcoat paint, etc. are appropriately applied as necessary. The coating method may be appropriately selected depending on the application, the shape of the object to be coated, etc. For example, spray coating, brush coating, electrodeposition coating, roll coating, curtain flow coating, etc. are preferably used. A film can be laminated instead of painting.

  Next, the present invention will be described more specifically with reference to production examples, examples and comparative examples. However, the present invention is not limited to the following examples. “Part” and “%” described in each example are based on mass.

Production Example 1 ( Production of metal surface treatment composition)
Add 100 parts by mass of deionized water into a container, add 30 parts by mass of 30% hydrogen peroxide water, add 15 parts by mass of ammonium metavanadate to a well-stirred solution at 25 ° C., and stir for 30 minutes. As a result, an aqueous solution of peroxovanadate was obtained.

Examples 1-13 and Comparative Examples 1-2
Each metal surface treatment composition was prepared according to the formulation shown in Tables 1 and 2 below. In addition, the compounding quantity of each raw material in Table 1, 2 was shown by solid content mass ratio in the composition for metal surface treatments which is an aqueous liquid.

  The metal surface treatment composition was prepared with deionized water so that the solid content was 15%.

  The following test was done about each metal surface treatment composition obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

In Table 1, the raw materials (* 1) to (* 4) have the following contents.
(* 1) Adekabon titer UX206: trade name, manufactured by ADEKA, water-based polyurethane resin.
(* 2) Aquabrid CC234: trade name, manufactured by Daicel Chemical Industries, Ltd., aqueous acrylic resin.
(* 3) Adeka Resin EM-0718: trade name, manufactured by ADEKA, water-based epoxy resin.
(* 4) Superflex E-2500: trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., aqueous polyurethane resin.

Test Example 1 (Storage stability test)
Each metal surface treatment composition adjusted to a solid content of 10% was placed in a glass bottle, sealed, and allowed to stand in a thermostatic chamber at 20 ° C. for 1 month, and then the appearance was visually observed and evaluated according to the following criteria.
a: No sediment or significant thickening is observed.
b: There is a sediment.

Test example 2 (corrosion resistance test)
(1) Preparation of test plate A hot-dip galvanized steel sheet with a plate thickness of 0.5 mm and a single-sided plating coating amount of 60 g / m ² was subjected to an alkaline degreasing agent (trade name “Chem Cleaner 561B” manufactured by Nippon CB Chemical Co., Ltd.). After degreasing and washing with an aqueous solution having a dissolved concentration of 2%, the metal surface treatment compositions obtained in the above Examples and Comparative Examples were applied so that the dry film weight was 1.0 g / m ² . The surface treatment film was formed by baking for 20 seconds such that the material arrival temperature was 100 ° C.
(2) Corrosion resistance test The test coating board which sealed the end surface part and back surface part of the obtained test coating board was subjected to the salt spray test prescribed | regulated to JISZ2371 for 72 hours, and the generation | occurrence | production degree of rust was evaluated by the following reference | standard.
a: Generation of white rust is not recognized.
b: The degree of occurrence of white rust is less than 5% of the coating area (practical range).
c: Generation of white rust is 5% or more and less than 10% of the coating film area.
d: The degree of occurrence of white rust is 10% or more and less than 50% of the coating film area.
e: The degree of occurrence of white rust is 50% or more of the coating film area.

Test Example 3 (Upper coating film adhesion test)
(1) Preparation of test plate A hot-dip galvanized steel sheet with a plate thickness of 0.5 mm and a single-sided plating coating amount of 60 g / m ² was subjected to an alkaline degreasing agent (trade name “Chem Cleaner 561B” manufactured by Nippon CB Chemical Co., Ltd.). After degreasing and washing with a dissolved 2% aqueous solution, the metal surface treatment compositions obtained in the above Examples and Comparative Examples were applied so that the dry film weight was 0.3 g / m ² . A surface treatment film was prepared by baking for 20 seconds so that the material arrival temperature was 100 ° C. Each test coated plate was coated with Amirac # 1000 White (manufactured by Kansai Paint Co., Ltd., thermosetting alkyd resin paint, white) to a dry film thickness of 30 μm, and baked at 130 ° C. for 20 minutes to obtain a top coated plate. It was.
(2) Upper layer coating film adhesion About the obtained test coating board, the vertical and horizontal 11 wounds which reach a base material with a knife were put in the checkerboard shape, and 100 squares of 1 mm square were produced. The degree of peeling of the upper layer coating film was evaluated according to the following criteria when the cellophane adhesive tape was brought into close contact with this grid and the tape was peeled off instantaneously.
a: No peeling of the upper coating film is observed.
b: Although complete peeling of the upper layer coating film is not observed, the edge of the grid is slightly peeled (practical range).
c: 1 to 9 peelings of the upper coating film are observed.
d: Ten or more peelings of the upper layer coating film are observed.

Claims (9)

A metal surface treatment composition comprising (A) peroxovanadic acid and (B) an organic phosphonic acid. The metal surface treatment composition according to claim 1, wherein the organic phosphonic acid (B) has a hydroxyl group-containing organic group. The organic phosphonic acid (B) is at least one selected from 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and 1-hydroxypropane-1,1-diphosphonic acid. The composition for metal surface treatment according to claim 1 or 2, which is contained. The composition for metal surface treatment according to any one of claims 1 to 3, wherein the organic phosphonic acid (B) is contained within a range of 1 to 250 parts by mass with respect to 100 parts by mass of the peroxovanadate (A). object. The metal surface treatment composition according to any one of claims 1 to 4, further comprising a water-soluble or water-dispersible organic resin (C). The metal surface treatment according to claim 5, wherein the water-soluble or water-dispersible organic resin (C) is contained within a range of 1 to 20,000 parts by mass with respect to 100 parts by mass of peroxovanadic acid (A). Composition. The metal surface treatment composition according to any one of claims 1 to 6, wherein the metal surface treatment composition is for a steel material plated with zinc or a zinc alloy. The surface treatment metal material which has a metal surface treatment layer obtained from the metal surface treatment composition in any one of Claims 1-6 on the steel materials plated with zinc or zinc alloy. A surface-treated steel sheet having a metal surface treatment layer obtained from the composition for metal surface treatment according to any one of claims 1 to 6 on a steel sheet plated with zinc or a zinc alloy.