TWI394864B - Metal surface treatment composition, and surface-treated metal material with metal surface treatment film obtained from the metal surface treatment composition - Google Patents

Description

Metal surface treatment group material and surface treated metal material having metal surface treatment film obtained from the metal surface treatment group Technical field

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

Background technique

In the past, chromate treatment and phosphate treatment were generally performed in order to improve the corrosion resistance of the metal surface. However, the toxicity of chromium has become a social problem in recent years. The surface treatment method using chromate has the problem of the smoke scattering of chromate in the treatment process, the huge cost in the drainage treatment equipment, and the problem caused by the dissolution of the outer membrane from the chemical conversion treatment. The hexavalent chromium compound is designated as a carcinogen to human body by most public agencies headed by the International Agency for Research on Cancer Review (IARC) and is extremely harmful.

Phosphate treatment is usually carried out by a zinc phosphate or iron phosphate surface treatment. After the phosphate treatment, for the purpose of imparting corrosion resistance, it is usually washed with chromic acid. Therefore, there are problems such as chromium treatment, drainage treatment of a reaction accelerator or metal ion in a phosphate treatment agent, and soft mud treatment caused by elution of metal ions from a phosphate-treated metal.

Zirconium-based and titanium-based surface treatment agents are known for their treatments other than chromate treatment and phosphate treatment (see Japanese Patent Publication No. S48-24618, etc.), and are mainly used in aluminum-based materials. However, zinc-based materials have a problem that corrosion resistance is inferior to conventional chromate treatment.

A vanadium-based treatment agent other than the zirconium-based and titanium-based materials has been studied. Japanese Patent Laid-Open Publication No. H9-95796 discloses metal surface treatments containing vanadate and/or inorganic acid vanadium salts and organic acids having a reducing power. Electrolytic chemical conversion treatment liquid. This is a chemical conversion treatment of the negative electrode, and the zinc material can also form an excellent outer film of corrosion resistance. However, the treatment method of the electrolytic chemical conversion treatment has its own limit, and is limited to a special use as compared with the treatment of only immersing or coating the treatment liquid at a high cost.

Vanadium is excellent in corrosion resistance and is used as a rust preventive agent by vanadate such as ammonium metavanadate. However, the stability of the vanadium compound in water is inferior, so that it is dispersed by a specific aqueous organic resin and redispersed in water. However, even with this method, it is impossible to add a large amount of the vanadium compound to the surface treatment agent, and the corrosion resistance of the metal surface of the layer formed of the surface treatment agent is unavoidable. Therefore, it has been studied to use peroxovanaic acid formed by reacting a vanadium compound with hydrogen peroxide.

A surface treatment agent using a peroxometal oxyacid salt, which is exemplified by vanadium, is disclosed in Japanese Laid-Open Patent Publication No. S54-147141. However, the stability of peroxovanaic acid in water is superior to the vanadate described above, but it is still insufficient.

Further, if peroxovanaic acid is present alone or if peroxovanaic acid is merely combined with an organic resin, the alkali resistance is already inferior. If the alkali resistance is inferior, there is a problem that the corrosion resistance after degreasing by alkali is lowered. Further, none of the patent documents describes an example of using peroxovanic acid, and sufficient research has not been conducted thereon.

Invention

An object of the present invention is to provide a metal surface treatment composition which has an antirust property comparable to a chromate treatment agent and a phosphate treatment agent, and which is excellent in alkali resistance and is non-polluting.

The inventors of the present invention have conducted a thorough review to solve the above object, and have found that a metal surface treatment composition containing peroxovanaic acid and a titanium compound and/or a zirconium compound has a match with a chromate treatment agent and a phosphate treatment agent. The invention is completed by an anti-rusting property and an excellent alkali resistance.

That is, the present invention provides the following metal surface treatment composition and a surface-treated metal material having the metal surface treatment film obtained from the metal surface treatment composition.

A composition for metal surface treatment, characterized in that it comprises:

(A) peroxovanaic acid; and

(B) a titanium compound and/or a zirconium compound.

2. The metal surface treatment composition according to the above item 1, wherein the titanium compound and/or the zirconium compound (B) contains a halide selected from titanium and a salt thereof, a halide of zirconium and a salt thereof, and zirconium carbonate and A salt thereof and at least one compound of zirconium nitrate.

3. The metal surface treatment composition according to the above item 2, wherein the titanium compound and/or the zirconium compound (B) contains a zirconium fluoride salt, a titanium fluoride salt, a zirconium carbonate and a salt thereof, and a zirconium nitrate. At least one compound.

4. The metal surface treatment composition according to any one of the above-mentioned item 3, wherein the titanium compound and/or the zirconium compound (B) contains ammonium zirconium fluoride, ammonium titanium fluoride, ammonium zirconium carbonate, and At least one compound of zirconium hydrofluoride.

5. The composition for metal surface treatment according to the above items 1 to 4, wherein the content of the titanium compound and/or the zirconium compound (B) is in the range of 1 part by mass based on 100 parts by mass of the peroxyvanadic acid (A). Within 2,000 mass parts.

6. The metal surface treatment composition according to the above items 1 to 4, which further comprises a water-soluble or water-dispersible organic resin (C).

7. The composition for metal surface treatment according to the above item 6, wherein the content of the water-soluble or water-dispersible organic resin (C) is 1 to 1 part by mass based on 100 parts by mass of the peroxyvanadate (A). Within 20,000 mass parts.

8. The metal surface treatment composition according to the above items 1 to 4, wherein the metal surface treatment composition is used for a steel plated with zinc or a zinc alloy.

A surface-treated metal material comprising a metal surface treatment film obtained from a metal surface treatment composition according to the above items 1 to 4, which is coated on a steel plated with zinc or a zinc alloy. .

A surface-treated steel sheet comprising a metal surface treatment film on a steel sheet coated with zinc or zinc alloy, the metal surface treatment film being obtained from the metal surface treatment composition according to the above items 1 to 4 .

The metal surface treatment composition of the present invention contains peroxovanaic acid (A), a titanium compound and/or a zirconium compound (B). It is described in detail below.

Peroxyvanadate (A)

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

Examples of the vanadium compound include vanadium oxides such as vanadium trioxide and vanadium pentoxide; vanadium oxyhalides such as vanadium oxychloride and vanadium oxychloride; vanadium halides such as vanadium trichloride; and ammonium metavanadate. , sodium metavanadate, sodium orthovanadate, vanadyl sulfate, sodium pyroantimonate, and the like. Among them, vanadium pentoxide and ammonium metavanadate are preferred from the viewpoints of ease of manufacture and the like.

The amount of hydrogen peroxide added to the vanadium compound is preferably from 10 to 5,000 parts by mass based on 100 parts by mass of the vanadium compound.

Further, the production of peroxovanaic acid is usually carried out by adding a vanadium compound to an aqueous hydrogen peroxide solution and heating at 20 to 100 ° C for 15 to 120 minutes.

The concentration of the peroxyvanadic acid (A) in the composition for metal surface treatment is not particularly limited, and may be appropriately changed depending on the use form, and for example, it is preferably 0.01 to 100 g/L in the metal surface treatment composition. More preferably 0.1 to 30 g / L. When the concentration of the peroxovanaic acid (A) is less than the above range, sufficient corrosion resistance tends to be insufficient, and when it exceeds the above range, the liquid storage stability tends to deteriorate.

Titanium compound and / or zirconium compound (B)

The titanium compound and/or the zirconium compound of the component (B) of the present invention can be significantly increased in alkali resistance by mixing with the above-mentioned peroxovanaic acid (A) at a specific ratio.

Examples of the titanium compound include titanium hydrofluoride, titanium ammonium fluoride, potassium fluoride fluoride, sodium titanium fluoride, and lithium titanium fluoride.

Examples of the zirconium compound include zirconium hydroxide, zirconium nitrate, zirconium acetate, zirconium carbonate, ammonium zirconium carbonate, zirconium octoate, zirconium hydrofluoride, ammonium zirconium fluoride, sodium zirconium fluoride, potassium zirconium fluoride, and lithium zirconium fluoride. , zirconium fluoride and the like. From the aspect of having a large effect of improving the alkali resistance of the treated film by combination with peroxovanaic acid, at least one of a halide selected from titanium and a salt thereof, a halide of zirconium and a salt thereof, and zirconium carbonate And a salt thereof, and a compound such as zirconium nitrate, preferably at least one selected from the group consisting of ammonium zirconium fluoride (ammonium fluorozirconate), ammonium titanium fluoride (ammonium fluorotitanate), ammonium zirconium carbonate and zirconium hydrofluoride. Such as compounds are preferred.

The content of the titanium compound and/or the zirconium compound (B) is preferably from 1 to 2,000 parts by mass, more preferably from 10 to 1,500 parts by mass, and from 20 to 800 parts per 100 parts by mass of the peroxyvanadic acid (A). The quality department is preferred, especially in the range of 100 to 700 mass parts. If the amount of the compound (B) is less than 1 part by mass, the effect of improving the alkali resistance tends to be small, and if it exceeds 2,000 parts by mass, the effect of improving the corrosion resistance by adding peroxovanaic acid (A) is small. The tendency.

Water-soluble or water-dispersible organic resin (C)

The metal surface treatment composition of the present invention contains peroxovanaic acid (A) and a titanium compound and/or a zirconium compound (B) as an essential component, and is coated on the outer film obtained from the metal surface treatment composition. When the film is attached, in order to improve the adhesion thereto, it is preferred to add a water-soluble or water-dispersible organic resin (C).

The water-soluble or water-dispersible organic resin (C) is an organic resin which is soluble in water or dispersed in water. The method of making the organic resin soluble in water or dispersing it in water can be carried out using a conventional technique.

Specifically, the water-soluble or water-dispersible resin may, for example, contain a functional group (for example, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, an amine (imine) group, a thio group or a phosphine which may be dissolved in water alone or dispersed in water. The resin of the base or the like, and a part or all of the functional groups of the above resins are neutralized as needed. a part or all of the above-mentioned functional group is a resin to be neutralized if necessary, and if the resin is an acidic resin (a resin containing a carboxyl group or the like), the following compounds may be mentioned, for example, an amine compound such as ethanolamine or triethylamine; Ammonia water; an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide. When the resin is a basic resin (an amine group-containing resin), the following compounds may, for example, be a fatty acid such as acetic acid or lactic acid or a mineral acid such as phosphoric acid.

The base resin of the water-soluble or water-dispersible organic resin to be added may, for example, be an epoxy resin, a phenol resin, an acrylic resin, a polyurethane resin, an olefin-carboxylic acid resin, a nylon resin, a resin having a polyoxyalkylene chain, or the like. Polyvinyl alcohol, polyglycerin, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and the like. The above resins may be used singly or in combination of two or more. From the viewpoint of storage stability of the metal surface treatment composition, among them, at least one selected from the group consisting of water-soluble or water-dispersible acrylic resins, polyurethane resins, and epoxy resins is preferred.

i) Acrylic resin

The water-soluble or water-dispersible acrylic resin can be obtained by a conventional method such as emulsion polymerization, suspension polymerization, synthesis of a polymer having a hydrophilic group by solution polymerization, neutralization as needed, and aqueous solution thereof. obtain.

The above hydrophilic group-containing polymer can be polymerized with other unsaturated monomers as needed by an unsaturated monomer having a hydrophilic group such as a carboxyl group, an amine group, a polyoxyalkylene group or the like and a derivative thereof. obtain.

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

The amine group-containing unsaturated monomer and its derivative may, for example, be dimethylaminoethyl N,N-(meth)acrylate, diethylamine ethyl N,N-(meth)acrylate, Nt-( A nitrogen-containing (meth)acrylic acid alkyl ester such as butylamine ethyl methacrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (methyl) Acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N,N-dimethylaminopropyl (meth) acrylamide, N,N-dimethylamine ethyl (meth) acrylamide, etc., polymerizable guanamine; acrylamide, etc. .

Further, a nitrogen-containing monomer such as 2-vinylpyridine, 1-vinyl-2-pyrrolidone or 4-vinylpyridine is also used as an unsaturated monomer having a hydrophilic group.

The hydroxyl group-containing unsaturated monomer may, for example, be 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxybutyl (meth)acrylate, or (meth)acrylic acid. A hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl ester.

The polyoxyalkylene group-containing unsaturated monomer may, for example, be a monoester of a polyhydric alcohol such as polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate and acrylic acid or methacrylic acid.

Further, in the above-mentioned (meth)acrylic acid hydroxyalkyl ester or a monoester of a polyhydric alcohol and acrylic acid or methacrylic acid, a compound in which ring-opening polymerization of e-caprolactone or the like can be used.

Examples of other unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. , isobutyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, ( A methyl (meth) acrylate having 1 to 24 carbons such as tridecyl methacrylate, octadecyl (meth) acrylate or isostearyl (meth) acrylate; vinyl acetate or the like. These compounds may be used singly 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 based on the total of the monomers, and preferably 80% by mass or less.

Further, from the viewpoint of corrosion resistance and the like, the water-soluble or water-dispersible acrylic resin is preferably a copolymer of styrene. The amount of styrene in all the unsaturated monomers is preferably 60% by mass or less, more preferably 10 to 60% by mass, still more preferably 15 to 50% by mass.

Moreover, from the viewpoint of obtaining the toughness of the outer film, etc., the Tg (glass transition point) of the acrylic resin obtained by copolymerization is preferably 30 to 80 ° C, and more preferably 40 to 70 ° C.

As a commercial product of the above acrylic resin, for example, Aquabrid CC234 (manufactured by Daicel Chemical Industries, Ltd.) can be mentioned.

Ii) polyurethane resin

As the above polyurethane resin, a polyurethane obtained by using a polyol such as a polyester polyol or a polyether polyol and a diisocyanate can be suitably used, and a low molecular weight having two or more active hydrogen atoms such as a diol or a diamine can be used as needed. A compound which is chain-extended in the presence of a chain extender and which is stably dispersed or dissolved in water can be widely used. (For example, refer to Japanese Patent Publication No. S42-24192, Japanese Patent Publication No. S42-24194, Japanese Patent Publication No. S42-5118, Japanese Patent Publication No. S49-986, Japanese Patent Publication No. S49-33104, Japanese Patent Publication No. S50-15027, and Japanese Patent Publication No. S53-29175.

The water-soluble or water-dispersible polyurethane resin can be suitably produced by, for example, the following method:

(1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, an amine group or a carboxyl group to a branch or a terminal of a polyurethane polymer, and dispersing or dissolving it in water by self-emulsification.

(2) The polyurethane ester polymer or the terminal isocyanate group blocked by a reaction agent such as hydrazine, ethanol, phenol, thiol, amine, sodium hydrogen sulfite or the like is blocked by an emulsifier and a mechanical shear. A method of forcing it to be dispersed in water. Further, there is a method in which an amine ester polymer having a terminal isocyanate group is mixed with water, an emulsifier, and a chain extender, and simultaneously subjected to mechanical shearing to carry out dispersion and high molecular weight.

(3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol of a main raw material of a polyurethane, and then the polyurethane is dispersed or dissolved in water like a water-soluble polyurethane polymer.

In the above polyurethane resin, the above-described dispersion or dissolution method is not limited to a single method, and a mixture obtained by various methods may be used.

Examples of the diisocyanate which can be used in the synthesis of the above polyurethane resin include aromatic, alicyclic and aliphatic diisocyanates, and specific examples thereof include hexamethylene diisocyanate, tetramethylene diisocyanate, and 3,3'-. Dimethoxy-4,4'-biphenyldiisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3-(diisocyanate)cyclohexanone, 1,4- (diisocyanate) cyclohexanone, 4,4'-diisocyanate cyclohexanone, 4,4'-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, 2, 4-toluene diisocyanate, 2,6-toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, isophthalic diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4, 4'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, and the like. Among them, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.

The polyester resin may be, for example, Adeka Bontiter UX206 (manufactured by ADEKA Corporation), Hydran HW-330, HW-340, and HW-350 (all manufactured by Dainippon Ink & Chemicals, Inc.), Superflex 100, 150, E-2500, and F-3438D (all manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.).

Iii) Epoxy resin

The epoxy resin may, for example, be a cationic epoxy resin obtained by adding an amine to an epoxy resin; a modified epoxy resin such as an acrylic acid modification or an amine ester modification may be suitably used.

The cationic epoxy resin may, for example, be an adduct of an epoxy compound with a primary monomer or a polyamine, a secondary monomer or a polyamine, a primary or secondary mixed polyamine (for example, refer to US Pat. No. 3,984,299); An addition product of an oxygen compound to a secondary monomer or a polyamine having a primary amine group which has been converted into a ketimine (for example, refer to the specification of US Pat. No. 4017438); an epoxy compound having a conversion to a ketimine A product of an etherification reaction of an amino group of a hydroxy compound (for example, see Japanese Patent Laid-Open Publication No. S59-43013).

Examples of the modified epoxy resin include an acrylic modified epoxy resin and an amine ester modified epoxy resin.

The acrylic modified epoxy resin may, for example, be a resin obtained by reacting an epoxy resin with a carboxyl group-containing acrylic resin; and graft polymerization of a polymerizable unsaturated monomer mixture having a carboxyl group-containing monomer on the epoxy resin. Or copolymerized resin.

The amine ester-modified epoxy resin may, for example, be a resin obtained by reacting an amine-containing epoxy resin obtained by reacting an amine with an epoxy compound with a polyisocyanate compound or a monoisocyanate compound; and an epoxy compound and a polyolefin-based diol; And a resin obtained by adding an amine of an alkanolamine or the like to an epoxy group of an amine ester-modified epoxy resin obtained by a reaction of a polyisocyanate compound; and an epoxy compound such as a bisphenol A type epoxy resin and The mixture of polyolefin-based diol diepoxypropyl ether is reacted with bisphenol A, and the epoxy gene of the amine ester-modified epoxy resin obtained by reacting the isocyanate compound with the alkanolamine is added as needed. The resin obtained after the amines, etc.

The amine ester modified epoxy resin is neutralized or dispersed in water by neutralizing a part or all of an anionic group or a cationic group with a neutralizing agent.

The number average molecular weight of the above epoxy compound is preferably from 400 to 4,000, more preferably from 800 to 2,000. Further, the epoxy equivalent is preferably from 190 to 2,000, more preferably from 400 to 1,000.

Such an epoxy compound can be obtained, for example, by reacting a polyphenol compound with epichlorohydrin.

The polyphenol compound may, for example, be bis(4-hydroxyphenyl)-2,2-propane, 4,4-dihydroxydiphenyl ketone, bis(4-hydroxyphenyl)-1,1-ethane, bis (4) -hydroxyphenyl)-1,1-isobutane, bis(4-hydroxytriphenylene)-2,2-propane, bis(2-hydroxynaphthalene)methane, 1,5-dihydroxynaphthalene, double (2 , 4-dihydroxybenzene)methane, tetrakis(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4-dihydroxydiphenylhydrazine, phenol aldehyde, cresol aldehyde, and the like.

The commercial product of the above epoxy resin may, for example, be Adeka Resin EM-0718 (manufactured by ADEKA Co., Ltd.) or the like.

The amount of the water-soluble or water-dispersible organic resin (C) to be added is preferably from 1 to 20,000 parts by mass based on 100 parts by mass of the peroxyvanadic acid (A), from the viewpoint of the adhesion of the overcoat coating material and the like. It is preferably 5 to 10,000 mass parts, and 20 to 5,000 mass parts, especially 500 to 2,500 mass parts.

Other ingredients

The metal surface treatment composition of the present invention may further contain a vanadium acid compound other than peroxovanaic acid as needed.

Examples of the vanaic acid compound include lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, and vanadium anhydride. Among them, ammonium metavanadate is preferred from the viewpoint of corrosion resistance and the like.

The amount of addition is preferably 1,500 parts by mass or less, and may be, for example, 1,500 parts by mass or less, and may be from 1 to 1,500 parts by mass, and from 10 to 800 parts by mass, from the viewpoint of corrosion resistance and the like.

In the metal surface treatment composition of the present invention, an organic acid is added in order to enhance the storage stability of the treatment agent, particularly an organic phosphonic acid.

The organic phosphonic acid may, for example, be 1-hydroxymethyl-1,1-diphosphonic acid, 1-hydroxyethyl-1,1-diphosphonic acid, 1-hydroxypropion-1,1-diphosphonic acid or the like having a hydroxyl group. Organic phosphonic acid of organic group; organic phosphonic acid having a carboxyl group-containing organic group, such as 2-hydroxyphosphoninoacetic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, and the like Salts of the compounds and the like are suitable.

The above organic phosphonic acid is excellent in improving the storage stability of the aqueous solution of the peroxovanadate (A). Among them, from the viewpoint of storage stability, it is preferred to use an organic phosphonic acid having a hydroxyl group-containing organic group, particularly 1-hydroxyethyl-1,1-diphosphonic acid, 1-hydroxymethyl-1,1-di. Phosphonic acid is preferred.

Since the stability of peroxovanaic acid (A) in water is inferior, the addition of the organic phosphonic acid is preferably added immediately after the production of peroxovanaic acid.

From the viewpoint of storage stability, the amount of the organic phosphonic acid to be added is preferably from 1 to 250 parts by mass based on 100 parts by mass of the peroxyvanadic acid (A), and preferably from 5 to 200 parts by mass. 25 to 160 mass parts are preferred.

The metal surface treatment composition of the present invention may be added with a ruthenium coupling agent as needed. The oxime coupling agent may, for example, be N-β(aminoethyl)γ-aminopropyltrimethoxy decane, N-β(aminoethyl)γ-aminopropylmethyldimethoxy decane, γ-methyl propylene carbonyl. Oxypropyl trimethoxy decane, N-β (vinylbenzylaminoethyl) γ-propyltrimethoxy decane hydrochloride, γ-dehydroglyceryloxypropyltrimethoxy decane, γ-thiol Propyltrimethoxyoxane, γ-thiolpropylmethyldimethoxydecane, methyltrimethoxyoxane, vinyltriethoxypropane, γ-chlorotrimethoxypropane, hexamethyldidecylamine Alkane, γ-anilinopropyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, dimethyl octadecyl [3-(trimethoxy decyl) propyl] ammonium chloride, trimethyl chloride Decane and so on.

The amount of the ruthenium coupling agent added is preferably 400 parts by mass or less per 100 parts by mass of the peroxyvanadic acid (A) from the viewpoint of the corrosion resistance of the outer film after the alkali degreasing treatment, and the like. 400 mass parts, 10~400 mass parts.

In the metal surface treatment composition of the present invention, organic fine particles and/or inorganic fine particles may be further added as needed. By adding the fine particles, the transparency of the coating film is lowered, and the interference color which is likely to occur in the film can be suppressed, and it is suitable for use in which the appearance is emphasized.

The particle diameter of the fine particles is preferably from 3 to 1,000 nm in average particle diameter, and particularly in the range of from 3 to 500 nm from the viewpoint of particle sedimentation stability and corrosion resistance.

Examples of the organic fine particles include resin fine particles such as acrylic acid, polyurethane, nylon, and polyethylene glycol. Further, examples of the inorganic fine particles include cerium oxide, titanium oxide, barium sulfate, calcium carbonate, and the like. Among them, cerium oxide, titanium oxide, barium sulfate, and the like are preferred from the viewpoint of cost and the like.

From the viewpoint of corrosion resistance, the amount of the organic fine particles and/or the inorganic fine particles added is preferably 30% by mass or less based on the solid content of the metal surface treatment composition, and is preferably 1 to 30% by mass, particularly 1 to 1%. 20% by mass range.

In the metal surface treatment composition, an etchant such as an inorganic phosphate compound or hydrofluoric acid, a heavy metal compound other than the component of the present invention, a tackifier, a surfactant, and a lubricant (polyethylene wax) may be contained in addition to the above components. , fluorine-containing wax, palm wax, etc.), rust inhibitors, coloring pigments, body pigments, anti-rust pigments, dyes, and the like.

The inorganic phosphate compound may, for example, be orthophosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, hypophosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, hexaphosphoric acid, trimellitic acid, pyrophosphoric acid, and phosphoric acid derived. Things and so on. One or two or more of these compounds may be used in combination. Further, the phosphate compound may form a salt with a basic compound. The basic compound may, for example, be an organic or inorganic basic compound containing lithium, sodium, potassium or ammonium. The inorganic phosphate compound is preferably one which has solubility in water.

The heavy metal compound may, for example, be a salt of a metal such as cobalt, iron, nickel or indium; molybdic acid, tungstic acid or a salt thereof.

Other rust inhibitors include polyhydric phenol compounds such as tannic acid; sulfur atom-containing compounds such as mercaptans and thiocarbonyls; nitrogen atom-containing compounds such as triazoles; thiazoles, thiadiazoles, and methylthiocarbonamides. a compound containing a sulfur atom and a nitrogen atom; a calcium atom-containing compound such as calcium ion exchange ruthenium dioxide; and boric acid, metaboric acid, and the like.

Further, the metal surface treatment composition may be diluted with a hydrophilic solvent such as methanol, ethanol, isopropanol, ethylene glycol solvent or propylene glycol solvent as needed.

The method for producing the metal surface treatment composition of the present invention is not particularly limited, and peroxyvanadate (A), a titanium compound, and/or a zirconium compound (B) may be used, and other components may be blended as needed, and the solid content is adjusted to 0.1. ~50% by mass (preferably 0.5 to 40% by mass).

Surface treated metal

The surface-treated metal material of the present invention is a metal surface treatment film obtained by the above metal surface treatment composition on a metal material. Specifically, the metal surface treatment composition of the present invention can be coated and baked on a substrate to obtain a surface-treated metal material.

The substrate suitable for the above metal surface treatment composition is not limited as long as it is a metal substrate. For example, iron, copper, aluminum, tin, zinc, and alloys containing the metals, and steels plated from the metals or products deposited from the metals may be mentioned. Among them, a steel plated with zinc or a zinc alloy is used, and in particular, when a steel plate of a galvanized steel plate or a galvanized alloy is used, the effect of improving corrosion resistance and the like is remarkable.

Here, the steel material refers to a block or a molded product containing iron (including an alloy), a plate shape, or a rod shape, and the steel plate is a plate in which iron (including an alloy) is formed into a plate shape.

The metal surface treatment composition of the present invention can be treated on a substrate by a conventionally known treatment method such as dip coating, spray coating, or roll coating.

The surface treatment film is usually baked (dried) at a maximum temperature of from about 60 ° C to about 250 ° C for about 2 seconds to about 30 seconds.

Further, if the treatment film thickness of the metal surface treatment composition is too thin, the properties such as corrosion resistance and water resistance are lowered, and on the other hand, if the treatment film thickness is too thick, the surface treatment film may be cracked or processed. If it is low, it is usually a dry film thickness of 0.001 to 10 g/m ² , particularly preferably 0.05 to 3 g/m ² . .

The use of the surface-treated steel sheet of the present invention can be used for applications such as building materials, home appliances, automobiles, cans, and precoated steel sheets, and is not particularly limited, and may be used as needed. Primer coatings, exterior coatings, etc. are suitable for coating. The coating method may be appropriately selected depending on the application, the shape of the object to be coated, and the like, and is suitable for use, for example, spray coating, brush coating, electrodeposition coating, roll coating, and curtain coating. It is also possible to replace the coating by a lamination method.

Best form for implementing the invention

Next, the examples and comparative examples will be described, and the present invention will be more specifically described. However, the invention is not limited by the following examples. The "parts" and "%" disclosed in each case are those based on quality.

Production Example 1 ( Manufacture of composition for metal surface treatment)

Adding 100 parts of deionized water to the vessel, adding 30 parts of 30% hydrogen peroxide water, stirring it, and adding 15 parts of ammonium metavanadate to the solution at a liquid temperature of 25 ° C, and stirring for 30 minutes. An aqueous solution of peroxovagic acid was obtained.

Examples 1 to 9 and Comparative Examples 1 to 2

Each metal surface treatment composition was prepared in accordance with the formulations shown in the following Tables 1 and 2. The formulation amount of each raw material of Tables 1 and 2 is represented by the solid content mass ratio in the metal surface treatment composition of the aqueous liquid.

The composition for metal surface treatment was prepared by deionized water to have a solid content of 15%.

In Table 1, the raw materials of (*1) to (*4) are the following contents.

(*1) Adeka Bontiter UX206: trade name, manufactured by ADEKA, water-based polyurethane resin.

(*2) Aquabrid CC234: trade name, manufactured by Dainippon Ink & Chemicals, Inc., water-based acrylic resin.

(*3) Adeka Resin EM-0718: Trade name, manufactured by ADEKA, waterborne epoxy resin.

(*4) Superflex E-2500: trade name, manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd., aqueous polyurethane resin.

Test 1

(1) Production of test panels

A hot-dip galvanized steel sheet having a thickness of 0.5 mm and a single-side plating adhesion of 60 g/m ² was degreased using an aqueous solution containing an alkaline degreasing agent (manufactured by Japan CB Chemical Co., Ltd., trade name "Chemicleaner 561B") at a concentration of 2%. After washing with water, the composition for metal surface treatment obtained by the above examples and comparative examples was applied thereon so that the weight of the dried outer film became 1.0 g/m ² , and the material reached a temperature of 100 ° C and baked for 20 seconds. A surface treatment film is formed. The test panels obtained were tested according to the following test methods. The results are combined in Tables 1 and 2.

(2) Alkali resistance test

Each test plate was immersed in a 0.1 standard sodium hydroxide standard solution for 120 seconds, and the state of the outer film was visually observed, and evaluated according to the following criteria.

a: The outer membrane remains.

b: The outer membrane does not remain.

(3) Corrosion resistance after alkali degreasing

The test plate coated with the end surface portion and the rear portion of the test coated plate was degreased and washed with an aqueous solution containing an alkaline degreaser (manufactured by Japan CB Chemical Co., Ltd., trade name "Chemicleaner 561B") at a concentration of 2%, and then subjected to JIS Z2371. The salt spray test was carried out up to 72 hours, and the degree of rust was evaluated on the basis of the following criteria.

a: No rust was observed.

b: The degree of rust was observed to be a practical range of 5% of the film area.

c: The degree of rust was observed to be 5% or more of the coating film area, and less than 10%.

d: The degree of rust was observed to be 10% or more of the coating area, and less than 50%.

e: The degree of rust was observed to be 50% or more of the coating area.

Test 2

(1) Production of test panels

A hot-dip galvanized steel sheet having a thickness of 0.5 mm and a single-side plating adhesion of 60 g/m ² was degreased using an aqueous solution containing an alkaline degreasing agent (manufactured by Japan CB Chemical Co., Ltd., trade name "Chemicleaner 561B") at a concentration of 2%. After washing with water, the composition for metal surface treatment obtained by the above examples and comparative examples was applied thereon so that the weight of the dried outer film became 0.3 g/m ² , and the temperature of the material reached 100 ° C and baked for 20 seconds. A surface treatment film is formed. Each test plate was coated with Amilac #1000 White (manufactured by Kansai Paint Co., Ltd., thermosetting acid alcohol resin paint, white) to have a dry film thickness of 30 μm, and baked at 130 ° C for 20 minutes to obtain an overcoat. Coating board.

With respect to each test plate obtained, the test of the adhesion of the upper layer coating film was carried out according to the following test method. The results are shown in Table 1 below.

(2) Upper coating film adhesion

For the test coating, a trace of 11 sections of the vertical and horizontal sides of the coated surface on the coated surface was used to draw a checkerboard pattern of 100 squares of 1 mm ² per square. The degree of peeling of the upper coating film when the portion of the checkerboard was attached to the checkerboard portion by the cellophane adhesive tape was evaluated by the following criteria.

a: The peeling of the upper coating film was not observed at all.

b: It was observed that although the upper coating film was not completely peeled off, the edge of the lattice was slightly peeled off (practical range).

c: 1 to 9 peeling of the upper coating film was observed.

d: It was observed that the upper coating film was peeled off by 10 or more.

The metal surface treatment composition of the present invention comprises peroxovanaic acid and a titanium compound and/or a zirconium compound.

It is expected that corrosion resistance can be improved by using peroxovanic acid, but only peroxyvanadic acid alone or in combination with an organic resin alone is inferior in alkali resistance, so that the surface-treated metal is degreased after use, There is a problem that the corrosion resistance is greatly reduced. However, by combining the titanium compound and/or the zirconium compound, the alkali resistance is remarkably improved, and it is also known by the combination with the aqueous organic resin. It can be widely used to achieve a balance of performance of the treatment film (for example, balance between corrosion resistance and workability, material adhesion, etc.), and performance comparable to chromate treatment and phosphate treatment can be obtained. Therefore, it is very useful to replace these treatment agents into a chromium-free surface treatment agent for metal surface treatment applications.

Claims (10)

A composition for metal surface treatment comprising: (A) peroxyvanadic acid; and (B) a titanium compound and/or a zirconium compound. The composition for metal surface treatment according to claim 1, wherein the titanium compound and/or the zirconium compound (B) contains a halide selected from titanium and a salt thereof, a halide of zirconium and a salt thereof, and zirconium carbonate and A salt thereof and at least one compound of zirconium nitrate. The metal surface treatment composition according to claim 2, wherein the titanium compound and/or the zirconium compound (B) contains a zirconium fluoride salt, a titanium fluoride salt, a zirconium carbonate and a salt thereof, and a zirconium nitrate. At least one compound. The composition for metal surface treatment according to claim 3, wherein the titanium compound and/or the zirconium compound (B) contains ammonium zirconium fluoride, ammonium titanium fluoride, ammonium zirconium carbonate, and zirconium hydrofluoride. At least one compound. The metal surface treatment composition according to any one of claims 1 to 4, wherein the content of the titanium compound and/or the zirconium compound (B) is 100 parts by mass relative to the peroxyvanadate (A). It is in the range of 1 to 2,000 parts by mass. The metal surface treatment composition according to any one of claims 1 to 4, which further comprises a water-soluble or water-dispersible organic resin (C). The metal surface treatment composition according to claim 6, wherein the water-soluble or water-dispersible organic resin (C) is contained in an amount of from 1 to 20,000 per 100 parts by mass of the peroxyvanadate (A). Within the quality department. The metal surface treatment composition according to any one of claims 1 to 4, wherein the metal surface treatment composition is used for a steel plated with zinc or a zinc alloy. A surface-treated metal material comprising a metal surface treatment film on a steel plated with zinc or a zinc alloy, the metal surface treatment film being used for metal surface treatment according to any one of claims 1 to 4. The person who obtained the composition. A surface-treated steel sheet comprising a metal surface treatment film on a steel plate plated with zinc or a zinc alloy, the metal surface treatment film being composed of a metal surface treatment according to any one of claims 1 to 4. The person who obtained the object.