TW200934888A - Metal surface treatment composition, and surface-treated metal material with metal surface treatment layer obtained from the metal surface treatment composition - Google Patents

Abstract

An object of the present invention is to provide a pollution-free metal surface treatment composition that has an anticorrosive power comparable to heretofore known chromating and phosphating agents, and is excellent in storage stability, processability, overcoatability, etc. ; and a surface-treated metal material obtained using the metal surface treatment composition. The present invention provides a metal surface treatment composition comprising (A) peroxovanadic acid, (B) an organic phosphonic acid, and, if necessity, (C) a water-soluble or water-dispersible organic resin.

Description

200934888 VI. Description of the Invention: [Technical Field] The present invention relates to a composition for metal surface treatment and a surface-treated metal having a metal surface treatment layer obtained from the composition for metal surface treatment material. [Prior Art 3] In the past, in order to improve the corrosion resistance of a metal surface, chromic acid salt treatment and phosphate treatment were generally performed. 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 engineering, the need for the magic treatment of the drainage treatment equipment, and the problem caused by the dissolution of the outer membrane by the chemical conversion treatment. . Most of the public agencies, headed by the IARC (International Agency for Research on 15 Cance1·Review), are designated as carcinogenic to humans and are extremely harmful substances. The sulphate treatment is usually carried out by surface treatment of a phosphate or iron phosphate system. After the acidification treatment, it is usually treated with chromic acid/monthly for the purpose of imparting corrosion resistance. Therefore, there are problems such as the treatment of the enthalpy, the treatment of the reaction accelerator or the metal ion in the sulphate treatment, and the treatment of the scum from the sulphate treatment of the metal ions. The treatment methods other than the treatment of 夂@夂盐 and sulphate treatment, the miscellaneous and the surface treatment agent are well-known (refer to the 曰48_24618A newspaper, etc.), which is mainly used in Ming materials. . However, for the lexicographic material, there will be 3 200934888 < the problem of poor corrosion compared to the previous chromate treatment. A vanadium-based treatment agent has been studied in addition to the erroneous system and the titanium system. Japanese Patent Laid-Open Publication No. H9-95796 discloses a metal surface treatment containing a bismuth citrate and/or an inorganic acid hunger salt and a reducing organic acid. Electrolytic chemical conversion treatment of 5 liquids. This is because the negative electrode chemical conversion treatment can also form an excellent outer layer of the corrosion-resistant outer layer of the zinc material. However, the so-called electrolytic chemical conversion treatment method has its own limit, and is limited to a special use as compared with the case where only the material is immersed or the treatment liquid is treated at a high cost. Vanadium is excellent in corrosion resistance and is used as a rust preventive 10 rust agent such as vanadate such as ammonium metavanadate. However, the vanadium compound has a poor stability in water, and therefore it is dispersed by a special 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 having the layer formed of the surface treatment agent is unavoidable. Therefore, it has been studied to use peroxic acid which is reacted with a hydrogen peroxide by a vanadium compound. A surface treatment agent using a peroxometal oxyacid salt is disclosed in the Japanese Patent Laid-Open Publication No. S54-147141, which is based on vanadium. However, the stability of yttrium vanadic acid in water is superior. The vanadate described above has a problem in terms of storage stability due to the tendency to precipitate. Further, no one of the patent documents describes an example of the use of peroxovanic acid, and sufficient research has not been conducted thereon. This is considered to be because the storage stability of the treating agent has not reached the point of practically no problem. DISCLOSURE OF INVENTION PROBLEMS TO BE SOLVED 4 200934888 5 The object of the present invention is to provide a metal surface treatment composition which has an anti-rusting property comparable to a chromate treatment agent and a phosphate treatment agent, and which has excellent storage stability and is non-polluting type. Things. The inventors of the present invention have carefully examined the above-mentioned objects and found that the metal surface treatment composition containing peroxovanaic acid and organic phosphonic acid has anti-rusting power comparable to chromate treating agent and phosphate treating agent. And the storage stability is excellent, and the present invention is completed. That is, the present invention provides the following composition for metal surface treatment and 10 10 surface-treated metal material having a metal surface treatment layer obtained from the metal surface treatment composition. A composition for metal surface treatment comprising: (A) peroxyvanadic acid; and (B) an organic phosphonic acid. The metal surface treatment composition according to the above item 1, wherein the organic phosphonic acid (B) has an organic group having a hydroxyl group. 3. The metal surface treatment composition according to the above item 1 or 2, wherein the organic phosphonic acid (B) contains a group selected from the group consisting of 1-hydroxymethyl-1,1-diphosphonic acid and 1-hydroxyethyl-1. And at least one compound of 1-diphosphonic acid and 1-hydroxypropyl-1,1-diphosphonic acid. The metal surface treatment composition according to any one of the above items 1 to 3, wherein the organic phosphonic acid (B) is contained in an amount of from 1 to 250 parts by mass relative to the mass of the peroxyvanadate (A) 100. Within the scope. 5. The metal surface treatment composition according to any one of items 1 to 4 above, which further comprises a water-soluble or water-dispersible organic resin (C). 5 200934888 6. The metal surface treatment composition according to item 5 above, which contains the water, the Du Du or the water-dispersible organic resin (C) relative to the peroxy sulphuric acid (A) 100 mass parts at 1 to 2 〇, within the scope of the quality department. 7. The metal surface treatment composition according to any one of the above items 1 to 6, wherein the metal surface treatment composition is used for a steel material which is subjected to zinc or zinc alloy electric ore. 8. A surface metal material having a metal surface treatment layer which is obtained on a steel material of a mineral or zinc alloy and which is obtained by a metal watch composition such as No. 6 to No. 6 . 〇 9. A surface-treated steel sheet having a metal surface treatment layer obtained by galvanizing or alloying a steel sheet and obtained by the metal surface treatment of any one of the items (5). 10. A method of producing a surface metal material by forming a metal surface obtained by a composition of a surface treatment of a metal sheet of the galvanized or zinc alloy and having a metal surface treatment according to any one of items 1-6 to 6. Processing layer. 11_ A method for producing a surface metal steel sheet which is formed by a metal surface treatment layer obtained by a metal surface treatment composition according to any one of Items 1-6 to 6 of the steel plated or zinc alloy. The metal surface treatment composition of the present invention contains peroxovanaic acid (A) 20 and an organic phosphonic acid (B). It is described in detail below. Peroxyvanadic acid (A) The peroxyvanadic 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 6 200934888 oxide such as vanadium trioxide or vanadium pentoxide; oxygen vanadium such as oxygen vanadium pentoxide or vanadium oxysulfide; and vanadium vanadium such as three gasification hunger; Ammonium metavanadate, sodium metavanadate, sodium orthovanadate, vanadyl sulfate, sodium pyrovanadate, and the like. Among them, in view of ease of manufacture, it is preferable to record ruthenium pentoxide and hunger. The amount of hydrogen peroxide added to the vanadium compound is preferably about 10 to 5,0 Å by mass based on 100 parts by mass of the compound.

10 Further, the production of peroxovanic acid can be carried out by adding a hunger compound to an aqueous hydrogen peroxide solution and heating at 20 to 1 ° C for 15 to 12 minutes to carry out peroxoic acid (A). The thick sound in the composition for metal surface treatment is not particularly limited, and may be appropriately changed according to the use form, for example, 0.01 to 100 g/L in the composition for metal surface treatment, and more preferably 〇i to 30 g/ L is better. When the concentration of peroxovanaic acid (A) is less than the above range, there is a tendency that sufficient corrosion resistance is not obtained, and when it exceeds the above range, there is a tendency for deterioration in liquid storage stability.

The organic phosphonic acid of the component (B) of the present invention may be, for example, κ light methyl-1,1-diphosphonic acid, 1·ethyl-1,1-diphosphonic acid, κ propyl propyl sulphate. An organic phosphonic acid having a transbasic organic group; an organic phosphonic acid having a carboxyl group-containing organic 20 such as 2-phosphoric acid, 2-phosphonic butane-quinone di-tricarboxylic acid And its salts. The above organic phosphonic acid has an excellent effect in improving the storage stability of the above aqueous solution of peroxic acid (Α), wherein from the viewpoint of storage stability, it is preferred to use an organic phosphonic acid having a hydroxyl group-containing organic group. And 丨, hydroxymethyl-1,1-diphosphonic acid, 1_ethyl-1,1-diphosphonic acid, hydrazine-propyl-i'l, diphosphine 7 200934888 acid is preferred 'special Preferably, 1-hydroxyethyl-1,1-diphosphonic acid is used. Since the stability of peroxovanaic acid (A) in water is poor, the addition of the organic phosphonic acid (B) is preferably added immediately after the production of peroxyvanadate. The metal surface treatment composition of the present invention contains peroxyvanadate (A) 5 and an organic phosphonic acid (B) and is excellent in storage stability. From the viewpoint of storage stability, the amount of the organic phosphonic acid (B) added is preferably from 1 to 250 parts by mass, and from 5 to 200 parts by mass, based on the mass fraction of the peroxyvanadic acid (A). It is better to use the quality of 25~160. Water-soluble or rice-dispersible organic resin (C) 10 The metal surface treatment composition of the present invention is improved in adhesion and workability when coating a coating layer on a layer formed of a metal surface treatment composition. It is preferable 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 sulfur group, which may be dissolved in water alone or dispersed in water. The resin of the phosphino group, etc., 20 and some or all of the functional groups of the above resins are neutralized as needed. a part or all of the above-mentioned functional groups are required to be neutralized, and if the resin is an acidic resin (a carboxyl group-containing resin or the like), the neutralizing compound may, for example, be an amine compound such as ethanolamine or triethylamine; Ammonia; an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide. If the resin in 200934888 is a basic resin (a resin containing an amine group), the following compounds may be exemplified by the following compounds: fatty acids such as acetic acid and lactic acid; and mineral acids such as phosphoric acid. 5 e 10 15 ❹ 20 Base resin of organic resin which can be dissolved or dispersed in water, for example, epoxy resin, phenol resin, acrylic resin, heteroester resin, olefinic resin, hetero resin, silk oxide The chain, polyglycol polyglycol/yellow, renegade-based cellulose, methyl cellulose, ethyl cellulose, etc. The above resins may be used singly or in combination. 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 (tetra) acid resins, poly-resin resins and epoxy resins is preferred. i) Acrylic resin Water-soluble or water-dispersible acrylic resin can be obtained by a conventional method, for example, emulsion polymerization, suspension polymerization, polymerization of a polymer having a hydrophilic group by solution polymerization, neutralization as needed, and aqueous solution thereof And other methods are obtained. The above hydrophilic group-containing polymer can be polymerized with other unsaturated monomers as needed by using a hydrophilic group such as a buffer group, an amine group, a polyoxygen group, and the like, and a monomer and a derivative thereof. obtain. Examples of the above-mentioned unsaturated group-containing unsaturated monomer and its derivative include benzoic acid, methacrylic acid, maleic acid, maleic acid, butyric acid, and decylene succinic acid. The amine group-containing unsaturated monomer and its derivative may, for example, be dimethylaminoethyl (meth)acrylate, hydrazine, diethylaminoethyl hydrazine-(meth)acrylate, or Nt-(meth)acrylate. Nitrogen (meth)acrylic acid base such as amine vinegar ^ 9 200934888 acrylamide, methacrylamide, N-mercapto (meth) acrylamide, N-ethyl (meth) propylene Indoleamine, N-methyl (indenyl) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (decyl) acrylamide, N, N-dimethyl ( Methyl) acrylamide, ν, Ν-dimethylaminopropyl (methyl) 5 acrylamide, hydrazine, hydrazine-dimethylamine ethyl (fluorenyl) acrylamide, etc., polymerizable guanamine; acrylamide, etc. . Further, a nitrogen-containing monomer such as 2-ethene "bite, 1-ethlyl-2-n-piperone or 4-ethyl acetonate is also utilized as an unsaturated monomer having a hydrophilic group. The hydroxyl group-containing unsaturated monomer may, for example, be 2-hydroxy10 ethyl (meth)acrylate, propyl (mercapto)propionate or 2,3-dibutyl butyl (meth)acrylate. (hydroxy) (meth) acrylate such as 4-hydroxybutyl (meth)acrylate. 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(decyl)acrylate and acrylic acid or methacrylic acid. Further, in the above-mentioned monoethyl ester of (meth) acrylate or a monoester of a polyhydric alcohol and acrylic acid or methyl acrylic acid, a compound obtained by ring-opening polymerization of e-caprolactone or the like may be used. Examples of other unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl 20 (meth) acrylate, and n-butyl (meth) acrylate. Ester, isobutyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, An alkyl (meth)acrylate of 1 to 24 carbons such as tridecyl (meth)acrylate, octadecyl (meth)acrylate or isostearyl (mercapto)acrylate; vinyl acetate or the like. These compounds 200934888 may be used alone or in combination of two or more. In the present invention, (mercapto) acrylate means acrylate or methyl acrylate. 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. 5 H is resistant to impurities, etc. It is preferred that the cleavable or water-dispersible acrylic resin is copolymerized with stupid ethylene. The amount of styrene in all the unsaturated monomers is preferably 60% by mass or less, more preferably 1 to 6 % by mass, still more preferably 15 to 50% by mass. Further, from the viewpoint of obtaining the toughness of the outer film, etc., the Tg (glass transition point) of the acrylic resin obtained by the polymerization is preferably 3 Torr to 8 〇 ° C, and 40 to 70 ° C. It is better. The commercial product of the above acrylic resin may, for example, be Aquabrid CC234 (manufactured by Daicel Chemical Industries, Ltd.). Ii) Polyurethane resin 15 As the above-mentioned water-soluble or water-dispersible 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, such as a diol or a binary. A low molecular weight compound having two or more active hydrogen atoms such as an amine, that is, a chain elongation in the presence of a chain extender, and then stably dispersed or dissolved in water can be widely used (for example, refer to Japanese Patent Special S42). -24192, and the public S42-24194, the special public S42-5118, the special public S49-986, the special public S49-33104, the special public S50-15027, and the special public S53-29175 Bulletin). The method for producing a water-soluble or water-dispersible polyurethane resin can be carried out, for example, by the method of 11 200934888: an amine, dispersed by self-emulsification or (1) by introducing a base group, a base group, or a thiol group to give a hydrophilic group in the domain or at the end of the compound. A method of dissolving in water. ♦After cutting off the isocyanate group, the poly(4-) polymerization temple is blocked by a plugging agent such as hydrazine, ethanol, thiol, amine, sodium sulfoxide, etc. The emulsifier and mechanical shear force force it to be dispersed. The method in the water. j has a polymer with a terminal isocyanate group with water, emulsifier 10

Chain Stretching _ Combining Occupational Shear Forces (4) Decentralization and & sub-quantization methods. (3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol of a polyurethane main raw material, and then the polyurethane is dispersed or dissolved in water like a water-soluble polyamine vinegar polymer. In the above polyamine resin, the above-mentioned dispersion or dissolution method is not limited to a single method, but a mixture obtained by various methods may also be used.

20 The diisocyanic acid vinegar which can be used for the synthesis of the above polyamine resin may, for example, be an alicyclic, aliphatic or aromatic diisocyanate, and specifically, for example, bismuth methylene diisocyanate , tetramethylene diisocyanate m (diiso-hydrogen acid) ring, 1,4 isocyanic acid methyl) cyclohexene, 4,4 isocyanate cyclohexanide, 4,4'· Base double (cyclohexyl isocyanate), isophorar diisocyanate, 3,3,_dimethoxy-4,4'-biphenyldiisocyanate, p-phenylenedione diiso Cyanate vinegar, m-xylylene diisocyanate δ, 2, " benzene diisocyanate vinegar, toluene diisocyanate vinegar, p-phenylene diisocyanate vinegar, diphenyl carbaryl Cyanic acid vinegar, interlayer 12 200934888 phenyl 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. 5 φ 10 15 ❹ 20 The above polyamine-based resin products include, for example, Adeka Bontiter UX206 (manufactured by ADEKA), Hydran HW-330, HW-340, and HW-350 (all by Dainippon Ink & Chemicals, Inc Manufactured), Superflex 100 'i5〇, e-2500, and F-3438D (all manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.). Iii) Epoxy resin The water-soluble or water-dispersible epoxy resin may, for example, be a cationic epoxy resin obtained by adding an amine to an epoxy resin; an acrylic modified epoxy resin; and an amine ester modified epoxy resin. Equivalent epoxy resin. Modified epoxy resin,

And a cationic epoxy resin, for example, an adduct of an epoxy compound and a primary monomer or a polyamine, a secondary monomeric silk amine, a secondary mixed polymer (for example, refer to US Pat. No. 3,984,299); An adduct of a compound with a secondary monomer or a polyamine having a ketimine (for example, see U.S. Patent No. 2004); an epoxy compound having a conversion to a amide The product of the hydrazine-based compounding and refining reaction (for example, see Japanese Patent Laid-Open No. 43013). a resin obtained by reacting a latex resin with a carboxyl group and an epoxy resin modified epoxy resin, for example, a cycloacrylic acid resin; 13 200934888 A polymerizable unsaturated monomer having a carboxyl group-containing monomer The mixture is subjected to graft polymerization or copolymerization of a resin or the like. The amine ester-modified epoxy resin may, for example, be a resin obtained by reacting an amine-containing cyclic latex resin obtained by reacting an amine with an epoxy compound with a polyisocyanate compound or a monoisocyanate 5 compound; An epoxy group obtained by reacting an epoxy compound with a polyolefin-based diol and a polyisocyanate compound, and an epoxy group obtained by adding an amine such as an alcoholic amine; and a bisphenol A mixture of an epoxy compound such as a type A epoxy resin and a polyolefin-based diol diepoxypropyl ether is reacted with bisphenol VIII, and an amine ester modified by reacting an isocyanate oxime compound with the same The epoxy resin of the epoxy resin is required to be added with a resin such as an alkanolamine or the like. 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 4 to 4, and 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 polypane compound with an epoxidized t oxime. The polyphenol compound may, for example, be bis(4-hydroxyphenyl)_2,2 propane, 4,4 dihydroxy 20 diphenyl ketone, bis(4-benzene)-1,1-ethyl benzene, bis (4_经Stupid mountain isobutane, bis(4-fluorenyl-tert-butylbenzene)_2,2-propane, bis(2-hydroxynaphthalene)methane, μ-dihydroxynaphthalene, bis(2,4-di-benzene)-methyl , four (4 · stupid Ethylene, 4,4_ di-based dibenzoquinone, stupid acid, sputum, etc.. For the above-mentioned products of the bad oxygen resin, for example, Adeka Resin EM-0718 14 200934888 (by ADEKA) (manufacturing), etc. 5 10 15 20 The amount of the water-soluble or water-dispersible organic resin (c) added is 20,000 in terms of the quality of the peroxy oxo acid (A) from the viewpoint of paint adhesion and the like. The following is appropriate, but in Bujia, the quality department is better, and the 5~10'_mass is better 'special (four)~5, the quality part is better. Water-soluble or water-dispersible organic resin (c) When the amount of addition is less than the above range, the adhesion of the outer coating material and the processability of the treated film tend to deteriorate, and the corrosion resistance tends to deteriorate beyond the above range. Other components The metal surface treatment composition of the present invention Can be used as needed Further, a metal compound such as a gorge compound, a fluorinated compound, a carbonic acid compound, or a titanium fluoride compound other than peroxy woven fabric is further included. The hunth acid compound may, for example, be a meta-acid, a potassium citrate or a bismuth citrate. Nano, partial subtraction, sharp acid liver, etc. Among them, (iv) lining and other viewpoints, especially ammonium metavanadate. Fluorinated compounds can be, for example, hydrofluoric acid, and sodium and potassium hydrofluoric acid, Salts such as lysine and ammonium, etc., from the viewpoint of corrosion resistance and the like, fluorinated ammonium amide and cesium hydrofluoric acid are preferred. The carbonic acid recording compound may, for example, be a carbonic acid _ m type, which is derived from the resistant material (four) It is preferable to refer to the secret book. * The titanium compound may, for example, be a sodium, potassium or a bell salt of titanium hydrogen hydride. Among them, from the viewpoint of corrosion resistance, etc., it is preferable to use titanium fluoride. The amount of the metal compound to be added is, for example, 2 from the viewpoint of corrosion resistance and the like, and is 2, and the surface quality portion is preferably 15 200934888 5 10 15 20 , and is 2, _The quality department is better, and it is called, the quality of the Qing is good, and the quality is better than the 2_ quality department. The metal surface treatment composition of the present invention may contain a wonderful coupling agent as needed. The oxime coupling agent may, for example, be (aminoethyl) [amine propoxy oxime, (aminoethyl) r-aminopropyl methyl dimethyl Oxygen-excellent soil, - methyl propyloxypropyltrimethoxy (tetra), ^ (ethyl bromide), propyltrimethoxy (tetra) hydrogen salt, r_dehydroglyceryloxypropyl Decane, r-thiol propyl trimethoxy decane, bromopropyl propyl dimethyl dimethyl oxalate, methyl trimethoxy decane, vinyl triethoxy decane, r-gas trimethoxy propylene, six曱基二销烧, Buaniline propyl trimethoxide, Ethylene trimethoxy, Ethyl triethoxy (tetra), Dimethyl 18 (trimethoxy oxi) propyl] gas, three Gas Wei 4. From the viewpoint of the anti-corrosion property after degreasing treatment of the outer film, etc., the acid (i) mass portion 'typically below the damage mass portion' is preferably the mass portion and the mass portion of 1 〇 to 4 (8). In the metal surface treatment composition of the present invention, organic "sub- and/or inorganic fine particles" may be added as needed. By adding the secret particles, the transparency of the coating film is lowered, and the interference color which is likely to occur in the film (mterfereneee GlG〇, which is suitable for the appearance of the appearance) can be suppressed. The particle diameter of the above-mentioned fine particles is in the average particle diameter, and the age is particularly limited to ^5. 〇ηη^_ is suitable from the viewpoint of particle sedimentation stability and corrosion resistance. The above organic fine particles may, for example, be acrylic acid, polyurethane, nylon, poly

16 200934888 Resin microparticles such as ethylene glycol. Further, examples of the inorganic fine particles include cerium oxide, titanium hydride, barium sulfate, and carbonic acid. From the viewpoint of cost and the like, it is preferred to use ruthenium dioxide, titanium oxide, barium sulfate or the like. 5 10 15 Ο 20 From the viewpoint of corrosion resistance, the amount of organic fine particles and/or inorganic fine particles added is not more than 3% by mass in the solid content of the metal surface treatment test, and is 0% by mass. . / It is also a load/ΰ, and a range of 1 to 20% by mass is preferable. In the metal surface treatment composition of the present invention, in addition to the above components, a paste such as an inorganic money compound or hydrofluoric acid, a heavy metal compound other than the component of the present invention, an increase in the amount of the interface, and a lubricant may be contained. Polyethylene ants, fluorine-containing ants, brown touches, etc.), rust inhibitors, coloring pigments, body pigments, anti-rust pigments, dyes, etc. The above-mentioned (10) acid-free compound may, for example, be n-decanoic acid, partial Wei, phosphorous acid, metaphosphoric acid, low Wei, hypotriic acid, pyroic acid, trimeric Wei, tetraphosphoric acid, hexa-, tri-negative, and pyro-wei And Wei derivatives. One or two sputum scale compounds may be used in combination. Further, these phosphoric acid compounds are formed together with the secret compound. The test compound can be exemplified by an organic or inorganic basic compound having lithium sodium potassium ammonium. The acid-free compound is preferably one which has a right-handed material and is soluble in water. The heavy metal compound may, for example, be indium acid, mineral acid or a salt thereof. t iron 'record, indium and other metal salts; other rust inhibitors can be mentioned, for example, "silk and other sputum 彳 = mash complex; thiol 4 supplement, ren face, / material; three _ and so on Nitrogen compound; sulphide exchange; carbon-containing compound such as sulfur atom and nitrogen atom; and boron 17 200934888 acid, metaboric acid, and the like. In the metal surface treatment composition of the present invention, methanol, ethanol, isopropanol, ethylene glycol: and hydrophilic two: the amount of use of the agent may be used for two changes. For example, a hydrophilic organic solvent-soluble metal surface treatment composition (4)% by mass or less is

The manufacturing method of the metal surface treatment composition of the present invention is not limited thereto, and Wei Wei (4), organic ship (8), and other components may be used, and if necessary, water dilution adjustment _ is divided into 〇Μ mass % (to 0.5~) 40% by mass is better). Surface Treatment Μ村 The surface-treated metal material of the present invention is a ruthenium metal material having a surface of a metal surface treatment layer obtained from the metal surface treatment composition of the present invention on a metal material. Specifically, the surface-treated metal material can be obtained by coating and baking (4) the metal surface treatment composition of the present invention on a substrate.

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 deposited from the metal may be mentioned. Among them, the steel material which is electroplated by rhetoric or alloying is used, and in particular, when a steel plate of a plated steel or a steel plate of 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 article containing iron (including an alloy), a plate shape, or a rod shape, and the steel plate is formed by forming iron (including an alloy) into a plate shape 18 200934888. The method of applying the composition for metal surface treatment to the substrate is not a method of coating, and can be carried out according to the coating method. The coating method may, for example, be a dip coating or a spray coating treatment film, and the conditions for the drying (drying) are usually (four) = the table is dry to fine under the condition of 峨 to about torn, and the second is for the metal surface treatment. The treatment medium thickness of the composition is usually preferably a dry film thickness of 〇.001 to 10 g/m2, more preferably 〇.〇5 to 3 g/nf. If the film thickness is too thin, the properties such as corrosion resistance and water resistance tend to be low. If the film thickness is too thick, the surface treatment film may be cracked or the processability may be lowered.

The use of the surface-treated steel sheet of the present invention can be used for the purpose of using a conventional surface-treated steel sheet for building materials, household appliances, eight-vehicle use, and pre-coated steel sheets, and is not particularly limited. In addition, it is possible to apply a suitable coating such as primer coating or exterior coating as needed. The coating method may be appropriately selected depending on the application, the shape of the object to be coated Q, and the like, and may be suitably used, 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 MODE FOR CARRYING OUT THE INVENTION Next, the production examples, 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 "%" that are not disclosed in the examples are those based on quality.皇造例1 (Manufacture of metal surface treatment composition) 200934888 Add 100 parts of deionized water to the vessel, add 3 质量% of hydrogen peroxide water to the mass part and stir it to a liquid temperature of 2 5 Further, 15 parts by mass of ammonium metavanadate was added to the solution, and the mixture was stirred for 30 minutes to obtain an aqueous solution of peroxovagic acid. 5 f Examples 1 to 13 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%. The following tests were carried out for each of the metal surface treatment compositions obtained in the examples and the comparative examples. The results are combined in Tables 1 and 2. The raw materials of '(※丨)~(※彳) in Table 1 are the following contents. (※丨) AdekaBontiterUX206: trade name, manufactured by ADEKA Corporation, water-based polyurethane resin. (※) AquabridCC234. Trade name, by DainipponInk&

Manufactured by Chemicals, Inc., aqueous acrylic resin. ® (*3) Adeka Resin EM-0718 : trade name, manufactured by ADEKA, waterborne epoxy resin. 20 (※ bucket) Superflex E-2500 : trade name, by Dai-Ichi Kogyo

Water-based polyurethane resin manufactured by Seiyaku Co., Ltd. Test Example 1 (Storage Stability Test) Each of the metal surface treatment compositions adjusted to have a solid content of 10% was placed in a glass bottle and sealed, and placed in a thermostatic chamber at 2 ° C for one month, to visually observe 20 200934888 The appearance was evaluated on the basis of the following criteria. A: There is no sediment or obvious viscosity. b: There is a sediment type test example 2 (resistance to corrosion resistance) 5 c- The test plate is made with a thickness of 0.5, and the plating amount of one side is 60g/m2. The hot-dip galvanized steel sheet is degreased with an aqueous solution having a concentration of 2% dissolved in an organic degreaser (manufactured by Japan CB Chemical Co., Ltd., trade name "Chemicleaner 561B"), and after washing with water, the metal surface obtained by the above examples and comparative examples will be used. The treatment 10 composition was applied thereon so that the weight of the dried outer film became 1. 〇g/m2, and the material reached a temperature of 10 ° C and baked for 20 seconds to form a surface treatment film. (2) Corrosion resistance test The salt spray test prescribed in JIS Z2371 was carried out on the test plate after the end face and the rear portion of the obtained test plate were sealed until 72 hours, and the degree of rust was evaluated on the following basis. A. There is no record of birth. B: The degree of rust was observed to be 5% of the film area (practical range). C: The degree of rust was observed to be 5% or more of the coating 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%. 20 E : The degree of rust was observed to be 50% or more of the coating area. Ci (adhesive film adhesion) C-test plate was prepared by hot-dip galvanized steel sheet with a thickness of 0.5 mm and a single-sided plating adhesion of 60 g/m2, using an alkaline degreasing agent (manufactured by japan CB Chemical). 21 200934888 * Product name "Chemicleaner 561B") After degreasing and washing with an aqueous solution having a concentration of 2%, the metal surface treatment composition obtained by the above examples and comparative examples was applied thereon to make the dry outer film weight 0.3 g/ M2, the material was allowed to reach a temperature of 100 ° C and baked for 20 seconds to form a surface treatment film. Amilac #1000 White (manufactured by Kansai Paint Co., Ltd., thermosetting acid alcohol resin paint, white) was applied to each test plate to make the dried film thickness 30 μm and baked at 130 ° C for 20 minutes. Obtain an outer coated plate. (2) Adhesiveness of the upper coating film For the obtained test coating plate, the traces of the vertical and horizontal sides of each of the 10 11 deep to uncoated substrate portions were made with a knife on the coated surface, and a checkerboard pattern was drawn. 2 grid. 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 · Yuan did not observe the peeling of the upper coating film. ‘ B : 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. ❹ 22 200934888 i啭Examples 100 150 700 220 cd cd cd 100 150 600 200 cd cd m 100 150 cd cd X) inch 100 〇IT) Η (N cd cd m 100 150 in CN cd cd CN 100 150 cd cd 〇150 cd cd X) peroxyl oxalate 1-hydroxymethyl-1, 1-diphosphonic acid 1-hydroxyethyl-1,1-diphosphonic acid 1-hydroxypropyl-1, 1-diphosphonic acid Adeka Bontiter UX206 (※ 1 ) Aquabrid CC234 (※) Adeka Resin EM-0718 (:* 3) Superflex E-2500 (:*4) Ammonium lanthanum fluoride carbonate misunderstanding titanium fluoride hydrofluoric acid zirconium storage stability resistance Corrosive surfacing film adhesion /-"NS-/PQ Ο 200934888 Comparative Example (Ν 100 <N Xi X) 150 in (N cd o Example m 100 2500 200 cd cd cd (Ν 100 100 3500 200 cd cd cd 100 2500 200 cd cd cd Ο 100 100 3000 200 cd cd cd Ον 100 ο 600 〇1—Η cd cd cd ΟΟ 100 150 700 170 cd cd cd Peroxyvanadate 1-hydroxymethyl-1,1 -Diphosphonic acid 1-hydroxyethyl-1, 1-diphosphonic acid 1-hydroxypropyl-1, 1- Phosphonic acid Adeka Bontiter UX206 (※ 1 ) Aquabrid CC234 (※) Adeka Resin EM-0718 (:* 3) Superflex E-2500 (*4) Ammonium lanthanum ammonium carbonate arsenic fluoride titanium ammonium hydroxide hydrofluoric acid storage stability Corrosion resistance 1 External coating film adhesion / - Ν Ν CQ o 200934888 Λ 5 The metal surface treatment composition of the present invention contains peroxovanaic acid and organic phosphonic acid. Permanganic acid It is excellent in its properties, but its stability in water alone is poor, and precipitation is likely to occur, which makes it difficult to use it practically. However, by combining organic phosphonic acid, the storage stability of the treatment liquid is remarkably improved, and the combination with the aqueous organic resin also enables it to be widely used, so that the performance of the treatment membrane is balanced (for example, the sulphur residue and processing) Equilibrium of properties, material adhesion, etc.) It is easy to achieve, and performance comparable to chromate treatment agent and phosphate treatment agent can be obtained. Therefore, instead of these treatment agents, it becomes a chromium-free surface treatment m agent on the metal surface. It is very useful for handling purposes. 10 « Further, the surface-treated metal material of the present invention is excellent in terms of workability, prosperousness, and coatability. [Simple description of the figure 3 (none) [Description of main component symbols] (none) Reference 25

Claims (1)

200934888 VII. Patent Application Range: 1. A composition for metal surface treatment comprising: (A) peroxyvanadic acid; and (B) an organic phosphonic acid. 5. The metal surface treatment composition according to the first aspect of the invention, wherein the organic phosphonic acid (B) has an organic group having a hydroxyl group. 3. The metal surface treatment composition according to claim 1 or 2, wherein the organic phosphonic acid (B) is selected from the group consisting of 1-hydroxymethyl-1,1-diphosphonic acid and 1-hydroxyethyl -1,1-diphosphonic acid, and at least one of 10 compounds of 1-hydroxypropyl-1,1-diphosphonic acid. 4. The metal surface treatment composition according to claim 1 or 2, wherein the organic phosphonic acid (B) is contained in the range of 1 to 250 parts by mass relative to 100 parts by mass of the peroxyvanadate (A). Insider. 5. The composition for metal surface treatment according to claim 1 or 2, further comprising a water-soluble or water-dispersible organic resin (C). 6. The metal surface treatment composition according to claim 5, wherein the water-soluble or water-dispersible organic resin (C) is contained in the range of 1 to 20,000 with respect to 100 parts by mass of the peroxyvanadate (A). Within the scope of the quality department. 7. The composition for metal surface treatment according to claim 1 or 2, wherein the composition for metal surface treatment is used for steel plated with zinc or alloy. A surface-treated metal material comprising a metal surface treatment layer obtained on a steel plated with zinc or an alloy and obtained by the metal surface treatment composition according to claim 1 or 2. 200934888 9. A surface-treated steel sheet having a metal surface treatment layer obtained from a steel surface-plated steel sheet and a metal surface treatment composition according to claim 1 or 2. 27 200934888 IV. Designation of Representative Representatives: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: (none) 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none)