JP5827053B2 - Water-based metal surface treatment agent and metal material treated with the treatment agent - Google Patents

Description

  The present invention relates to a water-based metal surface treatment agent for forming a surface-treated film excellent in adhesion and chemical-resistant adhesion maintenance capable of preventing peeling of a metal material and a laminate film or a resin coating film, and the metal The present invention relates to a metal material processed with a surface treatment agent. Specifically, even if a resin film is laminated to a metal material or a resin coating film is formed, and then severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing is performed, the laminated film etc. Forms a hexavalent chromium-free surface-treated film that is capable of imparting high adhesion that does not peel off and that is excellent in chemical adhesion maintenance that can maintain high adhesion even when exposed to acids, organic solvents, etc. The present invention relates to an aqueous metal surface treatment agent for the purpose.

  Lamination is a processing means for thermocompression bonding a resin film (hereinafter referred to as “resin film” or “laminate film”) to the surface of a metal material (hereinafter also simply referred to as “metal surface”). This is one of methods for coating a metal surface for the purpose of protecting the surface or imparting design properties, and is used in various fields. Compared with the method of forming a resin coating film by applying a resin composition dissolved or dispersed in a solvent to a metal surface and drying it, the laminating process is a waste gas such as a solvent generated during drying or carbon dioxide or the like. There is little generation of greenhouse gas. Therefore, it is preferably applied in terms of environmental protection, and its uses are expanded. For example, a body or lid of a food can made of aluminum thin plate material, steel thin plate material, aluminum foil for packaging or stainless steel foil, etc. Used in containers and dry battery containers.

  Recently, metal foils such as aluminum foil and stainless steel foil that are lightweight and have high barrier properties as exterior materials and tab lead materials for mobile lithium-ion secondary batteries used in mobile phones, electronic notebooks, notebook computers, video cameras, and the like. Is preferably used, and a lamination process is applied to the surface of the metal foil. In addition, lithium ion secondary batteries have been studied as driving energy for electric vehicles or hybrid vehicles, and laminated metal foils have also been examined as exterior materials.

  The laminate film used for such a lamination process is directly bonded to a metal material and then heat-pressed. Therefore, compared to a general resin coating film formed by applying and drying a resin composition, there are advantages such as suppression of waste of raw materials, fewer pinholes (defects), and excellent workability. As materials for the laminate film, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and polyolefins such as polyethylene and polypropylene are generally used.

  When laminating is performed without performing a chemical conversion treatment or the like on the metal surface, there is a problem that the laminate film is peeled off from the metal surface or the metal material is corroded. For example, in food containers or packaging materials, the contents are added to the container or packaging material after lamination, and then heat treatment for sterilization is performed, but the laminate film is peeled off from the metal surface during the heat treatment. There is. Moreover, in the exterior material etc. of a lithium ion secondary battery, processing with a high degree of processing is received in the manufacturing process. In addition, when used for a long time, moisture in the atmosphere enters the container, which reacts with the electrolyte to produce hydrofluoric acid, which permeates the laminate film and causes the metal surface and the laminate film to peel off. And the problem of corroding the metal surface.

  In order to improve the adhesion between the laminate film and the metal surface and the corrosion resistance of the metal surface when laminating the laminate film to the metal surface for such a problem, the metal surface is usually degreased and washed, and usually phosphoric acid chromate, etc. The chemical conversion treatment is performed. However, such a chemical conversion treatment requires a washing step for removing excess treatment liquid after the treatment, and costs for waste water treatment of washing water discharged from the washing step. In particular, chemical conversion treatment such as phosphoric acid chromate tends to be avoided from environmental considerations in recent years because a treatment solution containing hexavalent chromium is used.

  For example, Patent Document 1 proposes a base treatment agent containing a specific amount of a water-soluble zirconium compound, a water-soluble or water-dispersible acrylic resin having a specific structure, and a water-soluble or water-dispersible thermosetting crosslinking agent. ing. Patent Document 2 proposes a non-chromium metal surface treatment agent comprising a specific amount of a water-soluble zirconium compound and / or a water-soluble titanium compound, an organic phosphonic acid compound, and tannin. Patent Document 3 proposes a metal surface treatment agent containing an aminated phenol polymer and a specific metal compound such as Ti and Zr and having a pH in the range of 1.5 to 6.0. . Patent Document 4 proposes a resin film containing an aminated phenol polymer, an acrylic polymer, a metal compound, and, if necessary, a phosphorus compound.

International Patent Publication No. WO2002 / 063703 JP 2002-265821 A JP 2003-313680 A JP 2004-262143 A

  An object of the present invention is to provide an aqueous metal surface treatment agent for forming a surface-treated film excellent in adhesion and chemical-resistant adhesion maintenance that can prevent a metal material and a laminate film or a resin film from peeling off. It is providing and providing the metal material processed with the metal surface treating agent. Specifically, even if a resin film is laminated on a metal material or a resin coating film is formed, and then severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing is performed, the laminated film or resin Metal surface for forming a hexavalent chromium-free surface-treated film that has high adhesion such that the coating film does not peel off and has excellent chemical adhesion maintenance that can maintain high adhesion even when exposed to acids, etc. The object is to provide a treatment agent and a metal material treated with the metal surface treatment agent.

The water-based metal surface treatment agent according to the present invention for solving the above-mentioned problems is a polyvinyl alcohol compound (A) and a crosslinkable organic compound (B1) having a functional group capable of reacting with the polyvinyl alcohol compound (A). And one or more crosslinkable compounds (B) selected from crosslinkable inorganic compounds (B2) containing an element capable of reacting with the polyvinyl alcohol compound (A), and the crosslinkable compound (B ) At least the crosslinkable inorganic compound (B2) (however, it does not contain a vanadium compound) .

  According to this invention, since the polyvinyl alcohol compound (A) and the crosslinkable compound (B) described above are contained, the surface treatment film obtained by treatment with the aqueous metal surface treatment agent has high adhesion. In addition, high adhesion can be maintained even when exposed to an acid or the like. As a result, even when a resin film is laminated to a metal material or a resin coating film is formed, and then severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing is performed, an acid or Even when exposed to an organic solvent or the like, the laminate film or the resin coating film can be prevented from peeling off from the metal material.

  In the aqueous metal surface treatment agent according to the present invention, the crosslinkable organic compound (B1) has one or more functional groups selected from a glycidyl ether group, an isocyanate group, a methylol group, and an aldehyde group.

  According to this invention, since the crosslinkable organic compound (B1) has the functional group described above, the surface treatment film obtained by treatment with the aqueous metal surface treatment agent has better adhesion, and the organic solvent or Even when exposed to an acid, more stable adhesion can be maintained over a long period of time.

In the aqueous metal surface treatment agent according to the present invention, the crosslinkable inorganic compound (B2) contains one or more elements selected from Cr (III), Zr, Ti, Si, Ce, and Te .

  According to the present invention, since the crosslinkable inorganic compound (B2) contains the above-described elements, the surface treatment film obtained by treatment with the aqueous metal surface treatment agent has better adhesion, and an organic solvent or acid. Even when exposed to water, more stable adhesion can be maintained over a long period of time.

  The metal material according to the present invention for solving the above-described problems has a surface treatment film formed by applying the water-based metal surface treatment agent according to the present invention.

  According to this invention, since it has a surface treatment film formed by applying the aqueous metal surface treatment agent according to the present invention, the metal material having the surface treatment film is subjected to laminating, and then deep drawing, The laminate film or resin coating formed on the surface of the metal material is peeled off even when subjected to severe molding such as ironing or stretch drawing, or even when exposed to acid or the like. Can be prevented.

  According to the water-based metal surface treatment agent according to the present invention, in order to form a surface treatment film excellent in adhesion and chemical adhesion maintaining ability that can prevent the metal material and the laminate film or resin coating film from peeling off. An aqueous metal surface treatment agent can be provided.

  The metal material according to the present invention can provide a metal material having such a surface treatment film.

It is typical sectional drawing which shows an example of the metal material which has the surface treatment film | membrane formed by apply | coating the water-system metal surface treatment agent which concerns on this invention.

  Hereinafter, a metal material having a surface treatment film formed by applying the aqueous metal surface treatment agent according to the present invention and the metal surface treatment agent to the surface of the metal material will be described. The technical scope of the present invention is not limited by the following description and the form of the drawings.

[Water-based metal surface treatment agent]
As shown in FIG. 1, the water-based metal surface treatment agent according to the present invention is a base of a laminate film or a resin coating 3 on the surface of a metal material 1 (hereinafter referred to as “base metal 1”) as a base material. It is a processing agent for forming the surface treatment film 2 for use. The characteristic is that it contains a polyvinyl alcohol compound (A) and one or more crosslinkable compounds (B) selected from a crosslinkable organic compound (B1) and a crosslinkable inorganic compound (B2). is there. “Contains” means that the water-based metal surface treatment agent may contain a compound other than the polyvinyl alcohol-based compound (A) and the crosslinkable compound (B). Examples of such compounds include surfactants, antifoaming agents, leveling agents, antibacterial and antifungal agents, and coloring agents. These compounds can be contained within a range not impairing the gist and film performance of the present invention.

  Hereinafter, the configuration of the present invention will be described in detail.

(Polyvinyl alcohol compound (A))
The polyvinyl alcohol compound (A) is one or more compounds selected from polyvinyl alcohol and derivatives thereof. By including the polyvinyl alcohol compound (A) and the crosslinkable compound (B), it is possible to improve the adhesion and chemical adhesion maintenance of the surface treatment film obtained by treatment with the aqueous metal surface treatment agent.

  As polyvinyl alcohol and derivatives thereof, a saponified product of polyvinyl acetate, a saponified product of a copolymer of vinyl acetate and other monomers, or the like can be used. This saponified product may be a partially saponified product or a completely saponified product.

  Examples of other monomers copolymerized with vinyl acetate include anionic comonomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and salts thereof; styrene, acrylonitrile, vinyl ether, (meth) acrylamide, N-methylol. Nonionic comonomers such as (meth) acrylamide, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, acroylmorpholine, vinyl acetate; aminoethyl (meth) acrylate, N-hydroxypropylaminoethyl (meth) acrylate And cationic comonomers such as vinylimidazole and N, N-dimethyldiallylamine.

  Moreover, the above-mentioned polyvinyl alcohol and its derivatives may be acetoacetylated by reacting with diketene.

  The content of the polyvinyl alcohol compound (A) is preferably 10% by mass to 90% by mass, and preferably 10% by mass to 80% by mass with respect to the total solid content contained in the aqueous metal surface treatment agent. Is more preferable, and 20% by mass to 80% by mass is particularly preferable. By setting it as 10 mass%-90 mass%, the adhesiveness of the surface treatment film obtained and chemical-resistant adhesion maintenance property can be improved more.

  The “total solid content” is a solid content excluding volatile components such as a solvent among the components constituting the aqueous metal surface treatment agent. Specifically, the polyvinyl alcohol compound (A) And the total amount of one or more crosslinkable compounds (B) selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2). Therefore, the content of the polyvinyl alcohol compound (A) is 10% by mass to 90% by mass with respect to the total amount (total solid content) of the polyvinyl alcohol compound (A) and the crosslinkable compound (B). Is preferable, it is more preferable that it is 10 mass%-80 mass%, and it is especially preferable that it is 20 mass%-80 mass%.

(Crosslinkable compound (B))
The crosslinkable compound (B) is one or more compounds selected from a crosslinkable organic compound (B1) and a crosslinkable inorganic compound (B2). By including the crosslinkable compound (B) in the aqueous metal surface treatment agent, it is possible to improve the adhesion and chemical resistance adhesion maintaining property of the surface treatment film obtained by the treatment with the aqueous metal surface treatment agent.

(Crosslinkable organic compound (B1))
The crosslinkable organic compound (B1) is a compound having a functional group capable of reacting with the polyvinyl alcohol (A). “Can react” means that the polyvinyl alcohol (A) can be contacted to react with them. “Having” means that it may have other functional groups or bonding units in addition to these functional groups.

  As a crosslinkable organic compound (B1), the organic compound which has 1 type, or 2 or more types chosen from a glycidyl ether group, an isocyanate group, a methylol group, and an aldehyde group can be mentioned, for example.

  As the organic compound having a glycidyl ether group, a conventionally known polyvalent glycidyl ether compound can be used. Examples of the polyvalent glycidyl ether compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol polyglycidyl ether, and diglycerol. Examples include liglycidyl ether, polyglycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, and the like.

  Examples of the organic compound having an isocyanate group include isomers of tolylene diisocyanate; aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate; araliphatic diisocyanates such as xylylene diisocyanate; isophorone diisocyanate, 4,4 And alicyclic diisocyanates such as' -dicyclohexylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; and the like. These isocyanate compounds are not particularly limited, but it is preferable to use isocyanate compounds blocked with various blocking agents from the viewpoint of the stability of the aqueous metal surface treatment agent. Examples of the blocking agent include various blocking agents such as phenol, alcohol, oxime, active methylene, acid amide, carbamate, and sulfite.

  Examples of the organic compound having a methylol group include a resol type phenol resin, methylol melamine, a homopolymer of N-methylol acrylamide monomer, a copolymer of N-methylol acrylamide monomer and other monomers, and the like.

  Examples of organic compounds having an aldehyde group include dialdehyde compounds such as glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, adipine dialdehyde, heptane dial, and compounds having three or more aldehyde groups. Can be mentioned.

(Crosslinkable inorganic compound (B2))
The crosslinkable inorganic compound (B2) is a compound containing an element that can react with the polyvinyl alcohol compound (A). The term “reactable” means that the polyvinyl alcohol compound (A) can be contacted with and reacted with them. “Including” means that other elements may be included in addition to these elements.

  Examples of the crosslinkable inorganic compound (B2) include Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, and Sn. Inorganic compounds containing one or more elements selected from Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La can be used. Among these, inorganic compounds containing one or more elements selected from Mg, Al, Ca, Mn, Cr (III), Zn, Fe, Zr, Ti, Si, Ce, Te, and Hf are more preferable. Inorganic compounds containing one or more elements selected from (III), Zr, Ti, Si, Ce and Te are more preferred.

  Specifically, Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, A salt, complex compound or metal hydrated oxide (hereinafter referred to as “salt etc.”) containing one or more elements selected from In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and La. Say).

More specifically, bis (acetylacetonato) diaquamagnesium (II), magnesium aluminate, magnesium benzoate, magnesium formate, magnesium oxalate, magnesium tungstate, magnesium metaniobate, magnesium borate, magnesium molybdate, iodine Magnesium salts such as magnesium phosphide, magnesium diphosphate, magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, ammonium magnesium phosphate, magnesium hydrogen phosphate, magnesium oxide, etc .;
Aluminum nitrate, aluminum sulfate, potassium sulfate aluminum, sodium aluminum sulfate, aluminum sulfate aluminum, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum oxide, aluminum fluoride, aluminum iodide, aluminum acetate, aluminum benzoate, citric acid Aluminum salts such as aluminum acid, aluminum gluconate, aluminum selenate, aluminum oxalate, aluminum tartrate, aluminum lactate, aluminum palmitate, etc .;
Bis (acetylacetonato) diaqua calcium (II), calcium benzoate, calcium citrate, calcium metastannate, calcium selenate, calcium tungstate, calcium carbonate, calcium tetraborate, calcium molybdate, calcium maleate, apple Calcium salts such as calcium oxide, calcium diphosphate, calcium fluoride, calcium phosphinate, calcium nitrate, calcium hydroxide, calcium oxide, calcium oxalate, calcium oxide, and calcium acetate;
Bis (acetylacetonato) diaquamanganese (II), trimanganese tetraoxide, manganese (II) oxide, manganese (III) oxide, manganese (IV) oxide, manganese bromide (II), manganese oxalate (II), peroxy Manganic acid (VII), potassium permanganate (VII), sodium permanganate (VII), manganese dihydrogen phosphate (II), manganese nitrate (II), manganese sulfate (II), manganese sulfate (III), sulfuric acid Manganese (IV), manganese fluoride (II), manganese fluoride (III), manganese carbonate (II), manganese acetate (II), manganese acetate (III), ammonium manganese sulfate (II), manganese iodide (II), Manganese salts such as manganese hydroxide (II) or manganates;
Bis (acetylacetonato) diaquacobalt (II), Tris (acetylacetonato) cobalt (III), Cobalt (II) sulfamate, Cobalt (II) chloride, Chloropentamminecobalt chloride (III), Hexaamminecobalt Chloride (III), diammine tetranitrocobalt (III) ammonium, cobalt sulfate (II), ammonium cobalt sulfate, cobalt nitrate (II), cobalt aluminum oxide, cobalt hydroxide (II), cobalt oxide (II), phosphorus Cobalt oxide, cobalt acetate (II), cobalt formate (II), cobalt trioxide, cobalt bromide (II), cobalt oxalate (II), cobalt selenate (II), cobalt tungstate (II), hydroxy carbonate Cobalt (II), cobalt molybdate (II), cobalt iodide (II), cobalt phosphate II) cobalt salts such like;
Nickel (II) disulfamate, nickel (II) benzoate, nickel (II) nitrate, nickel (II) sulfate, nickel (II) carbonate, nickel acetylacetonate (II), nickel chloride (II), hexaammine nickel Chloride, nickel oxide, nickel hydroxide (II), nickel oxide (II), nickel acetate, nickel citrate (II), nickel succinate (II), nickel bromide (II), nickel oxalate (II), tartaric acid Nickel salts such as nickel (II), nickel selenate (II), nickel nickel carbonate (II), nickel lactate (II), nickel molybdate (II), nickel iodide (II), nickel diphosphate (II) etc;
Chromium formate (III), chromium fluoride (III), chromium nitrate (III), chromium sulfate (III), chromium oxalate (III), chromium acetate (III), chromium biphosphate (III), chromium hydroxide (III) Chromium salts such as chromium (III) oxide, chromium (III) bromide and chromium (III) iodide;
Bis (acetylacetonato) zinc (II), zinc benzoate (II), hydroxy zinc chloride (II), zinc formate (II), zinc citrate (II), zinc bromide (II), zinc oxalate (II) , Zinc tartrate (II), zinc metastannate (II), zinc selenate (II), zinc tungstate (II), zinc fluoride (II), zinc molybdate (II), zinc butyrate (II), diphosphoric acid Zinc salts such as zinc (II), zinc sulfate (II), zinc carbonate (II), zinc chloride (II), zinc iodide (II), zinc hydroxide (II), zinc oxide (II), etc .;
Bis (acetylacetonato) diaqua iron (II), tris (acetylacetonato) iron (III), tripotassium iron trisuccinate, iron (II) formate, iron (III) tetravanadate, iron (III) bromide, tartaric acid Iron (III), iron lactate (II), iron fluoride (II), iron fluoride (III), iron chloride (II), iron chloride (III), iron iodide (II), iron iodide (III) , Iron sulfate (II), iron sulfate (III), iron nitrate (II), iron nitrate (III), iron acetate (II), iron acetate (III), iron citrate (II) iron citrate (III), Glycine iron (II), glycine iron (III), iron oxalate (II), iron oxalate (III), iron picolinate (II), iron picolinate (III), L-phenylalanine iron (II), L-phenylalanine iron (III), iron malonate (II), iron malonate (III), iron hydroxide (II), iron hydroxide (III), iron oxide (II), iron oxide (III), triiron tetroxide, etc. Iron salt, etc .;
Bis (acetylacetonato) diaquastrontium (II), strontium formate (II), strontium citrate (II) strontium tungstate, strontium metastannate, strontium oxide (IV), strontium oxide (II), strontium oxalate, metaniobic acid Strontium salts such as strontium, strontium molybdate, strontium iodide, strontium nitrate, strontium sulfate, strontium carbonate, strontium acetate, strontium chloride, strontium phosphate, and strontium lactate;
Titanium diammonium oxalate, dipotassium oxybisuccinate, titanium (II) oxide, titanium (III) oxide, titanium (IV) oxide, titanium oxysulfate, basic titanium phosphate, titanium bromide (IV) , Metatitanic acid, zinc metatitanate (II), aluminum titanate (III), potassium metatitanate, trititanium tricobalt (II), zirconium titanate, strontium metatitanate, metatitanium triiron (III), copper metatitanate (II) , Sodium titanate, neodymium (III) dititanate, barium metatitanate, bismuth (III) metatitanate, magnesium metatitanate, magnesium titanate, manganese metatitanate (II), lanthanum dititanate (III), lithium metatitanate , Ammonium hexafluorotitanium (IV), hexafluorotitanium ( IV) Potassium acid, titanium iodide (IV), titanium sulfate (III), titanium sulfate (IV), titanium chloride, titanium nitrate, titanyl sulfate, titanium fluoride (III), titanium fluoride (IV), hexafluorotitanium Titanium salts such as acid, titanium lactate, peroxotitanic acid, titanium laurate, titanium acetylacetonate, titanium hydroxide (IV), etc. or titanates;
Tetrakis (acetylacetonato) zirconium (IV), zirconium chloride (IV), zirconium chloride (IV), zirconium silicate, zirconium acetate oxide (IV), zirconium oxide (IV), zirconium oxide nitrate (IV), metazirconium Cesium acid, Lithium metazirconate, Zinc (II) metazirconate, Aluminum (III) metazirconate, Calcium metazirconate, Cobalt (II) metazirconate, Strontium metazirconate, Copper (II) metazirconate, Sodium metazirconate, nickel metazirconate (II), barium metazirconate, bismuth metazirconate (III), magnesium metazirconate, zirconium oxycarbonate, hexafluorozirconium (IV) acid Monium, potassium hexafluorozirconium (IV), zirconium iodide, zirconium dihydrogen oxide (IV), basic zirconium carbonate, ammonium zirconium carbonate, zirconyl ammonium carbonate, zirconium nitrate, zirconyl nitrate, zirconium (IV) sulfate, Zirconyl sulfate, hexafluorozirconic acid, zirconium oxyphosphate, zirconium pyrophosphate, zirconium dihydrogen phosphate, zirconium oxychloride, zirconium fluoride, zirconium fluoride, zirconium acetate, zirconium oxide, zirconium hydroxide, etc .;
Silicates such as hexafluorosilicic acid and silica;
Tungsten chloride (VI), iron (III) oxide tungstate, tungsten chloride (VI), tungsten oxychloride, tungsten dioxide, tungsten trioxide, metatungstic acid, ammonium metatungstate, sodium metatungstate, paratungstic acid, Ammonium paratungstate, sodium paratungstate, zinc tungstate (II), potassium tungstate, calcium tungstate, cobalt tungstate (II), strontium tungstate, cesium tungstate, copper (II) tungstate, nickel tungstate , Barium tungstate, magnesium tungstate, manganese (II) tungstate, lithium tungstate, phosphotungstic acid, ammonium phosphotungstate Tungsten salt or tungstate such as sodium phosphotungstic acid;
Tris (acetylacetonato) cerium (III), cerium (III) chloride, cerium (III) oxide, cerium (IV) oxide, cerium bromide (III), cerium (III) oxalate, cerium hydroxide (IV), sulfuric acid Ceric ammonium (IV), ceric ammonium sulfate (III), cerium carbonate (III), cerium sulfate, cerium acetate (III), cerium nitrate (III), cerium sulfate (IV), cerium fluoride (III) Cerium salts such as cerium (III) iodide and cerium (III) phosphate;
Molybdenum chloride (V), molybdenum oxide (IV), molybdenum oxide (VI), zinc molybdate (II), potassium molybdate, calcium molybdate, cobalt molybdate (II), cesium molybdate, nickel (II) molybdate , Barium molybdate, bismuth molybdate (III), magnesium molybdate, lithium molybdate, lithium paramolybdate, strontium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, molybdate, ammonium molybdate, Molybdenum salts such as ammonium paramolybdate and sodium molybdate, or molybdates;
Vanadium oxydichloride, vanadium oxytrichloride, vanadium trichloride, vanadium oxide, iron (III) tetravanadate, vanadium (III) bromide, vanadium oxyoxalate, vanadium iodide (II), vanadium pentoxide, metavanadate, Sodium pyrovanadate, sodium vanadate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetyl acetate, vanadium acetyl acetate, phosphovanadomolybdic acid, etc. Vanadium salt or vanadate, etc .;
Tin (II) chloride, tin (II) acetate, tin (II) oxalate, tin (II) tartrate, tin (IV) oxide, tin nitrate, tin sulfate, tin fluoride (II), tin iodide (II), Tin salts such as tin (IV) iodide, tin (II) pyrophosphate, metastannic acid, zinc metastannate, calcium metastannate, strontium metastannate, barium metastannate, magnesium metastannate, etc .;
Bismuth (III) benzoate, bismuth chloride (III) chloride, bismuth citrate (III), bismuth oxyacetate (III), bismuth oxide tartrate (III), bismuth oxide (III), dibismuth oxysulfate, bismuth bromide ( III), bismuth tartrate (III), bismuth hydroxide (III), dibismuth oxycarbonate, bismuth zirconate (III), bismuth oxynitrate, bismuth tetratitanate, bismuth trititanate (III), fluoride Bismuth (III), bismuth molybdate (III), bismuth iodide (III), bismuth nitrate (III), bismuth chloride (III), bismuth sulfate (III), bismuth acetate (III), bismuth phosphate (III), etc. Bismuth salt, etc .;
Tantalum (V), tantalum oxide (V), tantalum bromide (V), tantalum acid, potassium hexatantalate, strontium metatantalate, sodium metatantalate, lithium metatantalate, tantalum iodide (V), tantalumoxyacetylacetate Tantalum salts such as nate, metatantalic acid, ammonium metatantalate, potassium heptafluorotantalate, etc. or tantalates;
Telluric acid, ammonium metatellurate, potassium metatellurate, sodium metatellurate, tellurium iodide (IV), potassium tellurate, sodium tellurate, tellurite, potassium tellurite, sodium tellurite, barium tellurite, sublimation Tellurium salts such as lithium tellurate, tellurium chloride (IV), tellurium oxide (IV), tellurium bromide (IV), ditellurium hydroxide trioxide, zinc tellurite, etc. or telluric acid salts;
Tris (acetylacetonato) indium (III), indium amidosulfate (III), indium dichloride, indium chloride (I), indium chloride (III), indium acetate (III), indium bromide (III), indium iodide Indium salts such as (III), indium (III) nitrate, indium (III) sulfate, indium (III) fluoride, indium (III) oxide, indium (III) hydroxide;
Bis (acetylacetonato) diaquabarium (II), barium selenite, barium tellurite, barium benzoate, barium aluminate, barium chloride, barium formate, barium citrate, barium oxide, barium bromide, barium oxalate , Barium tartrate, barium metazirconate, barium hydroxide, barium metastannate, barium tungstate, barium metatitanate, barium metaniobate, barium lactate, barium metaborate, barium molybdate, barium iodide, barium hydrogen phosphate, carbonic acid carbonate Barium salts such as barium and barium fluoride;
Tetrakis (acetylacetonato) hafnium (IV), hafnium chloride (IV), hafnium oxide (IV), hafnium iodide (IV), hafnium sulfate (IV), hafnium nitrate (IV), hafnium oxysuccinate (IV), fluoro Hafnium salts such as hafnium acid, fluorohafnate, hafnium fluoride, or the like;
Potassium selenite, potassium hydrogen selenite, cesium trihydrogen selenite, sodium hydrogen selenite, lithium hydrogen selenite, copper selenite (II), sodium selenite, barium selenite, oxychloride Selenium, selenium chloride (I), selenium chloride (IV), selenium oxide (IV), aluminum selenate, selenate, zinc selenite, potassium selenate, ammonium selenate, calcium selenate, cesium selenate, selenate Selenium salts such as cobalt, copper (II) selenate, nickel selenate, sodium selenate, barium selenate, zinc selenate, etc. or selenates;
Scandium chloride (III), scandium formate (III), scandium acetate (III), scandium nitrate (III), scandium oxide (III), scandium fluoride (III), scandium iodide (III), scandium sulfate (III), etc. Scandium salts of
Niobium (II) oxide, niobium (V) oxide, niobium (hydrogen oxalate), niobium hydroxide (V), niobium oxyacetylacetonate, metaniobic acid, calcium metaniobate, strontium metaniobate, barium metaniobate, magnesium metaniobate , Lithium metaniobate, ammonium metaniobate, sodium metaniobate, niobium salts such as niobium pentachloride, or niobate salts;
Copper amidosulfate (II), copper benzoate (II), tetraammine copper (II) nitrate, copper citrate (II), copper oxide (I), copper bromide (I), copper oxalate (II), copper formate ( II), copper acetate (II), copper propionate (II), copper (II) valerate, copper (II) gluconate, copper (II) tartrate, copper (II) chloride, copper (II) bromide, water Copper (II) oxide, Copper acetate (II), Copper nitrate (II), Copper sulfate (II), Copper carbonate (II), Copper oxide (II), Cupric hydroxy nitrate, Copper tungstate (II), Carbonic acid Copper salts such as copper hydroxide (II), copper lactate (II), copper fluoride (II), copper iodide (I), etc .;
Tris (acetylacetonato) yttrium (III), yttrium chloride (III), yttrium formate (III), yttrium citrate (III), yttrium acetate (III), yttrium oxide (III), yttrium oxalate (III), yttrium nitrate Yttrium salts such as (III), yttrium carbonate (III), yttrium fluoride (III), yttrium iodide (III), yttrium sulfate (III), and yttrium phosphate (III);
Tris (acetylacetonato) lanthanum (III), lanthanum chloride (III), lanthanum formate (III), lanthanum acetate (III), lanthanum oxide (III), lanthanum oxalate (III), lanthanum nitrate (III), lanthanum carbonate ( III), lanthanum salts such as lanthanum fluoride (III), lanthanum dititanate (III), lanthanum sulfate (III), lanthanum phosphate (III), lanthanum iodide (III), etc .;
Tris (acetylacetonato) neodymium (III), neodymium (III) chloride, neodymium (III) formate, neodymium (III) acetate, neodymium (III) oxide, neodymium (III) bromide, neodymium oxalate (III), neodymium nitrate Neodymium salts such as (III), neodymium carbonate (III), neodymium dititanate (III), neodymium fluoride (III), neodymium iodide (III), neodymium sulfate (III), and neodymium phosphate (III); Can be mentioned. These compounds may be anhydrides or hydrates. Moreover, you may use individually and may be used in combination of 2 or more type. Furthermore, it may be dissolved or dispersed in the aqueous metal surface treatment agent solvent.

  The total content (B = B1 + B2) of one or more crosslinkable compounds (B) selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) is included in the aqueous metal surface treatment agent. The total solid content is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 90% by mass, and particularly preferably 30% by mass to 85% by mass. When the content of the crosslinkable compound (B) is in the range of 10% by mass to 90% by mass, the adhesion of the surface treatment film obtained by the treatment with the aqueous metal treating agent and the chemical adhesion maintaining property are further improved. .

(solvent)
The aqueous metal surface treatment agent according to the present invention may contain various solvents as required in order to improve workability when applied to the surface of the metal material.

  Examples of the solvent include water; alkane solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; alcohol solvents such as ethanol, 1-butanol and ethyl cellosolve; ether solvents such as tetrahydrofuran and dioxane; Ester solvents such as ethyl acetate and butoxyethyl acetate; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfone solvents such as dimethyl sulfoxide; phosphoric acid amide solvents such as hexamethylphosphoric triamide; . One of these solvents may be used, or two or more of these solvents may be mixed and used. Of these, water is preferred because it is environmentally and economically advantageous.

(Other additives)
The water-based metal surface treatment agent according to the present invention can contain a surfactant, an antifoaming agent, a leveling agent, an antibacterial and antifungal agent, a colorant and the like within a range not impairing the gist and film performance of the present invention. .

(Method for preparing aqueous metal surface treatment agent)
The method for producing the aqueous metal surface treatment agent according to the present invention is not particularly limited. For example, the polyvinyl alcohol-based compound (A) and the crosslinkable compound (B) are prepared by mixing with an optional additive, an optional solvent, and the like, and sufficiently mixing using a stirrer such as a mixing mixer. be able to.

[Metal material]
As shown in FIG. 1, a metal material 10 according to the present invention has a base metal 1 and a surface treatment film 2 formed on the surface thereof by applying the aqueous metal surface treatment agent according to the present invention. “Applying” refers to applying a water-based metal surface treatment agent to the surface of the base metal 1 by an application process described later. “Having” means that the substrate metal 1 and the surface treatment film 2 may have other configurations. For example, you may have the resin film 3 formed on the surface treatment film 2 by the lamination process. Since the surface treatment film 2 is formed by applying the above-described aqueous metal surface treatment agent according to the present invention to the base metal 1, it is excellent in adhesion and chemical adhesion maintenance.

  Since the metal material 10 has such a surface treatment film 2, after forming the resin film 3 or the resin film 3 on the surface treatment film 2, severe molding such as deep drawing, ironing, or stretch drawing is performed. Even if it is a case where it processes and also when it is a case where it exposes to an acid etc., it can prevent that the resin film 3 or the resin coating film 3 peels from the metal material 10. FIG.

  In addition, in FIG. 1, although the example which formed the surface treatment film | membrane 2 and the resin film 3 or the resin coating film 3 on one surface of the base metal 1 is shown, on both surfaces of the base metal 1, ie, The surface treatment film 2 may be formed on the other surface, and a resin film 3 or a resin coating film 3 may be further provided.

  The kind of base metal 1 is not specifically limited, Various things can be applied. For example, a metal material applicable to a body or lid of a food can, a food container, a dry battery container, an exterior material of a secondary battery, and the like can be mentioned, but the present invention is not limited thereto and can be applied to a wide range of uses. Metal materials can be used. In particular, it can be used as a packaging material for mobile lithium-ion secondary batteries used in mobile phones, electronic notebooks, notebook computers, video cameras, etc., and as a packaging material for lithium-ion secondary batteries used as drive energy for electric vehicles or hybrid vehicles. Can be mentioned. Among these metal materials, a surface treatment film can be formed on the surface, and a resin film can be laminated on the surface treatment film, and then deep drawing, ironing or stretch drawing, etc. A metal material that can be subjected to severe forming processing can be preferably used.

  Examples of such metal materials include copper materials such as pure copper and copper alloys, aluminum materials such as pure aluminum and aluminum alloys, iron materials such as ordinary steel and alloy steel, and nickel materials such as pure nickel and nickel alloys. Can do.

  As a copper alloy, what contains 50 mass% or more of copper is preferable, For example, brass etc. can be used. Examples of alloy components other than copper in the copper alloy include Zn, P, Al, Fe, and Ni. As the aluminum alloy, one containing 50% by mass or more of aluminum is preferable. For example, an Al—Mg alloy or the like can be used. Examples of alloy components other than aluminum in the aluminum alloy include Si, Fe, Cu, Mn, Cr, Zn, and Ti. As alloy steel, what contains 50 mass% or more of iron is preferable, for example, stainless steel etc. can be used. Examples of alloy components other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr, and Mo. As a nickel alloy, what contains 50 mass% or more of nickel is preferable, for example, a Ni-P alloy etc. can be used. Examples of alloy components other than nickel in the nickel alloy include Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, and P.

  The base metal 1 may be formed by forming a film containing the above metal element on the surface of a metal material, ceramic material or organic material other than the above metal material. Such a metal film can be formed by a technique such as plating, vapor deposition, or cladding. Moreover, the shape of the base metal 1, a structure, etc. are not specifically limited, For example, a plate-shaped or foil-shaped metal material can be used.

  As described above, according to the water-based metal surface treatment agent according to the present invention, from the polyvinyl alcohol compound (A), the crosslinkable organic compound (B1), and the crosslinkable inorganic compound (B2) described above. Since one or two or more types of crosslinkable compounds (B) are selected, the surface treatment film obtained by treatment with the aqueous metal surface treatment agent has high adhesion and is exposed to an acid or the like. High adhesion can be maintained. As a result, when a resin film is laminated or a resin coating film is formed on a metal material on which a surface treatment film is formed, and then a severe forming process such as deep drawing, ironing or stretch drawing is performed. In addition, even when exposed to an acid, an organic solvent, or the like, the laminate film or the resin coating film can be prevented from peeling from the metal material.

[Surface treatment method]
A metal surface treatment method using a water-based metal surface treatment agent is a coating process in which a water-based metal surface treatment agent is applied to the surface of a base metal, and after the coating process, it is dried without washing to form a surface treatment film. And a drying step.

(Coating process)
An application process is a process of apply | coating an aqueous metal surface treating agent to the surface of a base metal. The method of applying is not particularly limited, and for example, spray coating, dip coating, roll coating, curtain coating, spin coating, or a combination of these can be used. The conditions for using the aqueous metal surface treatment agent are not particularly limited. For example, the temperature of the aqueous metal surface treatment agent and the metal material at the time of application is preferably 10 ° C to 90 ° C, and more preferably 20 ° C to 60 ° C. Use of useless energy can be suppressed as temperature is 60 degrees C or less. Moreover, the application time and the application amount can be appropriately set according to the required film thickness of the obtained surface treatment film.

(Drying process)
A drying process is a process of drying, without washing with water after an application process, and forming a surface treatment coat. The drying temperature can be a temperature that matches the solvent used. For example, when water is used as the solvent, the temperature is preferably in the range of 50 ° C to 260 ° C. The drying apparatus is not particularly limited, but a batch type, continuous type or hot air circulation type drying furnace, a conveyor type hot air drying furnace, an electromagnetic induction heating furnace using an IH heater, or the like can be used. Can be set to

  Even if the surface treatment film obtained in this way is subjected to severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing after forming a resin film (laminate film) or resin coating film thereon, Further, even when exposed to an acid or the like, it is possible to prevent the laminate film or the resin film made of the resin film from peeling off.

  In addition, it is preferable that it is 0.01 micrometer-1 micrometer, and, as for the film thickness of the surface treatment film | membrane obtained, it is more preferable to set it as 0.02 micrometer-0.05 micrometer. By setting it as this range, the adhesiveness of a surface treatment film and chemical-resistant adhesion maintenance property can be improved more.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited by the following examples. In the following, “part” means “part by mass”, “mass%” is synonymous with “wt%”, and hereinafter, it may be simply expressed as “%” unless otherwise specified. “Ppm” is synonymous with “mg / L”.

[Polyvinyl alcohol compound (A)]
The polyvinyl alcohol compound (A) used is shown below.
Aa: polyvinyl alcohol having a saponification degree of 96% and a viscosity of 25 mPa · S Ab: acetoacetylated polyvinyl alcohol having a saponification degree of 99%, a viscosity of 12 mPa · S, and an acetoacetylation degree of 9.8%

[Crosslinking Compound (B)]
(Crosslinkable organic compound (B1))
As the organic compound (B1a) having a glycidyl ether group, glycerol polyglycidyl ether (trifunctional, epoxy equivalent 144, viscosity 170 mPa · S) was used. Moreover, the hexamethylene diisocyanate-ethyl acetoacetate block body was used as an organic compound (B1b) which has an isocyanate group. Moreover, methylol melamine was used as an organic compound having a methylol group (symbol B1c). In addition, glyoxal was used as the organic compound (B1d) having an aldehyde group.

(Crosslinkable inorganic compound (B2))
The crosslinkable inorganic compound (B2) used is shown below.

B2a: Titanium hydrofluoric acid (concentration: 40.0% by mass)
B2b: zirconium hydrofluoric acid (concentration: 40.0% by mass)
B2c: silica sol (surface charge cation, particle size 10 to 20 nm, 19.0 mass%, pH = 4.7)
B2d: Titanium lactate (concentration 44.0% by mass)
B2e: Amorphous zirconia sol (nonvolatile content concentration 10.0% by mass, particle size 10 to 30 nm, pH = 2.8)
B2f: silicofluoric acid (concentration: 40.0% by mass)
B2g: Chromium fluoride (III) (Cr concentration: 1.0% by mass)
B2h: Iron (III) fluoride (Fe concentration: 2.5% by mass)
B2i; selenium oxide (IV)
B2j; cerium oxide sol (non-volatile content 15%, pH = 3.5)
B2k; chromium (III) acetate

[Water-based metal surface treatment agent]
A combination of polyvinyl alcohol compound Aa and / or Ab, one or more selected from crosslinkable organic compounds B1a to B1d and crosslinkable inorganic compounds B2a to B2g at a predetermined content, and a solvent as water. 1- Examples 1 to 41 shown in Table 3 and aqueous metal surface treatment agents of Comparative Examples 1 to 18 were prepared. In addition, "concentration" in Tables 1 to 3 indicates the nonvolatile content concentration (% by mass) of each compound contained in the aqueous metal surface treatment agent. “A concentration” indicates the total content (% by mass) of the polyvinyl alcohol compound (A) with respect to the total solid content in the aqueous metal surface treatment agent, and “B1 + B2 concentration” It is content of the crosslinkable compound (B) with respect to the total solid content, Comprising: Total content (mass%) of crosslinkable organic compound B1 and crosslinkable inorganic compound B2 is shown. In the following, Examples 35 and 40 containing crosslinkable inorganic compounds B2h and B2i containing metal elements other than Cr (III), Zr, Ti, Si, Ce and Te, and the crosslinkable inorganic compound (B2) Examples 1, 3, 5, 8, 9, 26, 28, and 39 not included are comparative examples.

[Metal material]
The metal material used as the base metal is shown below.
Al: A1100P, thickness 0.3mm
Cu: C1020P, thickness 0.3 mm
Ni: Pure nickel plate: (purity 99% by mass or more), thickness 0.3 mm
SUS: SUS304 plate, thickness 0.3mm
Ni plating Cu: Electric Ni plating Cu plate (thickness 0.3 mm, Ni plating thickness 2 μm)
From these metal materials, metal materials shown in the “base material” column of Tables 1 to 3 were selected and prepared as base metals of Examples 1 to 41 and Comparative Examples 1 to 22.

[Production of test materials]
(surface treatment)
Spray the base metals of Examples 1 to 41 and Comparative Examples 1 to 18 shown in Tables 1 to 3 with a 3% aqueous solution of Fine Cleaner 359E (alkali degreasing agent manufactured by Nihon Parkerizing Co., Ltd.) at 65 ° C. for 1 minute. After degreasing, it was washed with water to clean the surface. Then, in order to evaporate the water | moisture content on the surface of a metal material, it heat-dried at 80 degreeC for 1 minute. The surface of the base metal that has been degreased and washed is coated with the aqueous metal surface treatment agents of Examples 1 to 41 and Comparative Examples 1 to 18 shown in Tables 1 to 3 by bar coating using a # 3SUS Meyer bar, respectively. (Coating process), dried in a hot air circulation drying oven at 200 ° C. for 1 minute (drying process) to obtain a metal material having a surface treatment film. In addition, two metal materials each surface-treated with the same kind of water-based metal surface treatment agent were prepared, and as described below, lamination was performed on the surface treatment film by different methods.

  Moreover, the metal material as described in Comparative Examples 19-22 was prepared, and without applying an aqueous metal surface treating agent, it was heat-dried after degreasing and rinsing in the same manner as described above to obtain a metal material having no surface treatment film. . In addition, two metal materials of the same kind were prepared, and the surface was laminated by different methods as shown below.

(Lamination)
About one of the metal materials having the surface treatment film prepared two by two, lamination processing by heat lamination was performed on the surface treatment film. Lamination by dry lamination was performed on another surface treatment film. For the metal material having no surface treatment film, heat lamination was applied to one side surface of the two, and dry lamination was applied to the other one side surface.

  Lamination by heat lamination was performed as follows. A dispersion of acid-modified polypropylene (“R120K” manufactured by Mitsui Chemicals, Inc., nonvolatile content concentration 20 mass%) was applied by bar coating using a # 8SUS Meyer bar, and then heated at 200 ° C. in a hot-air circulating drying oven. The adhesive layer was formed by drying for minutes. Thereafter, this adhesive layer and a 30 μm-thick polypropylene film (“CPPS” manufactured by Tosero Co., Ltd.) are thermocompression bonded at 190 ° C. and 2 MPa for 10 minutes to perform lamination by heat lamination. A laminated metal material was obtained.

  Lamination by dry lamination was performed as follows. Apply urethane-type dry laminate adhesive (Toyo Morton Co., Ltd., “AD-503 / CAT10”, non-volatile content 25% by mass) by bar coating using # 8SUS Meyer bar, and then in hot air circulation drying oven The adhesive layer and a corona discharge-treated surface of an unstretched polypropylene film of 30 μm (manufactured by Futaki Chemical Co., Ltd., “FCZX”) at 100 ° C. and 1 MPa are then bonded. By curing at 4 ° C. for 4 days, laminating by dry lamination was performed to obtain a metal material on which a polypropylene film was laminated.

(Molding)
The polypropylene film laminated metal material obtained by heat lamination and the polypropylene film laminated metal material obtained by dry lamination were each deep drawn in a drawing and ironing test. The coated metal plate punched to a diameter of 160 mm was drawn (first time) to produce a cup having a diameter of 100 mm. Subsequently, the cup was again drawn to a diameter of 75 mm (second time), and further drawn to a diameter of 65 mm (third time) to prepare a can as a test material. Note that the ironing (thinning) ratios in the first drawing, the second drawing, and the third drawing were 5%, 15%, and 15%, respectively.

[Performance evaluation]
(Adhesion)
About the can after a shaping | molding process, the presence or absence of peeling of a polypropylene film (henceforth "initial adhesiveness") was evaluated. Cans were prepared, and there was no peeling of the film and excellent initial adhesion, and 3 points were given. A part of the film was peeled 2 points, and a case where the film was completely peeled was 1 point. The results of the evaluation test are shown in Tables 4 and 5.

(Chemical resistance adhesion maintenance)
Among the chemical resistance adhesion maintaining properties, here, the adhesion maintaining properties with respect to the electrolytic solution (hereinafter referred to as “electrolytic solution adhesion maintaining property”) were evaluated. In detail, the presence or absence of peeling of a polypropylene film was evaluated about the can after having been further immersed in electrolyte solution after a shaping | molding process as follows.

The can after deep drawing was filled in a sealed container, and an electrolyte solution for lithium ion secondary batteries to which 1000 ppm of ion exchange water was added (electrolyte; 1 mol / L LiPF ₆ , solvent; EC: DMC: DEC = After being immersed in 1: 1: 1 (volume%), it was put into a 60 ° C. constant temperature bath for 7 days. “EC” refers to ethylene carbonate, “DMC” refers to dimethyl carbonate, and “DEC” refers to diethyl carbonate.

  Thereafter, the sample material was taken out, washed by immersing in ion-exchanged water for 1 minute and swung, and then dried at 100 ° C. for 10 minutes in a hot-air circulating drying furnace. The film surface is then scratched with the tip of a tweezers, with 3 points for the film having no peeling of the film and excellent electrolyte solution adhesion maintaining ability, 2 points for partially peeling the film, and 1 point for peeling the entire film. As evaluated. The results of the evaluation test are shown in Tables 4 and 5.

  As shown in Table 4 and Table 5, the metal material having the surface treatment film formed by applying the aqueous metal surface treatment agent described in Examples 1-41 has an initial adhesion property and an electrolytic solution adhesion maintenance property. It was confirmed that it was excellent.

DESCRIPTION OF SYMBOLS 1 Base metal 2 Surface treatment film 3 Resin film (laminate film) or resin coating 10 Metal material which has surface treatment film

Claims (4)

Crosslinkability comprising a polyvinyl alcohol compound (A), a crosslinkable organic compound (B1) having a functional group capable of reacting with the polyvinyl alcohol compound (A), and an element capable of reacting with the polyvinyl alcohol compound (A). 1 type or 2 types or more of crosslinkable compounds (B) chosen from inorganic compound (B2) (however, it does not contain a vanadium compound) ,
Containing at least the crosslinkable inorganic compound (B2) as the crosslinkable compound (B),
The crosslinkable organic compound (B1) has one or more functional groups selected from a glycidyl ether group, an isocyanate group, a methylol group, and an aldehyde group,
A water-based metal surface treatment agent, wherein the crosslinkable inorganic compound (B2) contains one or more elements selected from Cr (III), Zr, Ti, Si, Ce, and Te .   Content of the said polyvinyl alcohol type compound (A) is 10 mass%-90 mass% with respect to the total solid contained in a water-system metal surface treating agent, The said crosslinkable organic compound (B1) and the said crosslinkability. The total content (B = B1 + B2) of one or more crosslinkable compounds (B) selected from the inorganic compound (B2) is 10 masses based on the total solid content contained in the aqueous metal surface treatment agent. The water-based metal surface treatment agent according to claim 1, wherein the water-based metal surface treatment agent is in a range of from% to 90% by mass.   The aqueous metal surface treatment agent according to claim 1 or 2, wherein both the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) are contained.   A metal material comprising a surface treatment film formed by applying the aqueous metal surface treatment agent according to any one of claims 1 to 3 to a metal material surface.

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