TWI554647B - An aqueous metal surface treatment agent and a metal material treated with the treatment agent - Google Patents

Description

Water metal surface treatment agent and metal material treated by the treatment agent

The present invention relates to an aqueous metal surface treatment agent for forming a surface treatment film capable of preventing adhesion between a metal material and a laminate film or a resin coating film, and excellent in adhesion resistance maintenance, and treatment with the metal surface treatment agent Made of metal material. More specifically, it relates to a severe forming process for forming a resin film or forming a resin coating film even if a metal material is laminated, and then subjected to deep drawing processing, stretching processing, or stretch drawing processing. In addition, it is also possible to provide a high-adhesiveness of the laminated film or the like without delamination, and it is also possible to provide a high-adhesive-resistant hexavalent chromium-free surface-treated film which is excellent in adhesion resistance and maintainability even when exposed to an acid or an organic solvent. Water metal surface treatment agent, etc.

The laminating process is a processing method in which a film made of a resin (hereinafter referred to as "resin film" or "laminated film") is heat-pressure-bonded to the surface of a metal material (hereinafter, simply referred to as "metal surface"). One of the coating methods for protecting a metal surface or imparting design to a metal surface is used in various fields. This laminating process is a method in which a resin composition is dried or dispersed in a solvent to form a resin coating film, and a solvent or a waste gas such as carbon dioxide or a warm gas generated during drying is produced as compared with a method in which a resin composition is dissolved or dispersed in a solvent. Less. Therefore, it is preferably applied to an environmentally friendly surface, and its use is expanded, for example, for use in a body or a lid of a food can, which is made of an aluminum thin plate, a steel thin plate, a packaging aluminum foil, or a stainless steel foil. Food containers or dry battery containers, etc.

In particular, metal foils such as aluminum foil or stainless steel foil which are lightweight and have high barrier properties have been preferably used as mobile lithium ion batteries for mobile phones, electronic notebooks, notebook computers, and camcorders. The material is packed and tab-lead, and lamination is applied to the surface of such a metal foil. Moreover, lithium ion batteries have been explored as driving energies for electric vehicles or hybrid vehicles; laminate metal foils have also been discussed as exterior materials.

The laminated film used for such lamination processing is subjected to heat and pressure bonding after being directly bonded to a metal material. Therefore, compared with the general resin coating film which apply|coated the dry resin composition, it has the advantage which can suppress waste of a raw material, a pinhole (defect part), and it is excellent in workability. As the material of the laminated film, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate or a polyolefin such as polyethylene or polypropylene is generally used.

When the metal surface is subjected to lamination processing without treatment such as chemical conversion treatment, there is a problem that the laminated film is peeled off from the metal surface or corroded in the metal material. For example, in the food container or the packaging material, the content of the container or the packaging material after the lamination processing is subjected to heat treatment for sterilization, but the laminated film may be peeled off from the metal surface during the heat treatment. Further, in a material other than a lithium ion battery, a processing having a high degree of processing is accepted in the manufacturing step. Further, when used for a long period of time, moisture in the atmosphere will invade the container, which will react with the electrolyte to form hydrofluoric acid, which will penetrate the laminated film to cause peeling of the metal surface and the laminated film, and corrosion will occur. The problem with metal surfaces.

For such a problem, in order to improve the adhesion between the laminated film and the metal surface and the corrosion resistance of the metal surface when the laminated film is laminated on the metal surface, phosphoric acid is usually applied after the metal surface is degreased and washed. Chromate or the like is converted into a treatment or the like. However, in such a chemical conversion process, it is necessary to perform a washing step for removing excess processing liquid after the treatment, and the wastewater treatment of the washing water discharged from the washing step is costly. In particular, since a treatment liquid containing hexavalent chromium is used for the chemical conversion treatment such as chromate phosphate, it has been avoided due to environmental awareness in recent years.

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. Further, Patent Document 2 proposes a chromium-free metal surface treatment agent composed of a specific amount of a water-soluble zirconium compound and/or a water-soluble titanium compound, an organic phosphine oxide compound, and tannin. Further, Patent Document 3 proposes a metal surface treatment agent containing an aminolated phenol polymer, a specific metal compound such as Ti or Zr, and a pH of 1.5 to 6.0. Further, Patent Document 4 proposes a resin film containing an aminated phenol polymer, an acrylic polymer, a metal compound, and a phosphorus compound further required.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Patent Publication WO2002/063703

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-265821

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-313680

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-262143

An object of the present invention is to provide an aqueous metal surface treatment agent for forming a surface treatment film capable of preventing adhesion between a metal material and a laminate film or a resin coating film, and excellent in adhesion resistance maintenance; and providing the metal A metal material treated with a surface treatment agent. Specifically, it is possible to provide a resin film for forming a metal material or to form a resin coating film, and to impart a severe molding process such as deep drawing, stretching, or drawing and drawing processing. The water-based metal surface treatment of the hexavalent chromium-free surface treatment film which is excellent in the adhesion resistance maintenance of the high-adhesion property, even if it is exposed to an acid or the like, even if it is exposed to an acid or the like. And a metal material treated with the metal surface treatment agent.

The aqueous metal surface treatment agent of the present invention for solving the above-mentioned problems is characterized by comprising: a polyvinyl alcohol compound (A); and crosslinking with a functional group reactive with the polyvinyl alcohol compound (A) One or two or more kinds of crosslinkable compounds (B) selected from the group consisting of the organic compound (B1) and the crosslinkable inorganic compound (B2) which is an element which can react with the polyvinyl alcohol compound (A).

According to the present invention, since the polyvinyl alcohol-based compound (A) and the above cross-linkable compound (B) are contained, the aqueous metal surface treatment agent is treated. The surface treated film has high adhesion and maintains high adhesion even when exposed to an acid or the like. As a result, even if a resin film is laminated on a metal material or a resin coating film is formed, and then subjected to a severe forming process such as deep drawing, stretching, or drawing, and the like, even if it is further exposed to an acid or an organic solvent. The laminated film or the resin coating film can also be prevented from being peeled off from the metal material at the same time.

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

According to the invention, since the crosslinkable organic compound (B1) has the above-mentioned functional group, the surface-treated film obtained by treating the aqueous metal surface treatment agent has better adhesion and is exposed to an organic solvent or an acid. Maintain a more stable adhesion for a long period of time.

In the aqueous metal surface treatment agent of the present invention, the crosslinkable inorganic compound (B2) contains Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, Ti, Si, Sr. One or more elements selected from the group consisting of W, Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La.

According to the invention, since the crosslinkable inorganic compound (B2) contains the above-mentioned elements, the surface-treated film obtained by treating the aqueous metal surface treatment agent has better adhesion and is exposed to an organic solvent or an acid. Maintain a more stable adhesion for a long period of time.

A metal material of the present invention for solving the above problems, characterized in that it has a surface-treated skin formed by applying the aqueous metal surface treatment agent of the present invention. membrane.

According to the present invention, there is provided a surface-treated film formed by applying the above-described aqueous metal surface treatment agent of the present invention, and therefore even a metal material having the surface treatment film is subjected to lamination processing, and then subjected to deep drawing processing and elongation processing. When a severe molding process such as stretching and drawing is performed and further exposed to an acid or the like, the laminated film or the resin coating film formed on the surface of the metal material can be prevented from being peeled off.

According to the water-based metal surface treatment agent of the present invention, it is possible to provide a water-based metal surface treatment agent for forming a surface-treated film which is excellent in adhesion prevention between the metal material and the laminated film or the resin coating film and excellent in adhesion resistance maintenance. .

According to the metal material of the present invention, a metal material having such a surface-treated film can be provided.

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

[Water metal surface treatment agent]

The water-based metal surface treatment agent of the present invention is as shown in FIG. A treatment agent for the surface treatment film 2 for the base of the laminate film or the resin coating film 3 is formed on the surface of the base material metal material 1 (hereinafter referred to as "base material metal 1"). It is characterized in that it contains a polyvinyl alcohol-based compound (A) and one or two or more kinds of crosslinkable compounds (B) selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2). "Contained" means that the aqueous metal surface treatment agent may contain a compound other than the polyvinyl alcohol compound (A) and the crosslinkable compound (B). Examples of such a compound include a surfactant, an antifoaming agent, a leveling agent, an antibacterial and antifungal agent, and a coloring agent. Such compounds may be included within the scope of the present invention and the properties of the film.

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

(polyvinyl alcohol compound (A))

The polyvinyl alcohol-based compound (A) is one or two or more compounds selected from the group consisting of polyvinyl alcohol and derivatives thereof. By containing the polyvinyl alcohol-based compound (A) and the crosslinkable compound (B), the adhesion of the surface-treated film obtained by the aqueous metal surface treatment agent and the adhesion resistance of the drug can be improved.

As the polyvinyl alcohol and its derivative, a saponified product of polyvinyl acetate, a saponified product of a copolymer of vinyl acetate and another monomer, or the like can be used. The saponified product may be a partially saponified product or a fully saponified product.

Examples of the other monomer copolymerized with vinyl acetate include anionic comonomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and the like; styrene, acrylonitrile, vinyl ether, (methyl) propylene Amine, N-methylol (meth) acrylamide, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, vinyl pyrrolidone, acryl morpholine, vinyl acetate, etc. An ionic comonomer; a cationic group of aminoethyl (meth) acrylate, N-hydroxypropylaminoethyl (meth) acrylate, vinyl imidazole, N, N-dimethyldiallylamine, etc. monomer.

Further, it is also possible to react the polyvinyl alcohol and its derivative with diketene by acetylation.

The content of the polyvinyl alcohol-based compound (A) is preferably from 10% by mass to 90% by mass, more preferably from 10% by mass to 80% by mass, based on the total solid content of the aqueous metal surface treating agent. It is 20% by mass to 80% by mass. When the content is 10% by mass to 90% by mass, the adhesion of the obtained surface-treated film and the adhesion resistance of the drug can be further improved.

In addition, the "solid content" means a solid component obtained by removing a volatile component such as a solvent from among the components of the aqueous metal surface treatment agent, and specifically, a polyvinyl alcohol-based compound (A) and cross-linked. The total amount of one or two or more kinds of crosslinkable compounds (B) selected from the group consisting of the organic compound (B1) and the crosslinkable inorganic compound (B2). Therefore, the content of the polyvinyl alcohol-based compound (A) is preferably 10% by mass to 90% by mass based on the total amount (all solid components) of the polyvinyl alcohol-based compound (A) and the crosslinkable compound (B). More preferably, it is 10% by mass to 80% by mass, and particularly preferably 20% by mass to 80% by mass.

(crosslinkable compound (B))

Crosslinkable compound (B), which is composed of a crosslinkable organic compound (B1) And one or more compounds selected from the crosslinkable inorganic compound (B2). When the water-based metal surface treatment agent contains the crosslinkable compound (B), the adhesion of the surface-treated film obtained by the aqueous metal surface treatment agent and the adhesion resistance of the drug can be improved.

(crosslinkable organic compound (B1))

The crosslinkable organic compound (B1) is a compound having a functional group reactive with polyvinyl alcohol (A). "Reactive" means that it can be reacted with the polyvinyl alcohol (A) to react with the same. By "having" is meant any other functional group or bonding unit other than the functional groups.

The crosslinkable organic compound (B1) may, for example, be one or two or more organic compounds selected from the group consisting of glycidyl ether groups, isocyanate groups, methylol groups and aldehyde groups.

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, and glycerin. Triglycidyl ether, glycerol polyglycidyl ether, diglycerin glycidyl 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 tolyl diisocyanate; aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate; and aromatic esters such as xylylene diisocyanate; Aliphatic diisocyanates; alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate; hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene An aliphatic diisocyanate such as a bis-isocyanate or the like. The isocyanate compound is not particularly limited, but from the viewpoint of the stability of the aqueous metal surface treatment agent, it is preferred to use an isocyanate compound which is blocked with various blocking agents. Examples of the blocking agent include various blocking agents such as a phenol type, an alcohol type, an anthraquinone type, an active methylene type, an acid amide type, an aminoformate type, and a sulfite type.

Examples of the organic compound having a methylol group include a soluble phenol resin, a methylol melamine, a homopolymer of an N-methylol acrylamide monomer, an N-methylol acrylamide monomer, and other single substances. Copolymers and the like.

Examples of the organic compound having an aldehyde group include a dialdehyde compound such as glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, and pimediol; or a compound having three or more aldehyde groups.

(crosslinkable inorganic compound (B2))

The crosslinkable inorganic compound (B2) is a compound containing an element reactive with the polyvinyl alcohol-based compound (A). "Reactive" means that it can be reacted with the polyvinyl alcohol-based compound (A) to react with the above. "Include" means that other elements may be included in addition to those elements.

The crosslinkable inorganic compound (B2) may, for example, be composed of Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, One or two selected from Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La An inorganic compound of the above elements. In particular, an inorganic compound containing one or more elements selected from the group consisting of Mg, Al, Ca, Mn, Cr(III), Zn, Fe, Zr, Ti, Si, Ce, Te, and Hf is more preferable; An inorganic compound containing one or two or more elements selected from the group consisting of Cr(III), Zr, Ti, Si, Ce, and Te is more preferable.

Specifically, it includes Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta. a salt, a wrong compound or a metal hydrated oxide of one or more elements selected from the group consisting of Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La (hereinafter also referred to as "salt" Wait").

More specifically, bis(ethylmercaptopyruvate) magnesium dihydrate (II), magnesium aluminate, magnesium benzoate, magnesium formate, magnesium oxalate, magnesium tungstate, magnesium metasilicate, magnesium borate, molybdic acid Magnesium salt of magnesium, magnesium iodide, magnesium pyrophosphate, magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, magnesium ammonium phosphate, magnesium hydrogen phosphate, magnesium oxide, etc.; aluminum nitrate, aluminum sulfate, sulfuric acid Potassium aluminum, aluminum sulfate aluminum, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum oxide, aluminum fluoride, aluminum iodide, aluminum acetate, aluminum benzoate, aluminum citrate, aluminum gluconate, Aluminum salts of aluminum selenate, aluminum oxalate, aluminum tartrate, aluminum lactate, aluminum palmitate, etc.; bis(acetylthiopyruvate) calcium (II) dihydrate, calcium benzoate, calcium citrate, calcium metastannate, Calcium selenate, calcium tungstate, calcium carbonate, calcium tetraborate, calcium molybdate, calcium maleate, calcium malate, calcium pyrophosphate, calcium fluoride, calcium hypophosphite, calcium nitrate, calcium hydroxide, calcium oxide, Calcium oxalate, oxidation Calcium salts such as calcium and calcium acetate; bis(acetylthiopyruvate) manganese (II) dihydrate, trimanganese tetraoxide, manganese (II) oxide, manganese (III) oxide, manganese (IV) oxide, bromination Manganese (II), Manganese oxalate (II), Permanganic acid (VII), Potassium permanganate (VII), Sodium permanganate (VII), Manganese dihydrogen phosphate (II), Manganese nitrate (II), Manganese sulfate (II), manganese (III) sulfate, manganese (IV) sulfate, manganese (II) fluoride, manganese (III) fluoride, manganese (II) carbonate, manganese (II) acetate, manganese (III) acetate, ammonium sulfate a manganese salt such as manganese (II), manganese (II) iodide or manganese (II) or a manganate; bis(ethylmercaptopyruvate) cobalt (II) dihydrate, ginseng (acetonitrile) Acid)cobalt(III), cobalt (II) amine sulfonate, cobalt (II) chloride, chloropentaamine cobalt chloride (III), hexaammine cobalt chloride (III), diammonium tetranitrocobalt (III) Ammonium acid, cobalt (II) sulfate, cobalt ammonium sulfate, cobalt (II) nitrate, cobalt aluminum oxide, cobalt (II) hydroxide, cobalt (II) oxide, cobalt phosphate, cobalt (II) acetate, cobalt formate (II) ), cobalt trioxide, cobalt (II) bromide, cobalt (II) oxalate, cobalt (II) selenate, cobalt (II) tungstate, cobalt (II) hydroxycarbonate, cobalt (II) molybdate, cobalt iodide (II) ), cobalt salt of cobalt (II) phosphate, etc.; diamine Nickel (II) acid, nickel (II) benzoate, nickel (II) nitrate, nickel (II) sulfate, nickel (II) carbonate, nickel pyridinium (II) pyruvate, nickel (II) chloride, hexamine Nickel chloride, nickel oxide, nickel (II) hydroxide, nickel (II) oxide, nickel acetate, nickel (II) citrate, nickel (II) succinate, nickel (II) bromide, nickel (II) oxalate, Nickel (II) tartrate, nickel (II) selenate, nickel (II) hydroxycarbonate, nickel lactic acid (II), nickel salt of nickel (II) molybdate, nickel (II) iodide, nickel (II) diphosphate, etc.; chromium (III) formate, chromium (III) fluoride, chromium (III) nitrate, sulfuric acid Chromium (III), chromium (III) oxalate, chromium (III) acetate, chromium (III) ruthenate, chromium (III) hydroxide, chromium (III) oxide, chromium (III) bromide, chromium (III) Such as chromium salts, etc.; bis(ethylmercaptopyruvate) zinc (II), zinc benzoate (II), zinc hydroxychloride (II), zinc (II) hydride, zinc (II) citrate, 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 tyrosinate (II), zinc (II) pyrophosphate, zinc (II) sulfate, zinc (II) carbonate, zinc (II) chloride, zinc (II) iodide, zinc (II) hydroxide, zinc oxide (II) such as zinc salt, etc.; bis(acetylthiopyruvate) iron (II) dihydrate, iron (III) ginseng (ethylpyruvate), tripotassium trioxalate, iron (II) formate, four Iron (III) vanadate, iron (III) bromide, iron (III) tartrate, iron (II) lactate, iron (II) fluoride, iron (III) fluoride, iron (II) chloride, ferric chloride (III), iron (II) iodide, iron (III) iodide, iron (II) sulfate, iron (III) sulfate, nitric acid Iron (II), iron (III) nitrate, iron (II) acetate, iron (III) acetate, iron (III) citrate, iron (II) gluconate, iron (Glycerate) ), iron (II) oxalate, iron (III) oxalate, iron (II) picolinate, iron (III) picolinate, iron (II) L-phenylalanine, iron (III) L-phenylalanine, Iron (II) malonate, iron (III) malonate, iron hydroxide (II) iron salt of iron (III) hydroxide, iron (II) oxide, iron (III) oxide, iron trioxide, etc.; bis(ethylmercaptopyruvate) ruthenium (II) dihydrate, cesium formate (II), bismuth citrate (II) bismuth tungstate, bismuth metastannate, cerium (IV) oxide, cerium (II) oxide, cerium oxalate, cerium metasilicate, cerium molybdate, cerium iodide, cerium nitrate, Barium sulfate, barium carbonate, barium acetate, barium chloride, barium phosphate, barium lactate, etc.; barium diammonium dioxalate, titanium dipotassium dioxalate, titanium oxide (II), titanium oxide (III), Titanium oxide (IV), second titanium oxysulfate, alkaline titanium phosphate, titanium (IV) bromide, metatitanic acid, zinc (II) metasilicate, aluminum (III) titanate, potassium metatitadate, titanium Cobalt (II) acid, zirconium titanate, barium titanate, iron (III) metasilicate, copper (II) metasilicate, sodium titanate, barium (III) titanate, barium titanate, titanium Barium (III), magnesium metatluminate, magnesium titanate, manganese (II) metasilicate, barium (III) dititanate, lithium metasilicate, ammonium hexafluorotitanium (IV), titanium hexafluoride (IV) Potassium acid, titanium (IV) iodide, titanium (III) sulfate, titanium (IV) sulfate, titanium chloride, titanium nitrate, titanium oxysulfate, titanium (III) fluoride, titanium (IV) fluoride, hexafluoride titanium Titanium lactate, peroxotitanic acid, titanium laurate, titanium acetate of pyruvate, titanium salt of titanium hydroxide (IV), etc. or titanate; zirconium (IV) of bismuth (acetyl acetonate) Zirconium chloride (IV) chloride, zirconium (IV) chloride, zirconium silicate, zirconium oxide (IV) acetate, zirconium oxide (IV), zirconium oxide (IV) nitrate, barium zirconate, lithium meta-zirconate, partial Zinc zirconate (II), aluminum (III) meta-cobaltate, calcium meta-zirconate, cobalt (II) meta-zirconate, bismuth meta-zirconate, copper (II) meta-zirconate, sodium meta-zirconate, meta-zirconic acid Nickel (II), barium meta-zirconate, barium zirconate (III), magnesium meta-zirconate, zirconium oxycarbonate, ammonium hexafluorozirconate (IV), potassium hexafluorozirconate (IV), zirconium iodide, phosphoric acid Zirconium hydroxide (IV), basic zirconium carbonate, ammonium zirconium carbonate, ammonium zirconium carbonate, zirconium nitrate, zirconium nitrate, zirconium sulfate (IV), zirconyl sulfate, hexafluorozirconic acid, zirconyl oxyphosphate, pyrophosphoric acid a zirconium salt such as zirconium, zirconyl phosphate, zirconium oxychloride, zirconium fluoride, zirconyl acetate, zirconium oxide or zirconium hydroxide; ceric acid salt such as hexafluoroantimonic acid or cerium oxide; Tungsten (VI), iron (III) oxide, tungsten (VI), tungsten dichloride, tungsten dioxide, tungsten trioxide, metatungstic acid, ammonium metatungstate, sodium metatungstate, secondary tungsten Acid, ammonium paratungstate, sodium paratungstate, zinc (II) tungstate, potassium tungstate, calcium tungstate, cobalt (II) tungstate, barium tungstate, barium tungstate, copper (II) tungstate, nickel tungstate, Tungsten tungstate, magnesium tungstate, manganese (II) tungstate, lithium tungstate, phosphotungstic acid, ammonium phosphotungstate, sodium tungstate, etc. or tungstate; ginsengyl pyruvate ) bismuth (III), cerium (III) chloride, cerium (III) oxide, cerium (IV) oxide, cerium (III) bromide, cerium (III) oxalate , cerium (IV) hydroxide, ammonium cerium (IV) sulfate, ammonium cerium (III) sulfate, cerium (III) carbonate, cerium sulfate, cerium (III) acetate, cerium (III) nitrate, cerium (IV) sulfate, Barium salts of cerium (III) fluoride, cerium (III) iodide, cerium (III) phosphate, etc.; molybdenum chloride (V), molybdenum oxide (IV), molybdenum oxide (VI), zinc molybdate (II) , potassium molybdate, calcium molybdate, cobalt (II) molybdate, bismuth molybdate, nickel (II) molybdate, bismuth molybdate, bismuth molybdate (III), magnesium molybdate, lithium molybdate, lithium paramolybdate , bismuth molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, molybdenum Acid, ammonium molybdate, ammonium molybdate, sodium molybdate, etc. or molybdate; oxygen vanadium dichloride, oxygen vanadium trichloride, vanadium trichloride, vanadium oxide, iron tetravanadate ( III), vanadium (III) bromide, vanadium oxalate, vanadium (II) iodide, vanadium pentoxide, metavanadic acid, sodium metavanadate, sodium vanadate, ammonium metavanadate, sodium metavanadate, vanadium Acid vanadium, oxygen vanadium trichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyethanoacetate, vanadium acetyl acetate, vanadium salt of phosphorus vanadium molybdate, etc. or vanadic acid Salt, etc.; tin (II) chloride, tin (II) acetate, tin (II) oxalate, tin (II) tartrate, tin (IV) oxide, tin nitrate, tin sulfate, tin (II) fluoride, tin iodide (II), tin salts of tin (IV) iodide, tin (II) pyrophosphate, zinc metastannate, zinc metastannate, calcium metastannate, barium metastannate, barium metastannate, magnesium metastannate, etc. Or stannate, etc.; bismuth benzoate (III), cerium (III) chloride, cerium (III) citrate, cerium (III) oxychloride, cerium (III) oxytartanate, cerium (III) oxide, oxysulfuric acid Diterpenes, cerium (III) bromide, cerium (III) tartrate, cerium (III) hydroxide, cerium oxycarbonate, cerium (III) zirconate, oxynitric acid Barium, strontium tetratitanate (III), barium (III) barium titanate, barium (III) fluoride, barium (III) molybdate, barium (III) iodide, barium (III) nitrate, barium chloride (III) ), cerium (III) sulfate, cerium (III) acetate, cerium (III) phosphate, etc.; cerium chloride (V), cerium oxide (V), cerium bromide (V), citric acid, hexamidine Potassium acid, bismuth citrate, sodium metasilicate, lithium metasilicate, strontium iodide (V), pyruvate oxime oxime, hexamic acid, ammonium hexanoate, potassium hexafluoroantimonate, etc. Salt or the like; Capric acid, ammonium bismuth citrate, potassium metasilicate, sodium metasilicate, cerium (IV) iodide, potassium citrate, sodium citrate, sulfonic acid, potassium citrate, sodium citrate, citrate钡, lithium niobium hydride, ruthenium (IV) chloride, ruthenium (IV) oxide, ruthenium (IV) bromide, ruthenium hydroxide, antimony trioxide, zinc ruthenium or the like, or ruthenium salt; Indium (III) (acetyl) pyruvate, indium (III) amide, indium dichloride, indium (I) chloride, indium (III) chloride, indium (III) acetate, indium bromide ( III), indium (III) iodide, indium (III) nitrate, indium (III) sulfate, indium (III) fluoride, indium (III) oxide, indium (III) hydroxide, etc.; Mercaptopyruvate) bismuth (II) dihydrate, bismuth selenite, bismuth citrate, bismuth benzoate, strontium aluminate, strontium chloride, cesium formate, bismuth citrate, strontium oxide, strontium bromide, bismuth oxalate , barium tartrate, barium metadylate, barium hydroxide, barium metasilicate, barium tungstate, barium metasilicate, barium metasilicate, barium lactate, barium metaborate, barium molybdate, barium iodide, barium hydrogen phosphate , barium carbonate, barium fluoride, etc.; barium (ethionyl pyruvate) barium (IV), barium chloride (IV), barium oxide (IV), Antimony (IV), barium sulfate (IV), barium nitrate (IV), barium oxymethane (IV), fluoroantimonic acid, fluoroantimonate, barium fluoride, etc. or barium salts; Potassium acid, potassium hydrogen selenite, trihydroanthracene selenite, sodium hydrogen selenite, lithium hydrogen selenite, copper (II) selenite, sodium selenite, barium selenite, selenium oxychloride , selenium chloride (I), selenium (IV) chloride, selenium (IV) oxide, aluminum selenate, selenate, zinc selenite, potassium selenate, ammonium selenate, selenium Calcium acid, barium selenate, cobalt selenate, copper (II) selenate, nickel selenate, sodium selenate, selenate sulphate, zinc selenate, etc. or selenite; cerium chloride (III) , cerium (III) carboxylate, cerium (III) acetate, cerium (III) nitrate, cerium (III) oxide, cerium (III) fluoride, cerium (III) hydride, cerium (III) sulfate, etc.; Cerium (II) oxide, strontium oxide (V), bismuth (hydrogen oxalate), strontium hydroxide (V), pyruvate oxime, bismuthic acid, calcium metasilicate, bismuth citrate, hemiplegia Barium salts such as barium acid, magnesium metasilicate, lithium metasilicate, ammonium metamonate, sodium metasilicate, barium pentachloride, etc. or barium salts; copper (II) sulfate and copper benzoate ( II), tetraammine copper (II) nitrate, copper (II) citrate, copper (I), copper (I) bromide, copper (II) oxalate, copper (II) formate, copper (II) acetate, Copper (II) propionate, copper (II) oxalate, copper (II) gluconate, copper (II) tartrate, copper (II) chloride, copper (II) bromide, copper (II) hydroxide, copper acetate (II), copper (II) nitrate, copper (II) sulfate, copper (II) carbonate, copper (II) oxide, copper (II) hydroxy nitrate, copper (II) tungstate, copper (II) carbonate, Copper (II) lactate, copper fluoride (II), copper salt of copper (I) or the like; ginseng (III), cerium (III) chloride, cerium (III) carboxylic acid, cerium (III) citrate, acetic acid钇(III), cerium (III) oxide, cerium (III) oxalate, cerium (III) nitrate, cerium (III) carbonate, cerium (III) fluoride, cerium (III) hydride, cerium (III) sulfate, phosphoric acid钇(III), etc. 钇 salt; ginsengyl pyruvate, ruthenium (III), ruthenium (III) chloride, Barium (III), barium (III) acetate, barium (III) oxide, barium (III) oxalate, barium (III) nitrate, barium (III) carbonate, barium (III) fluoride, barium (III) barium titanate , barium salt of cerium (III) sulfate, cerium (III) phosphate, cerium (III) hydride, etc.: ginseng (III), cerium (III) chloride, cerium (III) , cerium (III) acetate, cerium (III) oxide, cerium (III) bromide, cerium (III) oxalate, cerium (III) nitrate, cerium (III) carbonate, cerium (III) dititanate, cerium fluoride ( III), cerium salt of cerium (III) iodide, cerium (III) sulfate, cerium (III) phosphate, and the like. These compounds may be anhydrous or hydrated. Further, these may be used alone or in combination of two or more. Further, it may be dissolved in the aqueous metal surface treatment solvent or may be dispersed.

The total amount of the content of the crosslinkable compound (B) selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) (B=B1+B2), relative to the water system The total solid content contained in the metal surface treatment agent is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 90% by mass, even more 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-treated film obtained by the aqueous metal treating agent and the durability of the chemical-resistant film are further improved.

(solvent)

The water-based metal surface treatment agent of the present invention contains various solvents as needed in order to improve the workability when applied to the surface of the metal material.

Examples of the solvent include water; an alkane solvent such as hexane or pentane; an aromatic solvent such as benzene or toluene; an alcohol solvent such as ethanol, 1-butanol or ethyl cellosolve; tetrahydrofuran or dioxane; An ether solvent such as an ester solvent such as ethyl acetate or butoxyethyl acetate; a guanamine solvent such as dimethylformamide or N-methylpyrrolidone; An oxime-based solvent; a guanidinium phosphate-based solvent such as hexamethylenephosphoric acid triamide or the like. These solvents may be used alone or in combination of two or more. Among them, water is preferred for environmentally and economically advantageous reasons.

(other additives)

The aqueous metal surface treatment agent of the present invention may contain a surfactant, an antifoaming agent, a leveling agent, an antibacterial fungicide, a coloring agent, etc., within a range not impairing the taste of the present invention and the film properties.

(Modulation method of water metal surface treatment agent)

The method for producing the aqueous metal surface treatment agent of the present invention is not particularly limited. For example, the polyvinyl alcohol-based compound (A) and the crosslinkable compound (B) can be prepared by mixing with any additives and any solvent contained therein, and mixing them sufficiently using a mixer such as a mixer.

[metallic material]

As shown in Fig. 1, the metal material 10 of the present invention has a base metal 1 and a surface treatment film 2 formed by applying the aqueous metal surface treatment agent of the present invention to the surface thereof. "Coating" means by the coating step described later The surface of the base metal 1 is coated with a water-based metal surface treatment agent. "Yes" means that the base metal 1 and the surface treatment film 2 may have other configurations. For example, the resin film 3 formed by lamination processing on the surface treatment film 2 may be provided. Since the surface-treated film 2 is formed by applying the aqueous metal surface treatment agent of the present invention to the base metal 1, the adhesion and the adhesion resistance of the drug are excellent.

Since the metal material 10 has such a surface treatment film 2, even after the resin film 3 or the resin coating film 3 is formed on the surface treatment film 2, it is subjected to severe drawing such as deep drawing, stretching, or drawing. Further, even if it is further exposed to an acid or the like, the resin film 3 or the resin coating film 3 can be prevented from being peeled off from the metal material 10.

In addition, although the surface treatment film 2 and the resin film 3 or the resin coating film 3 are formed on the surface of one side of the base metal 1 in FIG. 1, it is good also on the both surfaces of the base metal 1, that is, another The surface treatment film 2 is also formed on the surface of one side, and further, the resin film 3 or the resin coating film 3 is provided.

The type of the base metal 1 is not particularly limited and can be applied to various types. For example, it can be applied to a metal material such as a main body or a lid material for a food can, a food container, a dry battery container, or a battery exterior material, but is not limited thereto, and a metal material which can be used for a wide range of applications can be used. . In particular, a lithium ion battery that can be used as a mobile lithium ion battery for use in a mobile phone, an electronic notebook, a notebook computer, or a video camera, and a lithium ion battery that is used as a driving power of an electric vehicle or a hybrid electric vehicle can be cited. Metal material for external materials. Among these metal materials, it is preferable to use a surface treatment film formed on the surface thereof, and to further coat the surface layer of the surface film. A metal material such as a resin film or the like which can be subjected to severe forming processing such as deep drawing, stretching, or drawing and drawing processing.

Examples of such a metal material include copper materials such as pure copper and copper alloy; aluminum materials such as pure aluminum and aluminum alloy; iron materials such as ordinary steel and alloy steel; and nickel materials such as pure nickel and nickel alloy.

As the copper alloy, it is preferable to contain 50% by mass or more of copper, and for example, brass or the like can be used. Examples of the alloy component other than copper in the copper alloy include Zn, P, Al, Fe, Ni, and the like. As the aluminum alloy, those containing 50% by mass or more of aluminum are preferable, and for example, an Al-Mg-based alloy or the like can be used. Examples of the alloy component other than aluminum in the aluminum alloy include Si, Fe, Cu, Mn, Cr, Zn, Ti, and the like. As the alloy steel, those containing 50% by mass or more of iron are preferable, and for example, stainless steel or the like can be used. Examples of the alloy component other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr, Mo, and the like. As the nickel alloy, those containing 50% by mass or more of nickel are preferable, and for example, a Ni-P alloy or the like can be used. Examples of the alloy component 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 on the surface of a metal material, a ceramic material or an organic material other than the above-mentioned metal material to form a film containing the above metal element. Such a metal film can be formed, for example, by a method such as plating, vapor deposition, or coating. Further, the shape, structure, and the like of the base metal 1 are not particularly limited, and for example, a plate-shaped or foil-shaped metal material can be used.

As described above, the aqueous metal surface treatment agent according to the present invention contains the above polyvinyl alcohol compound (A) and the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2). It Since one type or two or more types of cross-linking compound (B) are obtained, the surface-treated film obtained by treating with the aqueous metal surface treatment agent has high adhesion, and can maintain high adhesion even when exposed to an acid or the like. As a result, even if a resin film is laminated on the metal material on which the surface treatment film is formed or a resin coating film is formed, and then subjected to severe drawing processing such as deep drawing processing, stretching processing, or stretching drawing processing, even if exposed It is also possible to prevent the laminated film or the resin coating film from being peeled off from the metal material in an acid or an organic solvent or the like.

[Surface treatment method]

A method of treating a metal surface using a water-based metal surface treatment agent by applying a water-based metal surface treatment agent to a surface of a substrate metal; and drying the surface without a water washing after the coating step to form a surface It is formed by treating the drying step of the film.

(coating step)

The coating step is a step of applying an aqueous metal surface treatment agent to the surface of the base metal. The coating method is not particularly limited, and for example, a spray coating, dip coating, roll coating, curtain coating, spin coating, or a combination thereof may be used. The conditions of use of the aqueous metal surface treatment agent are not particularly limited. For example, the temperature of the water-based metal surface treatment agent and the metal material at the time of coating is preferably from 10 ° C to 90 ° C, more preferably from 20 ° C to 60 ° C. When the temperature is 60 ° C or less, excessive energy use can be suppressed. Further, the coating time and the coating amount can be appropriately set in accordance with the film thickness required for the obtained surface treatment film.

(drying step)

The drying step is a step of drying the surface after the coating step without water washing to form a surface-treated film. The drying temperature can be set to match the temperature of the solvent used. For example, when water is used as the solvent, it is preferably in the range of 50 ° C to 260 ° C. Although the drying apparatus is not particularly limited, an electromagnetic induction heating furnace using a batch type, a continuous type or a hot air circulation type drying furnace, a conveying type hot air drying furnace or an IH heater can be used, and the air volume and the wind speed can be arbitrarily set. .

Even if a resin film (laminated film) or a resin coating film is further formed thereon, the surface-treated film thus obtained is subjected to a severe forming process such as deep drawing, stretching, or drawing, and further, even further It is also possible to prevent peeling of the resin film composed of the laminated film or the resin coating film by exposure to an acid or the like.

Further, the film thickness of the obtained surface treated film is preferably from 0.01 μm to 1 μm, more preferably from 0.02 μm to 0.05 μm. By setting the film thickness to this range, the adhesion of the surface treatment film and the adhesion resistance of the drug can be further improved.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples and comparative examples. The invention is not limited by the following examples. In the following, the "parts" are "mass parts" and "% by mass" are synonymous with "% by weight". Unless otherwise specified, the following is also indicated as "%". "ppm" is synonymous with "mg/L".

[Polyvinyl alcohol compound (A)]

The polyvinyl alcohol-based compound (A) used is as follows.

Aa: saponification degree 96%, viscosity 25mPa. S polyvinyl alcohol

Ab: saponification degree 99%, viscosity 12mPa. S, ethyl acetonitrile, hexamethylene thiolated polyvinyl alcohol

[Crosslinking Compound (B)] (crosslinkable organic compound (B1))

Glycerol polyglycidyl ether (3-functional, epoxy equivalent 144, viscosity 170 mPa.S) was used as the organic compound (B1a) having a glycidyl ether group. Further, a hexamethylene diisocyanate-acetonitrile ethyl acetate block was used as the organic compound (B1b) having an isocyanate group. Further, methylol melamine was used as an organic compound having a methylol group (symbol B1c). Further, glyoxal is used as the organic compound (B1d) having an aldehyde group.

(crosslinkable inorganic compound (B2))

The crosslinkable inorganic compound (B2) used is as follows.

B2a: titanium hydrofluoric acid (concentration 40.0% by mass)

B2b: zirconium hydrofluoric acid (concentration 40.0% by mass)

B2c: cerium oxide sol (surface charge cation, particle diameter 10-20 nm, 19.0 mass%, pH=4.7)

B2d: titanium lactate (concentration 44.0% by mass)

B2e: amorphous zirconia sol (nonvolatile content concentration 10.0 mass %, particle diameter 10~30nm, pH=2.8)

B2f: hydrazine hydrofluoric acid (concentration 40.0% by mass)

B2g: chromium (III) fluoride (Cr concentration 1.0% by mass)

B2h: iron (III) fluoride (Fe concentration: 2.5% by mass)

B2i: Selenium oxide (IV)

B2j: cerium oxide sol (nonvolatile content 15%, pH=3.5)

B2k: chromium (III) acetate

[Water metal surface treatment agent]

The polyvinyl alcohol-based compound Aa and/or Ab and one or more selected from the crosslinkable organic compounds B1a to B1d and the crosslinkable inorganic compounds B2a to B2g are combined at a predetermined content, and water is used as a solvent. The aqueous metal surface treatment agents of Examples 1 to 41 and Comparative Examples 1 to 18 shown in Tables 1 to 3 were prepared. In addition, the "concentration" in Tables 1 to 3 indicates the concentration (% by mass) of the nonvolatile component of each compound contained in the aqueous metal surface treatment agent. In addition, the "A concentration" means the total content (% by mass) of the polyvinyl alcohol-based compound (A) with respect to all the solid components in the aqueous metal surface treatment agent, and the "B1 + B2 concentration" means the relative to the aqueous metal. The content of the crosslinkable compound (B) of all the solid components in the surface treatment agent is the total content (% by mass) of the crosslinkable organic compound B1 and the crosslinkable inorganic compound B2.

[metallic material]

The metal material used as the base metal is as follows.

Al: A1100P, thickness 0.3mm

Cu: C1020P, thickness 0.3mm

Ni: pure nickel plate: (purity of 99% by mass or more), thickness of 0.3 mm

SUS: SUS304 plate, thickness 0.3mm

Ni-plated Cu: Cu plated with Ni (thickness 0.3 mm, Ni plating thickness 2 μm)

The metal materials shown in the "substrate" column of Tables 1 to 3 were selected from the metal materials, and the base metals of Examples 1 to 41 and Comparative Examples 1 to 22 were prepared.

[Manufacture of test materials] (surface treatment)

The base metals of Examples 1 to 41 and Comparative Examples 1 to 18 shown in Tables 1 to 3 were sprayed at 5% aqueous solution of FINE CLEANER 359E (alkaline degreaser manufactured by Nippon Parkerizing Co., Ltd.) at 65 ° C. After 1 minute by degreasing, wash with water to clean the surface. Next, in order to evaporate the water on the surface of the metal material, it was dried by heating at 80 ° C for 1 minute. On the surface of the base metal which was degreased and washed, the water-based metal surface treatments of Examples 1 to 41 and Comparative Examples 1 to 18 shown in Tables 1 to 3 were respectively applied by bar coating using #3SUS Mayer bar. The agent (coating step) was dried in a hot air circulating type drying oven at 200 ° C for 1 minute (drying step) to obtain a metal material having a surface-treated film. Further, two metal materials which were surface-treated with the same aqueous metal surface treatment agent were prepared, and the lamination processing was applied to the surface treatment film by a different method as described below.

Further, the metal materials described in Comparative Examples 19 to 22 were prepared, and the water-based metal surface treatment agent was applied, and the mixture was degreased, washed with water, and dried by heating, to obtain a metal material having no surface-treated film. Further, two metal materials of the same kind were prepared, and lamination processing was applied to the surface in different ways as shown below.

(lamination processing)

One of the two metal materials having the surface-treated coatings prepared thereon was subjected to a lamination process of thermal lamination on the surface-treated coating. Another The outer surface of the outer surface treatment film is subjected to a lamination process of dry lamination. For the metal material which does not have the surface treatment film, one of the two side surfaces is also thermally laminated, and the other one side surface is subjected to dry lamination.

The lamination processing of the thermal lamination is carried out as follows. Using a #8SUS Mayer bar, a dispersion of acid-modified polypropylene ("R120K", a nonvolatile content of 20% by mass) manufactured by a bar coating was applied to the hot air circulating drying furnace. The inside was dried at 200 ° C for 1 minute to form an adhesive layer. Thereafter, this adhesive layer and a polypropylene film ("CPPS" manufactured by Tohcello Co., Ltd.) having a thickness of 30 μm were thermocompression bonded at 190 ° C and 2 MPa for 10 minutes, thereby performing lamination processing by thermal lamination to obtain a layer. A metal material combined with a polypropylene film.

The lamination processing of the dry lamination is carried out as follows. Using a #8SUS Mayer bar, a urethane-based dry laminating adhesive ("AD-503/CAT10", manufactured by Toyo Morton Co., Ltd., nonvolatile content: 25% by mass) was applied by bar coating. After drying at 80 ° C for 1 minute in a hot air circulating drying oven, the adhesive layer and the 30 μm unstretched polypropylene film ("FCZX" manufactured by Nakamura Chemical Co., Ltd.) were subjected to a corona discharge treatment surface. After crimping at 100 ° C and 1 MPa, the film was cured at 40 ° C for 4 days, thereby performing a lamination process of dry lamination to obtain a metal material in which a polypropylene film was laminated.

(forming processing)

a polypropylene film laminated metal material obtained by thermal lamination, and a polypropylene film laminated metal material obtained by dry lamination, respectively The stretching test is carried out for deep drawing. The coated metal sheet having a diameter of 160 mm was subjected to drawing (first time) to produce a cup having a diameter of 100 mm. Next, 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 produce a can for the test material. In addition, the ironing rate (thinning fraction) in the first drawing process, the second drawing process, and the third drawing process is 5%, 15%, and 15%, respectively. .

[Performance Evaluation] (adhesion)

The presence or absence of peeling of the polypropylene film (hereinafter referred to as "initial adhesion") was evaluated for the can after the forming process. In the case where the can was produced, the film was peeled off without peeling of the film, and the initial adhesion was 3 minutes, the peeling of the film was 2 minutes, and the film peeling was 1 minute. The results of the evaluation test are shown in Tables 4 and 5.

(drug tightness maintenance)

In the adhesion durability maintenance, the adhesion retention property to the electrolyte solution (hereinafter referred to as "electrolyte adhesion retention resistance") is evaluated. Specifically, the presence or absence of peeling of the polypropylene film was evaluated in a can after the molding process was further immersed in the electrolytic solution.

The deep-drawn can is immersed in an electrolyte solution for lithium ion battery (electrolyte; 1 mol/L of LiPF6, solvent; EC:DMC:DEC=1:1:) filled with 1000 ppm of ion-exchanged water filled in a sealed container. 1 After (vol%)), it was placed in a thermostat at 60 ° C for 7 days. Further, "EC" is ethyl carbonate, "DMC" is dimethyl carbonate, and "DEC" is diethyl carbonate.

Thereafter, the test piece was taken out, immersed in ion-exchanged water for 1 minute, washed by shaking, and then dried in a hot air circulating type drying oven at 100 ° C for 10 minutes. Then, the film surface was grasped by the tip of the tweezers, and it was evaluated as 3 points without peeling of the film and excellent durability of the electrolyte solution adhesion resistance, 2 points for one part of the film peeling, and 1 point for the film peeling. The results of the evaluation test are shown in Tables 4 and 5.

As shown in Table 4 and Table 5, it was confirmed that the metal material having the surface-treated film formed by applying the aqueous metal surface treatment agents described in Examples 1 to 41 has excellent initial adhesion and electrolyte solution adhesion retention. excellent.

1‧‧‧Substrate metal

2‧‧‧Surface treatment film

3‧‧‧Resin film (laminated film) or resin film

10‧‧‧Metal materials with surface treated film

Fig. 1 is a schematic cross-sectional view showing an example of a metal material having a surface-treated film formed by applying the aqueous metal surface treatment agent of the present invention.

Claims (5)

An aqueous metal surface treatment agent for treating a surface of a metal material to form a surface treatment film for a substrate for a laminate film or a resin coating film, comprising: a polyvinyl alcohol compound (A); a crosslinkable organic compound (B1) capable of reacting with the polyvinyl alcohol-based compound (A) and a crosslinkable inorganic compound (B2) containing an element capable of reacting with the polyvinyl alcohol-based compound (A) One or two or more kinds of crosslinkable compounds (B) are selected, and the crosslinkable organic compound (B1) has one or more selected from the group consisting of a glycidyl ether group, an isocyanate group, a methylol group, and an aldehyde group. The functional group, the crosslinkable inorganic compound (B2) contains Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, One or two or more elements selected from the group consisting of Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La. The water-based metal surface treatment agent according to the first aspect of the invention, wherein the content of the polyvinyl alcohol-based compound (A) is from 10% by mass to 90% by mass based on the total solid content of the aqueous metal surface treatment agent. The total amount (B=B1+B2) of the content of the crosslinkable compound (B) selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) is relative to The total solid content contained in the aqueous metal surface treatment agent is from 10% by mass to 90% by mass. The aqueous metal surface treatment agent according to claim 1 or 2, which comprises both the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2). An aqueous metal surface treatment agent according to claim 1 or 2, which does not contain a vanadium compound. A metal material characterized by having a surface treatment film formed by applying an aqueous metal surface treatment agent according to any one of claims 1 to 4 to a surface of a metal material.