KR101610428B1 - Metal-surface treatment agent and metal material - Google Patents

Abstract

(Problem) Even when a resin film is laminated on the surface of a metal material or a resin coating film is formed and then a strong forming process such as a deep drawing process is performed, high adhesion such that the laminate film or the resin coating film is not peeled The present invention provides a metal surface treatment agent for forming a surface treatment film which can be used as a surface treatment agent.
(A) a Zr compound that releases a zirconyl ion (ZrO ²⁺ ) in an aqueous solution, and a Ti compound that releases a titanyl ion (TiO ²⁺ ) in an aqueous solution, And an organic compound (b) having at least two functional groups in the same molecule selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group and a sulfonic acid group in the same molecule . It is preferable that the organic compound (b) has a molecular weight of 100 or more and 1000 or less, and the organic compound (b) has one functional group per 30 to 300 molecular weight.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal surface treatment agent and a metal material obtained by treating the metal surface treatment agent with the treatment agent.

The present invention relates to a metal surface treatment agent for forming a surface treatment film excellent in adhesion property and adhesion holding property of a metal material and a laminate film or a resin coating film which can prevent peeling off of the metal material and the resin coating film and a metal material treated with the metal surface treatment agent will be. Specifically, even when a resin film is laminated to a metal material or a resin coating film is formed and rigid molding processing such as deep drawing processing, ironing processing or stretch drawing processing is performed thereafter, the laminate film or the like is not peeled off And a metal surface treatment agent for forming a surface treatment film excellent in adhesion and retention of chemical agents which can maintain high adhesiveness even when exposed to acids, organic solvents and the like.

Lamination is a processing means for heating and pressing a resin film (hereinafter referred to as "resin film" or "laminate film") onto the surface of a metal material (hereinafter simply referred to as "metal surface" Or a method of coating a metal surface for the purpose of imparting decorative properties to the metal surface. This laminating process generates less waste gas or warming gas such as solvent, carbon dioxide, or the like that occurs during drying, as compared with a method in which the resin composition is dissolved or dispersed in a solvent to form a resin coating film by coating and drying on a metal surface. Therefore, the present invention is preferably applied in terms of environmental preservation, and its application is expanded, for example, the body or lid material of a food can using aluminum foil, steel thin plate, aluminum foil or stainless steel foil for packaging, Containers, or battery containers.

In recent years, a metal foil such as an aluminum foil or a stainless steel foil having a light weight and high barrier properties is preferably used as a jacket material and a tab lead material for a mobile lithium ion secondary battery used in a mobile phone, an electronic notebook, a notebook computer, And the surface of such metal foil is subjected to lamination. In addition, a lithium ion secondary battery has been studied as driving energy for an electric automobile or a hybrid automobile, but a metal foil that has been laminated is also considered as its exterior material.

The laminate film to be used for such laminate processing is directly bonded to a metal material, followed by hot pressing. Therefore, compared to a general resin coating film formed by applying and drying a resin composition, waste of raw materials can be suppressed, pinholes (defective portions) are reduced, and workability is excellent. As a material of the laminate film, generally, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and polyolefins such as polyethylene and polypropylene are used.

There is a problem in that when the laminate is subjected to a laminating process without a chemical treatment or the like on the metal surface, the laminate film peels off from the metal surface or corrosion occurs in the metal material. For example, in the case of a food container or a wrapping material, a heat treatment for sterilization is carried out after putting the contents into a container or a post-processed laminate, and the laminated film may peel off from the metal surface during the heat treatment . In the case of the outer sheath of the lithium ion secondary battery, a high degree of processing is performed in the manufacturing process. In addition, when used for a long period of time, moisture in the atmosphere penetrates into the container, which reacts with the electrolyte to form hydrofluoric acid, which permeates the laminate film to cause peeling of the metal surface and the laminate film, There is a problem.

In order to improve the adhesion between the laminate film and the metal surface and the corrosion resistance of the metal surface when the laminate film is laminated to the metal surface, a chemical treatment such as phosphoric acid chromate or the like . However, such a chemical treatment requires a cleaning step for removing surplus treatment liquid after the treatment, and the wastewater treatment of the washing water discharged from the cleaning step requires a cost. Particularly, the chemical treatment such as phosphoric acid chromate tends to be away from the recent environmental consideration because a treatment liquid containing hexavalent chromium is used.

For example, Patent Document 1 proposes a ground 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. In Patent Document 2, 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 has been proposed. 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.

Japanese Patent Application Laid-Open No. 2002-265821 Japanese Patent Application Laid-Open No. 2003-313680 Japanese Patent Application Laid-Open No. 2003-138382 Japanese Patent Application Laid-Open No. 2004-262143

It is an object of the present invention to provide a laminated film or resin laminated film or laminated film which can be used as a laminated film or a laminate film even when a resin film is laminated on the surface of a metal material or a resin coating film is formed thereon and then a strong forming process such as deep drawing, There is provided a metal surface treatment agent for forming a surface treatment film capable of imparting high adhesiveness without peeling of a coating film and a metal material treated with the metal surface treatment agent

The metal surface treatment agent according to the present invention for solving the above-mentioned problems is a Zr compound releasing zirconyl ion (ZrO ²⁺ ) in an aqueous solution and a Zr compound releasing a titanyl ion (TiO ²⁺ ) (B) an organic compound having two or more quaternary transition metal compounds (a) and at least one functional group selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group and a sulfonic acid group in the same molecule .

According to the present invention, the Group 4 transition metal compound (a) contained in the metal surface treatment agent is an oxide of a metal such as zirconium ion (ZrO ²⁺ ) or titanyl ion (TiO ²⁺ ) Metal ions react strongly with metal surfaces and are strongly adsorbed to metal surfaces. When moisture is removed by subsequent heating and drying or the like, a zirconium ion (ZrO ²⁺ ) bond by a condensation reaction, a titanyl ion (TiO ²⁺ ) bond by a condensation reaction, or a zirconium ion ²⁺ ) and titanyl ion (TiO ²⁺ ) is formed by a condensation reaction. As a result, by using the metal surface treatment agent of the present invention, it is possible to form a strong surface treatment film which gives high adhesion to the metal surface.

The organic compound (b) contained in the metal surface treatment agent is preferably a salt of an oxymetal ion such as zirconium ion (ZrO ²⁺ ) or titanyl ion (TiO ²⁺ ) released from the quaternary transition metal compound (a) Or a complex salt, so that the stability of the oxy metal ion is improved. Further, when moisture is removed by heat drying or the like after the metal surface treatment agent is coated on the metal surface, the organic compound (b) is strongly bound to Zr or Ti, thereby improving the film composition of the coating.

In the metal surface treatment agent according to the present invention, it is preferable that the organic compound (b) has a molecular weight of 100 or more and 1000 or less, and the organic compound (b) is a compound having one functional group per 30 to 300 molecular weight , And excellent adhesion can be realized.

In the metal surface treatment agent according to the present invention, the ratio [Mb / Ma] of the mass (Mb) of the organic compound (b) to the mass (Ma) of the metal in the quaternary transition metal compound Is preferable, and excellent adhesion can be realized.

In the metal surface treatment agent according to the present invention, it is preferable that one or two or more nonionic or anionic types selected from urethane resin, epoxy resin, acrylic resin, phenol resin, polyester resin, polyvinyl resin and polyolefin resin Based resin (c), and it is possible to impart flexibility and an additional film-forming composition to the obtained surface-treated coating film.

The metal surface treatment agent according to the present invention preferably contains a metal compound (d) having one or more metal elements selected from Zr, Ti, V, Mo, W, Ce and Nb, As a bitter, it is effective to further improve the corrosion resistance.

The metal material according to the present invention for solving the above problems is characterized by having a surface treatment film formed by applying the surface treatment agent according to the present invention to a metal surface.

According to the present invention, since the surface treatment film formed by applying the metal surface treatment agent according to the present invention to the surface of the metal material is laminated, a resin film is further laminated on the surface treatment film or a resin film is formed on the surface treatment film. It is possible to prevent the laminated film or the resin coating film from being peeled off from the metal material even when strong forming processing such as deep drawing processing, ironing processing or stretch drawing processing is performed thereafter. Further, even when exposed to an acid or the like, the laminated film or resin coated film can be prevented from being peeled off from the metal material.

According to the metal surface treatment agent and the metal material treated with the treatment agent according to the present invention, the adhesion between the surface of the metal material and the obtained surface treated film and the adhesion between the laminated film and the obtained surface treated film are both increased And even when exposed to an acid or the like, high adhesion can be maintained. As a result, even when the resin film is laminated to the metal material on which the surface-treated film is formed or after the resin film is formed, strong molding such as deep drawing, ironing or stretch drawing is carried out, It is possible to prevent the laminate film or the resin coating film from being peeled off from the metal material even when exposed to a solvent or the like. Particularly, excellent adhesion can be maintained even in a corrosive environment in a retort treatment or an electrolytic solution immersion.

1 is a schematic cross-sectional view showing an embodiment of a surface treatment film according to the present invention.

Hereinafter, the metal surface treatment agent according to the present invention and the metal material treated with the treatment agent will be described. The technical scope of the present invention is not limited by the following description and drawings.

[Metal surface treatment agent]

As shown in Fig. 1, the metal surface treatment agent according to the present invention is formed by laminating a laminate film or a resin coating film 3 on the surface of a metal material 1 (hereinafter referred to as "base metal 1" Is a treating agent for forming the surface treatment film (2) for grounding. It is characterized in that a Zr compound that releases zirconyl ion (ZrO ²⁺ ) in an aqueous solution and one or more quaternary transition metal compounds (a) selected from a Ti compound that releases titanyl ion (TiO ²⁺ ) (B) having at least two functional groups selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group and a sulfonic acid group in the same molecule.

Means that the metal surface treatment agent may contain a compound other than the above-mentioned four-group transition metal compound (a) and the organic compound (b). Examples of such a compound include a surfactant, a defoaming agent, a leveling agent, an antiseptic agent, a colorant, and the like. These compounds may be contained within the range that does not impair the object of the present invention and the coating performance. The base metal 1 to be subjected to the surface treatment will be described later.

Hereinafter, each component will be described in detail.

(Group 4 transition metal compound)

The quaternary transition metal compound (a) is a zirconium compound which releases Zirconium ion (ZrO ²⁺ ) in an aqueous solution, and at least one compound selected from a Ti compound releasing titanyl ion (TiO ²⁺ ) in an aqueous solution to be. When the metal surface treating agent is applied to the surface of the base metal 1 (also referred to as a "metal surface"), the four-group transition metal compound (a) is a zirconium ion (ZrO ^{2 +} ) or a titanyl ion (TiO ^{2 +} ) Are strongly adsorbed on the metal surface by reacting with the metal surface. The adsorbed oxymetal ion can be removed by condensation reaction between zirconyl ion (ZrO ^{2 +} ) and condensation reaction between titanyl ion (TiO ^{2 +} ) when the moisture is removed by subsequent heating and drying or the like. , Or a bond formed by a condensation reaction between a zirconyl ion (ZrO ²⁺ ) and a titanyl ion (TiO ²⁺ ). As a result, it is possible to form a strong surface-treated coating which gives high adhesion to the metal surface by the bonding.

The zirconium compound is not particularly limited as long as it is a compound capable of releasing zirconyl ion (ZrO ²⁺ ) when dissolved in water. In such a zirconium compound is, for example, a basic carbonate, zirconyl _{(Zr 2 (CO 3) (} OH) 2 O 2), the basic chloride, zirconyl (ZrO (OH) Cl), acid zirconyl ammonium ((NH _{4) 2} ZrO (CO _{3) 2),} acid zirconyl potassium _{(K 2 ZrO (CO 3)} 2 K 2), acid zirconyl sodium _{(Na 2 ZrO (CO 3)} 2 K 2), zirconyl nitrate (ZrO (NO ₃ ) _2), acid zirconyl (ZrO (CH ₃ COO) _2), sulfate, zirconyl (ZrOSO _4), dihydrogen phosphate zirconyl (ZrO (H ₂ PO _{4) 2),} stearic acid zirconyl (ZrO (C ₁₈ H ₃₅ O ₂ ) ₂ ) and the like.

The titanium compound is not particularly limited as long as it is a compound capable of releasing titanyl ion (TiO ²⁺ ) in an aqueous solution. Examples of such titanium compounds include titanium ammonium oxalate 2 oxalate ((NH ₄ ) ₂ [Ti (C ₂ O ₄ ) ₂ O] .nH ₂ O), titanyl sulfate (TiOSO ₄ ), diisopropoxy there may be mentioned titanium bis acetylacetone _{(Ti (OiC 3 H 7)} 2 (C 5 H 7 O 2) 2), and titanium lactate _{(Ti (OH) 2 [OCH} (CH 3) COOH] 2) and so on.

The zirconium compound and the titanium compound may be contained individually or both in the metal surface treatment agent. The content of the compound contained in the metal surface treatment agent is preferably from 0.001% by mass to 70% by mass, more preferably from 0.01% by mass to 50% by mass, in the case where the zirconium compound and the titanium compound are contained singly. By setting the content to 0.001 mass% to 70 mass%, it is possible to further improve the adhesiveness of the obtained surface treated film and the maintenance of adhesion of the chemical agent.

The reason why the surface treated film is formed of a metal surface treating agent in which a titanium compound is blended in a treating agent based on a zirconium compound is not clear but can bring about higher adhesion. The compounding ratio of both of the zirconium compound and the titanium compound in the metal surface treatment agent is preferably 0.005 to 1 in terms of the metal mass ratio in the compound [titanium mass in the titanium compound: Mat] / [zirconium mass in the zirconium compound: Maz] , And more preferably 0.01 to 0.43. A metal surface treatment agent compounded in such a range of metal mass ratio [Mat / Maz] can form a surface treatment film exhibiting higher adhesion.

(Organic compound)

The organic compound (b) is a compound having at least two functional groups selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group and a sulfonic acid group in the same molecule. The organic compound (b) acts on an oxymetal ion such as a zirconium ion (ZrO ²⁺ ) and / or a titanyl ion (TiO ²⁺ ) emitted from the above-mentioned quaternary transition metal compound (a) Or complexes. The water-soluble salt or complex salt thus formed has an effect of enhancing the stability of the oxy metal ion. Therefore, it is possible to stably maintain the above-described effect of the oxy metal ion and to provide a strong surface treatment film Can be stably formed. When moisture is removed by heat drying or the like after the metal surface treatment agent is coated on the metal surface, the organic compound (b) is strongly bonded to Zr and / or Ti constituting the oxy metal ion, There is an effect of improving the film-forming composition of the coating film.

The functional group of the organic compound (b) is any of a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group and a sulfonic acid group, and these functional groups have two or more functional groups in the same molecule of the organic compound (b). Two or more, three, four, or more. The upper limit of the number is not particularly limited, but may be 10, for example. The two or more functional groups may be of the same kind selected from the above-mentioned hydroxyl group, carboxyl group, phosphonic acid group, phosphoric acid group and sulfonic acid group, or may be of different kinds.

The molecular weight of the organic compound (b) is preferably 100 or more and 1000 or less, more preferably 100 or more and 900 or less. The organic compound (b) having a molecular weight within this range has functional groups at a ratio of one to 30 to 300 in molecular weight. The other chemical structures of the organic compound (b) are not particularly limited.

Specific examples of the organic compound (b) include, for example, ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, dibutylene glycol, glycerin, pentaerythritol, catechol, pyrogallol, catechin, Polyhydric hydroxy compounds such as pullulan; Polyvalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid and maleic acid; Hydroxycarboxylic acids such as glycolic acid, lactic acid, glyceric acid, tartronic acid, tartaric acid, malic acid, citric acid, pantoic acid, ascorbic acid, salicylic acid, protocatechiacarbic acid, gallic acid and mandelic acid; 1-hydroxyethyl-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetra (methylenephosphonic acid) (Methylenephosphonic acid), diethylenetriamine-N, N, N ', N ", N" -penta (methylenephosphonic acid), 2- Organic phosphonic acids such as phosphonobutane-1,2,4-tricarboxylic acid; Organic phosphoric acids such as phytic acid, phosphoric acid starch and glucose monophosphate; .

The organic compound (b) is coordinated to zirconyl ion (ZrO ^{2 +} ) and / or titanyl ion (TiO ^{2 +} ) released from the aqueous solution of the titanium compound in the zirconium compound released from the aqueous solution, . When the surface treatment film is formed of the metal surface treatment agent, the organic compound (b) is also strongly bonded to the zirconyl ion and / or titanyl ion to improve the film composition. As a result, the corrosion resistance of the surface treated film and the adhesion to the laminated film or the resin coated film formed on the surface treated film are excellent.

The content of the organic compound (b) contained in the metal surface treatment agent is preferably such that the ratio of the mass Mb of the organic compound (b) to the mass Ma of the metal element (Zr and / or Ti) in the quaternary transition metal compound (a) = Mb / Ma] is preferably 0.05 to 0.6, more preferably 0.1 to 0.4. By containing the organic compound (b) and the Group 4 transition metal compound (a) in the range of the mass ratio, the corrosion resistance of the surface treated film and the adhesion to the laminate film or the resin coated film formed on the surface treated film are good do. When the mass ratio [Mb / Ma] is less than 0.05, the film-coated composition of the surface treated film may decrease. When the mass ratio [Mb / Ma] exceeds 0.6, the surface treated film and the laminate film Or the adhesion between the resin coating film may be lowered.

(Water-based resin)

The water-based resin (c) may contain one or more nonionic or anionic organic compounds selected from urethane resins, epoxy resins, acrylic resins, phenol resins, polyester resins, polyvinyl resins and polyolefin resins to be. The organic compound has an anionic group or a non-ionic group, and can be stably present in the metal surface treatment agent of the present invention, and the kind of the organic compound is not limited as long as a desired effect can be obtained. Further, in the form of the aqueous solution of the organic compound, the organic compound may be water-soluble or water-dispersible (emulsion, dispersion).

Examples of the urethane resin include a urethane resin which is an axial polymer of a polyol such as a polyester polyol, a polyether polyol and a polycarbonate polyol and an aliphatic polyisocyanate, an alicyclic isocyanate and / or an aromatic polyisocyanate compound, And polyurethane obtained by using a polyol having a polyoxyethylene chain such as polyethylene glycol or polypropylene glycol. Such a polyurethane can be subjected to a nonionic ionization or moisture oxidation by increasing the introduction ratio of the above-mentioned polyoxyethylene chain.

It is also possible to prepare a urethane prepolymer having an isocyanato group at both ends from a polyisocyanate and a polyol and reacting the urethane prepolymer with a carboxylic acid having two or more hydroxyl groups or a reactive derivative thereof to obtain a derivative having isocyanate groups at both ends And triethanolamine or the like is added thereto to prepare an ionomer (triethanolamine salt). The ionomer is added to water to prepare an emulsion or dispersion, and further, a chain extension is carried out by adding a diamine as required. By doing so, an anionic water-dispersible urethane resin can be obtained.

The carboxylic acid and the reactive derivative used in producing the above water-dispersible urethane resin having an anionic property are used for introducing an acidic group into the urethane resin and for making the urethane resin water-dispersible. As the carboxylic acid to be used, dimethylolalkanoic acid such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolhexanoic acid and the like can be mentioned. Examples of the reactive derivative include hydrolyzable esters such as acid anhydrides.

Examples of the epoxy resin include an epoxy compound having two or more glycidyl groups, an epoxy compound having bisphenol A or bisphenol F as a unit in the skeleton, an epoxy compound having two or more glycidyl groups, and a diamine such as ethylenediamine, A nonionic epoxy resin in which polyethylene glycol is added to the side chain of an epoxy compound having bisphenol A or bisphenol F as a unit in the skeleton or another epoxy compound having two or more glycidyl groups, .

As the epoxy resin, an epoxy resin having bisphenol A or bisphenol F as a unit in the skeleton can be used. A part or all of the glycidyl group of the epoxy resin may be a silane-modified or phosphoric acid-modified epoxy resin.

Examples of the epoxy resin having bisphenol A or bisphenol F as a unit in the skeleton include those obtained by repeating a dehydrochlorination reaction and addition reaction of epichlorohydrin and bisphenol A or bisphenol F, Include those obtained by repeating an addition reaction between two epoxy compounds and bisphenols (A and F).

Examples of the epoxy compound include diglycidyl ether of bisphenol (A, F), diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl ester of terephthalic acid, diglycidyl ester of p-oxybenzoic acid A diglycidyl ester of hexahydrophthalic acid, a diglycidyl ester of succinic acid, a diglycidyl ester of adipic acid, a diglycidyl ester of sebacic acid, a diglycidyl ester of ethylene glycol diglycidyl Diallyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol diglycidyl ether , Trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-glycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane Triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like. These may be used alone or in combination.

The degree of silane modification of the epoxy resin is not particularly limited as far as the effects of these modifications are recognized. The silane modification can be carried out using a well-known silane coupling agent.

Examples of the acrylic resin include a single polymer or copolymer of an acrylic monomer, and a copolymer of an acrylic monomer and an addition polymerizable monomer copolymerizable with the acrylic monomer. Such an acrylic resin is not particularly limited as long as it can stably exist in a surface treatment agent.

Examples of the acrylic monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate Acrylate, methacrylic acid, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate , Glycidyl methacrylate, sulfoethyl acrylate, and polyethylene glycol methacrylate. Examples of the addition-polymerizable monomer copolymerizable with the acrylic monomer include maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, diacetone acrylamide, styrene, acrylonitrile and vinylsulfonic acid.

Examples of the vinyl resin include polyvinyl acetate, partially saponified or fully saponified polyvinyl acetate, and polyvinyl pyrrolidone.

The vinyl acetate may be a saponified polymer obtained by copolymerizing a vinyl acetate copolymerizable monomer. Further, it is also possible to use a modified polymer obtained by introducing an anionic group such as a carboxylic acid, a sulfonic acid, or a phosphoric acid into the polymer after the polymerization, or a modified polymer obtained by introducing an anion group such as a diacetone acrylamide group, an acetacetyl group, a mercapto group, Modified polymer having a functional group introduced thereinto can be applied.

Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid and (meth) acrylic acid and esters thereof; ? -Olefins such as ethylene and propylene; Olefin sulfonic acids such as (meth) acryl sulfonic acid, ethylene sulfonic acid and sulfonic acid maleate; (Meth) allylsulfonate, sodium oleate sulfonate such as sodium ethylene sulfonate, sodium sulfonate (meth) acrylate, sodium sulfonate (monoalkyl maleate), and disulfonic acid sodium alkyl malate; Amide group-containing monomers such as N-methylol acrylamide and acrylamide alkylsulfonic acid alkali salts; N-vinylpyrrolidone, N-vinylpyrrolidone derivatives; And the like.

Examples of the phenol resin include a low molecular weight water-soluble resin or an emulsion resin as a polycondensation product of phenols (phenol, naphthol, bisphenol and the like) and formaldehyde. Of these, resol-type phenol resins having a methylol group having a self-axis synthesis are preferable.

Examples of natural polymers include cellulose, starch, dextrin, inulin, xanthan gum, tamarind gum, tannic acid, and ligninsulfonic acid.

Examples of the polyolefin-based resin include polyolefins obtained by modifying polyolefins such as polypropylene, polyethylene, and propylene or copolymers of ethylene and -olefins with unsaturated carboxylic acids (such as acrylic acid or methacrylic acid), or copolymers of ethylene and acrylic acid (Methacrylic acid). Further, a small amount of other ethylenic unsaturated monomer may be copolymerized. As means for hydration, means for neutralizing the carboxylic acid introduced into the polyolefin resin with ammonia or amines may be mentioned.

These nonionic or anionic aqueous resin (c) is a binder effect due to the film-forming property of the water-based resin (c) itself, and is a binder effect of (1) a surface treatment film formed of a quaternary transition metal compound (2) the reactive functional group of the water-based resin (c) reacts with the Group 4 transition metal compound (a) or the metal compound (b) and is firmly fixed to the surface treated film. Therefore, the metal surface treatment agent containing the water-based resin (c) can form a more robust surface-treated coating capable of enduring strong processing by these effects of the water-based resin (c).

Examples of the nonionic or anionic aqueous resin (c) include aqueous crosslinked resins such as water-soluble resins, aqueous emulsions forcibly emulsified by a self-emulsifying or emulsifying agent, water-based dispersions, or water-based polymer resins. Among them, a crosslinkable resin in which a monomer or oligomer having a number average molecular weight of less than 1000 is polymerized by self-crosslinking by heating, ultraviolet rays, electron beam or the like at the time of forming a film, or a cross- can do. Further, a polymer resin having a number average molecular weight of 1,000 to 1,000,000 and produced by heat or the like may be applied. These polymer resins may be those having a crosslinkable reactive functional group unless the effect of the present invention is impaired.

The content of the aqueous resin (c) contained in the metal surface treatment agent is preferably such that the ratio of the mass Mc of the water-based resin (c) to the mass Ma of the metal elements (Zr and / or Ti) in the quaternary transition metal compound = Mc / Ma] is preferably 0.05 to 1.5, more preferably 0.1 to 0.8. By containing the water-based resin (c) and the Group 4 transition metal compound (a) within the range of the mass ratio, flexibility and additional film-forming composition can be imparted to the obtained surface treated coating film and a more robust surface treatment A coating film can be formed.

(Metal compound)

The metal compound (d) is a water-soluble compound having one or two or more metal elements selected from Zr, Ti, V, Mo, W, Ce and Nb.

Among these metal compounds (d), the metal compound having a metal element selected from Zr and Ti is a metal compound which does not release zirconyl ion (ZrO ²⁺ ) or titanyl ion (TiO ²⁺ ) in an aqueous solution, Is distinguished from a quaternary transition metal compound (a). Examples of such a metal compound (d) include zirconium hydrofluoric acid, zirconium ammonium hydrofluoride, zirconium potassium hydrogensulfate, sodium zirconium hydrogencarbonate, titanium hydrofluoric acid, titanium ammonium hydrofluoride, potassium titanium hydrofluoride and sodium titanium hydrofluoride. have.

V, Mo, W, Ce, and Nb is a salt, a complex compound or a coordination compound of one or more of the metal elements. Specifically, for example, a vanadium compound having a pentavalent oxidation such as vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, and oxy trichloride; Vanadium compounds wherein the oxidation number of vanadium such as vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetyl acetate, vanadium acetylacetate, vanadium trichloride, and vanadium molybdate is 5, 4 or 3; Molybdenum compounds such as molybdic acid, ammonium molybdate, sodium molybdate, and molybdophosphoric acid compounds (e.g., ammonium molybdophosphate, sodium molybdophosphate and the like); Tungsten compounds such as metatungstic acid, ammonium metatungstate, sodium metatungstate, paratungstic acid, ammonium paratungstate, and sodium paratungstate; Cerium compounds such as cerium acetate, cerium (III) nitrate or (IV), and cerium chloride; Niobium compounds such as niobium fluoride, and niobium phosphate; And the like.

The predetermined amount of the metal compound added to the metal surface treatment agent can be received in the surface treatment film formed by bonding the Group 4 transition metal compound (a), thereby enhancing the corrosion resistance and adhesion between the laminate films. As a result, excellent adhesion can be maintained even in the corrosive environment in the retort treatment or electrolyte solution immersion.

The content of the metal compound (d) contained in the metal surface treatment agent is preferably such that the ratio of the mass Md of the metal compound (d) to the mass Ma of the metal element (Zr and / or Ti) in the quaternary transition metal compound (a) = Md / Ma] is preferably 0.05 to 2.0, more preferably 0.1 to 1.5. By containing the metal compound (d) and the Group 4 transition metal compound (a) in the range of the mass ratio, the adhesion between the metal surface and the obtained surface treatment film is prevented from lowering, . In particular, it is possible to prevent deterioration of adhesion between the metal surface and the obtained surface treatment film in a high humidity environment, to prevent the obtained surface treatment film from being weakened, to improve the flexibility of the surface treatment film itself, There is an advantage that the adhesion between the film and the laminated film is not deteriorated.

(solvent)

The metal surface treatment agent according to the present invention may contain various kinds of solvents as needed in order to improve the workability upon application to the surface of the metal material. Although such a solvent is mainly composed of water, it is also possible to use a water-soluble organic solvent of the alcohol type, the ketone type, or the cellosolve type, if necessary, such as improving the dryness of the surface treated film.

Solvents include, for example, 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 type solvents such as hexamethylphosphoric triamide; And the like. These solvents may be used alone or in combination of two or more. Of these, water is preferable in terms of environmental and economical advantages.

(Other additives)

The metal surface treatment agent according to the present invention may contain a surfactant, a defoaming agent, a leveling agent, an antiseptic agent, a colorant, a curing agent, and the like within the range that does not impair the object of the present invention and the coating performance. In order to improve the corrosion resistance of the surface treated film, an organic crosslinking agent such as methylol melamine, carbodiimide, and isocyanate may be added to the effect of the present invention and to the extent that the coating performance is not impaired. Silane coupling agents such as glycidoxypropyltriethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Aminopropyltriethoxysilane, and N -? - aminoethyl -? - aminopropyltrimethoxysilane May be added within the range that does not impair the object of the present invention and the coating performance.

(Method for preparing metal surface treatment agent)

The method for producing the metal surface treatment agent according to the present invention is not particularly limited. For example, the Group 4 transition metal compound (a) and the organic compound (b) may be mixed with an optional aqueous resin (c), a metal compound (d), other additives, a solvent and the like, And then sufficiently mixing them.

[Metal material]

As shown in Fig. 1, the metal material 10 according to the present invention has a base metal 1 and a surface treatment film 2 formed by applying a metal surface treatment agent according to the present invention on its surface. In the present invention, the metal material 1 on which the surface treated film 2 is not formed is referred to as "base metal 1", and the metal material on which the surface treated film 2 is formed on the base metal 1 Metal material 10 ". 1 shows an example in which a surface treated film 2 and a resin film 3 or a resin coated film 3 are formed on one surface of a base metal 1, The surface treated film 2 may be formed on both surfaces of the resin film 3, that is, the other surface, and further the resin film 3 or the resin film 3 may be formed.

Means that the base metal 1 and the surface treated film 2 may have different structures. For example, it may have a resin film 3 formed by laminating on the surface treated film 2 or a resin coated film 3 formed by coating. &Quot; Application " refers to applying a metal surface treatment agent to the surface of the base metal 1 by the above-described application step. The surface-treated film 2 is formed by applying the above-described metal surface treatment agent according to the present invention to the base metal 1, so that the surface-treated film 2 is excellent in adhesion and maintenance of adhesion to chemicals.

The shape and structure of the base metal 1 are not particularly limited, and examples thereof include plate-like and thin-film form. The kind of the base metal 1 is not particularly limited, and various kinds of base metal 1 can be used. For example, a metal material applicable to a body or lid material of a food can, a container for food, a battery container, a casing of a secondary battery, and the like can be used. . In particular, the present invention relates to an outer cover material for a mobile lithium ion secondary battery used for a mobile phone, an electronic notebook, a notebook computer, a video camera, or the like, a metal material usable as an outer cover of a lithium ion secondary battery used as driving energy for an electric automobile or a hybrid automobile . The surface treated film 2 can be formed on the surface of these metal materials and the resin film 3 can be laminated on the surface treated film 2 and then subjected to deep drawing processing, Or a metal material capable of performing a strong forming process such as a stretch draw process can be preferably used.

Examples of such a metal material include copper materials such as pure copper and copper alloys, aluminum materials such as pure aluminum and aluminum alloys, iron materials such as ordinary steels and alloy steels, nickel materials such as pure nickel and nickel alloys, .

As the copper alloy, copper is preferably contained in an amount of 50 mass% or more, and for example, brass or the like can be used. Examples of alloy components other than copper in the copper alloy include Zn, P, Al, Fe, Ni and the like. The aluminum alloy preferably contains 50 mass% or more of aluminum, and for example, an Al-Mg-based 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. The alloy steel preferably contains 50 mass% or more of iron, and for example, stainless steel or the like can be used. Examples of alloy components other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr, Mo and the like. As the nickel alloy, it is preferable that nickel is contained in an amount of 50 mass% or more, and for example, Ni-P alloy or the like 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-described metal element on the surface of a metal material, a ceramics material or an organic material other than the above-described metal material. Such a metal coating can be formed by a method such as plating, vapor deposition, cladding or the like. The shape, structure, and the like of the base metal 1 are not particularly limited, and for example, a plate or a thin metal material may be used.

As described above, according to the metal material 10 of the present invention, since the surface treated film 2 is provided, the resin film 3 or the resin coated film 3 is formed on the surface treated film 2, (3) or the resin coating film (3) is formed from the metal material (10) even when subjected to strong molding such as deep drawing, ironing or stretch drawing, It is possible to prevent peeling.

[Surface treatment method]

A method for treating a metal surface using a metal surface treatment agent is a method for obtaining a coating having an adhesion amount of 10 to 3000 mg / m 2 by applying the metal surface treatment agent described above to a metal surface and drying the metal surface treatment agent, And a drying step of forming a surface treated coating film by drying without water washing after the application step.

Further, the surface of the metal material is degreased and cleaned beforehand if necessary. The degreasing agent can be selected from various kinds suitable for the metal substrate. As the cleaning liquid, usually water is used, but a water-soluble solvent or a surfactant aqueous solution may be used. The degreasing means and the cleaning means are not particularly limited, and a spraying method, a dipping method, or the like is preferably used.

(Coating step)

The application step is a step of applying a metal surface treatment agent to the surface of the base metal. The coating method is not particularly limited, and for example, a spray coat, a dip coat, a roll coat, a curtain coat, a spin coat, or a combination thereof can be used. The conditions for using the metal surface treatment agent are not particularly limited. For example, the liquid temperature of the metal surface treatment agent at the time of application is preferably within the range of 10 ° C to 50 ° C. The contact time of the metal surface treatment agent with respect to the metal surface is usually about 0.5 to 180 seconds. The metal surface treating agent according to the present invention is a coating type treating agent, and therefore, after contact with the metal surface treating agent, the metal surface treating film is formed by performing drying described later without washing.

(Drying step)

The drying step is a step of forming a surface treated coating film by drying after the coating step without washing with water. The drying temperature may be a temperature suitable for the solvent to be used. For example, when water is used as the solvent, it is preferably in the range of 60 ° C to 250 ° C. This temperature range can be arbitrarily changed depending on the type of the resin component within the range, more preferably 80 to 200 ° C. The drying apparatus is not particularly limited, but a drying furnace of a batch type, a continuous type or a hot air circulation type, a conveyor type hot air drying furnace, or an electromagnetic induction heating furnace using an IH heater can be used. have.

The surface-treated film thus obtained can be obtained even when a resin film (laminate film) or a resin coating film is further formed thereon and then subjected to strong molding such as deep drawing, ironing or stretch drawing, It is possible to prevent the resin film made of the laminate film or resin film from being peeled off.

The film thickness of the obtained surface treatment film is preferably 0.01 탆 to 1 탆, more preferably 0.02 탆 to 0.05 탆. By setting this range, it is possible to further improve the adhesion of the surface treated film and the maintenance of adhesion of the chemical agent.

Example

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 description, " part " refers to " part by mass ", and " mass% " means the same as "% by weight " &Quot; ppm " has the same meaning as " mg / L ".

[Metal material]

The metal material (base metal) used as the base material is shown below.

Al: A1100P, thickness 0.3 mm

Cu: C1020P, thickness 0.3 mm

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

SUS: SUS304 plate, 0.3 mm thick

Ni plated Cu: Electric Ni plated Cu plated (0.3 mm thick, 2 탆 after Ni plating)

The metal materials shown in the " Base " column of Tables 1 to 4 were selected from these metal materials and prepared as the base metals of Examples 1 to 98 and Comparative Examples 1 to 18.

[Metal surface treatment agent]

(C) and a metal compound (d) which can be used as needed, and the solvent is used as a water to prepare a coating solution containing the Group 4 transition metal compound (a) and the organic compound (b) shown in Tables 1 to 4 And the metal surface treatment agents of Comparative Examples 1 to 13 were prepared. The " concentration " in the table indicates the concentration (mass%) of the non-volatile component in each of the above-mentioned compounds in the metal surface treatment agent. And the metal concentration (% by mass) for the four-group transition metal compound (a) and the metal compound (d).

[Group 4 transition metal compound (a)]

az1: Zirconium carbonate ammonium

az2: Zirconyl acetate

az3: Zirconyl nitrate

at1: oxy 2 oxalate titanium 2 ammonium

at2: Titanactate

[Organic compound (b)]

b1: diethylene glycol (molecular weight: 106, functional group content: 53.1 g solid / eq)

b2: pentaerythritol (molecular weight: 136, functional group content: 34 g solid / eq)

b3: catechol (molecular weight: 110, functional group content: 55.1 g solid / eq)

b4: tartaric acid (molecular weight: 150, functional group content: 37.5 g solid / eq)

b5: L-ascorbic acid (molecular weight: 175, functional group content: 43.8 g solid / eq)

b6: glycolic acid (molecular weight: 78, functional group content: 38.0 g solid / eq)

b7: 1-Hydroxyethylidene-1,1-diphosphonic acid (molecular weight: 206, functional group content: 68.7 g solid / eq)

b8: Ammonium pitate (molecular weight: 738, functional group content: 123.0 g solid / eq)

b9: Polymaleic acid (molecular weight: 3000, functional group content: 58 g solid / eq)

b10: Polyethylene glycol (molecular weight: 800, functional group content: 400 g solid / eq)

(G solid / eq means the mass (calculated value) of the solid content of the hydroxyl group, carboxyl group, phosphonic acid group, phosphoric acid group and sulfonic acid group per equivalent of the organic compound (b)).

[Water-soluble polymer (c)]

(c1: urethane resin - anionic)

100 parts of a polyester polyol (adipic acid / 3-methyl-1,5-pentanediol, number average molecular weight: 1000, number of functional groups: 2, hydroxyl value: 112.2), 3 parts of trimethylolpropane, 25 parts of dimethylolpropionic acid, And 85 parts of isophorone diisocyanate were reacted in MEK (methyl ethyl ketone) to obtain a urethane prepolymer. This was mixed with 9.4 parts of triethylamine, and the mixture was poured into water. The urethane prepolymer was dispersed in water and elongated with ethylenediamine to obtain a dispersion. Methyl ethyl ketone was distilled off to obtain an aqueous urethane resin dispersion containing 30 mass% of nonvolatile matter. The acid value of the carboxyl group-containing polyurethane dispersed in the obtained urethane resin aqueous dispersion was 49 (KOH mg / g).

(c2: epoxy resin - anionic)

85 g of orthophosphoric acid and 140 g of propylene glycol monomethyl ether were charged and 425 g of a bisphenol A type epoxy resin having an epoxy equivalent of 250 was slowly added thereto and reacted at 80 DEG C for 2 hours. After completion of the reaction, 150 g of a 29 mass% aqueous ammonia solution was slowly added at 50 DEG C or lower, and further 1150 g of water was added to obtain an ammonia neutralized product of a phosphoric acid modified epoxy resin having an acid value of 35 and a solid content concentration of 25 mass%.

(c3: acrylic resin-nonionic)

40 parts of butyl acrylate (molecular weight: 128), 10 parts of 2-hydroxypropyl methacrylate (molecular weight: 144), 10 parts of styrene (molecular weight: 104) , And 20 parts of N, N-dimethylaminopropyl methacrylate (molecular weight: 175) were used. Synthesis of acrylic resin c was carried out in the same manner as in Synthesis Example 1 except that a 10 mass% emulsifier aqueous solution (a mixture of Adeka Asob NE-20 (manufactured by ADEKA) and a nonionic emulsifier "Elmagen 840S" (Kao Corporation) S-1), the above monomers were mixed and emulsified at 5000 rpm for 10 minutes using a homogenizer to obtain a monomer emulsion (ER). Subsequently, 150 parts of the above-mentioned emulsifier solution (S-1) was added to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a monomer feed pump and maintained at 40 to 50 캜. A 5 mass% aqueous solution of ammonium persulfate 50 parts) and the monomer emulsion (ER) were placed in a dropping funnel, respectively, and mounted on the other inlet of the flask. The mixture was dropped over about 2 hours, the temperature was raised to 60 캜 and stirred for about 1 hour. The mixture was cooled to room temperature while stirring to obtain an acrylic resin emulsion solution.

(c4: acrylic resin-nonionic)

An aqueous solution of acrylamide polymer (nonvolatile matter concentration of 22.0 mass%, viscosity of 90 mPa 占 퐏) was used.

(c5: phenolic resin-nonionic)

A resol resin (dimer) having a methylol group was used.

(c6: polyester resin-anionic)

(40 mol%), terephthalic acid (41 mol%), sodium dimethyl isosulphate (2 mol%), and an alcohol component composed of ethylene glycol (90 mol%) and trimethylol propane (NVC. 30%) by the condensation reaction of an acid component composed of trimellitic anhydride (17 mol%) and anhydrous trimellitic acid (17 mol%) was synthesized by the following method. A catalyst (calcium acetate: 0.25 g, N-butyl titanate: 0.1 g) was charged to a 1000 mL round bottom flask equipped with a nitrogen gas inlet tube, a Clizen tube and an air cooler, with a total of 1 mol of the acid component and 2 mol of the total alcohol component. The inside of the system was purged with nitrogen, and the contents were heated at 180 DEG C to melt the contents. Then, the temperature of the bath was raised to 200 ° C, and the mixture was heated and stirred for about 2 hours to carry out an esterification reaction or an ester exchange reaction. Subsequently, the temperature of the bath was raised to 260 DEG C, and after about 15 minutes, the pressure in the system was reduced to 0.5 mmHg and the reaction (polycondensation reaction) was performed for about 3 hours. After completion of the reaction, the mixture was allowed to cool under nitrogen introduction, and the contents were taken out. An appropriate amount of ammonia water (amount of water to give a solid content of 25%) was added to the resin thus obtained to have a final pH of 6 to 7, and the mixture was heated and stirred in an autoclave at 100 占 폚 for 2 hours to obtain an aqueous emulsion resin. The term " solid component " refers to a component excluding a volatile component such as a solvent.

(c7: polyvinyl alcohol-nonionic)

Acetacetylated polyvinyl alcohol having a degree of saponification of 99%, a viscosity of 12 mPa · S, an acetacetylation degree of 9.8% and an average molecular weight of 50,000 was used.

(c8: polyolefin-anionic)

100 parts of a propylene-ethylene-? -Olefin copolymer (propylene component: 68 mol%, ethylene component: 8 mol%, butene component: 24 mol%, weight average molecular weight: 60,000), 10 parts of maleic anhydride, 10 parts of methyl methacrylate and 1 part of dicumyl peroxide were added and stirred at 180 DEG C for 2 hours to carry out a reaction. To obtain a modified polyolefin resin composition having a weight average molecular weight of 45,000 and a graft weight of maleic anhydride of 8.4% by weight. Thereafter, 100 parts of the modified polyolefin, 10 parts of dimethylethanolamine and 10 parts of polyoxyethylene alkyl ether sulfate were uniformly stirred in a four-necked flask with a stirring blade under the conditions of 100 占 폚 for 2 hours, melted, 300 parts of ion-exchanged water at 90 DEG C was added and further stirred for 1 hour to prepare an aqueous resin composition having a pH of 8.0.

[Metal compound (d)]

The water-soluble metal compound (d) used is shown below.

d1: Zirconium hydrofluoric acid

d2: Ammonium molybdate

d3: Vanadium acetylacetonate

[Production of the disclosure material]

Each substrate shown in Tables 1 to 4 was spray-degreased with a 3% aqueous solution of Fine Cleaner 359E (Nippon Packerizing Co., Ltd.) at 65 ° C for 1 minute, and then washed with water to clean the surface. Subsequently, in order to evaporate the moisture on the surface of the substrate, it was heated and dried at 80 DEG C for 1 minute. The metal surface treatment agents of Examples 1 to 98 and Comparative Examples 1 to 13 shown in Tables 1 to 4 were applied to the surface of the degreased cleaned substrate by a bar coater method using a # 3 SAS Meyer bar, At 180 캜 for 1 minute to form a surface-treated film on the surface of the substrate. The substrates of Comparative Examples 14 to 18 shown in Table 4 were subjected to the same tests as described above for degreasing, rinsing and drying.

In Table 1 to Table 4, Maz represents the zirconium mass in the zirconium compound, Mat represents the titanium mass in the titanium compound, and Ma represents the mass of the metal (Zr and / or Ti) in the quaternary transition metal compound , Mb represents the mass of the organic compound (b), Mc represents the mass of the water-based resin (c), and Md represents the mass of the metal compound (d).

A polypropylene film was laminated by the heat lamination or dry lamination shown below to the surface treated film formed of the metal surface treating agent of Examples 1 to 98 and Comparative Examples 1 to 13 and the substrates of Comparative Examples 14 to 18.

(Heat lamination)

Next, a dispersion of acid-denatured polypropylene ("R120K" manufactured by Mitsui Chemicals, Inc., nonvolatile content concentration: 20%) was applied by a bar coating method using a # 8 SAS Meyer bar to the surface of the substrate having the surface treated film formed thereon, And dried at 200 DEG C for 1 minute in a hot air circulating drying furnace to form an adhesive layer. Thereafter, a PP film (CPPS, manufactured by Toray Industries, Inc.) having a thickness of 30 占 퐉 and the adhesive layer were thermocompression bonded at 190 占 폚 and 2 MPa for 10 minutes to produce a laminated base material of a polypropylene film.

(Dry lamination)

("AD-503 / CAT10", non-volatile matter content: 25%) was applied by a # 8 SAS Meyer bar by a bar coating method and then dried in a hot air circulating drying oven at 80 ° C, And dried for 1 minute to form an adhesive layer. Thereafter, the corona discharge treated surface of the adhesive layer and the unoriented polypropylene film ("FCZX" manufactured by Futamura Chemical Co., Ltd.) of 30 μm was pressed at 100 ° C. and 1 MPa, and then cured at 40 ° C. for 4 days To prepare a laminated substrate of a polypropylene film.

Thereafter, each of the laminated polypropylene film substrates produced by heat lamination or dry lamination was subjected to deep drawing processing by a drawing ironing working test. The above laminated base material having a diameter of 160 mm was drawn (first time) to prepare a cup having a diameter of 100 mm. Subsequently, the cup was further drawn (second time) at a diameter of 75 mm and further drawn (third time) at a diameter of 65 mm to prepare a can as a visible material. The ironing (thin wall flower pots) ratio in the first drawing processing, the second drawing processing, and the third drawing processing were set to 5%, 15%, and 15%, respectively.

[Performance evaluation]

Initial adhesion, durability, electrolyte-adhering retention, and liquid stability after deep-drawing the respective polypropylene film laminated substrates were evaluated as follows. The results are shown in Tables 5 to 8.

(Initial adhesion)

The initial adhesion was evaluated by a post-deep drawing material. Quot ;, and a piece of the film which was peeled off was regarded as " 2 points ", and the film peeled off the entire surface was regarded as " one point " . Of the three points, no peeling was observed at all, and particularly excellent appearance and excellent initial adhesion were determined as " 4 points ".

(Durability)

The durability of the specimens after the deep drawing was evaluated by performing the retort test in the atmosphere of the heated pressurized steam. The retort test was conducted using a commercially available sterilization apparatus (autoclave) in a heated and pressurized steam atmosphere at 125 ° C for 1 hour. Thereafter, the film surface was scratched with the tip of the tweezers so that no peeling of the film occurred at all. The film was evaluated as " 6 points " 2 points "indicating that the film was peeled off with a very weak force, and" 1 point "having the film already peeled off.

(Holding property of electrolyte solution)

The adhesiveness of the electrolyte to the electrolyte was evaluated as to the after-dipping treatment of the sealing material after immersion test in an electrolyte solution for a lithium ion secondary battery. Specifically, after the deep drawn drawing, the sealing material was immersed in an electrolytic solution for a lithium ion secondary battery (electrolyte: 1 M-LiPF ₆ , solvent; EC: DMC: DEC = 1 : 1: 1 (% by volume)), and then placed in a thermostatic chamber at 60 캜 for 7 days. Also, "EC" is ethylene carbonate, "DMC" is dimethyl carbonate, and "DEC" is diethyl carbonate.

Thereafter, the specimen was taken out, washed by immersing and shaking in ion-exchanged water for 1 minute, and then dried in a hot-air circulation type drying oven at 100 ° C for 10 minutes. Thereafter, the film surface was scratched with the tip of the tweezers so that no peeling of the film occurred at all. The film was evaluated as " 6 points " 2 points "indicating that the film was peeled off with a very weak force, and" 1 point "having the film already peeled off.

(Drug stability)

The drug stability evaluated the long term stability of the metal surface treatment agent. Specifically, 200 mL of each of the metal surface treatment agents of Examples 1 to 98 and Comparative Examples 1 to 13 shown in Tables 1 to 4 was sealed in a 300 mL plastic container, and the container was kept still for 2 weeks in an atmosphere at 20 캜 (Metal surface treatment agent) was evaluated. , "Solid", "solid", "solid", "solid", "solid", "solid" and "solid" Respectively.

As shown in Tables 5 to 8, the metal surface treatment agent of Examples 1 to 98 and the metal material on which the surface treatment film treated with the metal base material was formed exhibited an initial adhesion property and an adhesion resistance of the electrolyte solution in both heat lamination and dry lamination It was confirmed that the retention property was excellent.

1 metal material
2 surface treated coating
3 laminate film or resin coating film
10 Metal material with surface treated coating

Claims (6)

A Zr compound that releases zirconyl ion (ZrO ²⁺ ) in an aqueous solution, and a Ti compound that releases a titanyl ion (TiO ²⁺ ) in an aqueous solution, and at least one quaternary Group IV transition metal compound (a)
(B) having at least two functional groups selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group and a sulfonic acid group in the same molecule,
Wherein the ratio [Mb / Ma] of the mass (Mb) of the organic compound (b) to the mass (Ma) of the metal in the quaternary transition metal compound (a) is 0.05 to 0.6. The method according to claim 1,
Wherein the organic compound (b) has a molecular weight of 100 or more and 1000 or less, and the organic compound (b) is a compound having the functional group in a ratio of one per 30 to 300 molecular weight. delete 3. The method according to claim 1 or 2,
(C) containing one or more nonionic or anionic water-based resins selected from urethane resins, epoxy resins, acrylic resins, phenol resins, polyester resins, polyvinyl resins and polyolefin resins, Surface treatment agent. 3. The method according to claim 1 or 2,
(D) having one or two or more metal elements selected from Zr, Ti, V, Mo, W, Ce and Nb,
Wherein the metal compound having a metal element selected from Zr and Ti in the metal compound (d) is a metal compound that does not release zirconyl ion (ZrO ²⁺ ) or titanyl ion (TiO ²⁺ ) in an aqueous solution. A metal material having a surface treatment film formed by applying the metal surface treatment agent according to any one of claims 1 to 3 on a metal surface.

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