CN102877055A - Metal surface treatment agent and metal material obtained through processing with same - Google Patents

Abstract

The present invention relates to a metal surface treatment agent for forming a surface treatment film when a resin film is laminated on the surface of a metal material or a resin coating film is formed on the surface of a metal material, followed by severe forming such as deep drawing , can also impart high adhesion without peeling off the laminated film or resin coating film. For this reason, the present invention provides a metal surface treatment agent, which contains a Zr compound that releases zirconyl ions (ZrO ²⁺ ) in an aqueous solution and a Ti compound that releases titanyl ions (TiO ²⁺ ) in an aqueous solution. One or more Group 4 transition metal compounds (a), and one or more functional groups selected from the group consisting of hydroxyl, carboxyl, phosphonic acid, phosphoric acid and sulfonic acid in the same molecule organic compound (b). Preferably, the molecular weight of the organic compound (b) is 100 to 1000, and the organic compound (b) has a functional group in a ratio of 1 per molecular weight of 30 to 300.

Description

Metal surface treatment agent and metal material obtained by treating with the treatment agent

technical field

The present invention relates to a metal surface treatment agent and a metal material obtained by treating the metal surface treatment agent. And a surface treatment film with excellent chemical resistance and adhesion retention. Specifically, the present invention relates to a metal surface treatment agent and the like for forming a surface treatment film excellent in chemical-resistant adhesion retention even when a resin film is laminated on a metal material or on a metal material. In the case of forming a resin coating film and then performing severe forming processing such as deep drawing, thinning processing (しごき processing), or stretching processing, high adhesion can be imparted without peeling off the laminated film, etc., and in High adhesion can be maintained even when exposed to acids, organic solvents, etc.

Background technique

Lamination processing is a processing method in which a resin film (hereinafter referred to as "resin film" or "lamination film") is heated and pressed on the surface of a metal material (hereinafter referred to as "metal surface"). It is one of the metal surface coating methods for the purpose of imparting a metal surface or designability, and can be used in various fields. Compared with the method of forming a resin coating film by applying a coating solution obtained by dissolving or dispersing a resin composition in a solvent on a metal surface and drying it to form a resin coating film, the lamination process generates less solvent during drying, and waste gas such as carbon dioxide or The amount of greenhouse gas produced is also small. Therefore, from the viewpoint of environmental protection, lamination is preferably used, and its applications have expanded, and it has been used, for example, in the main body or lid of food cans made of aluminum sheet materials, steel sheet materials, aluminum foil for packaging, or stainless steel foil. materials, food containers or dry battery containers, etc.

Especially recently, aluminum foil or stainless steel foil, which is lightweight and has high barrier properties, is preferably used as the exterior material and tab lead material of portable lithium-ion secondary batteries used in mobile phones, electronic notebooks, notebook computers, and video cameras. The surface of such a metal foil is laminated. In addition, lithium-ion secondary batteries are being studied as driving energy for electric vehicles or hybrid vehicles, and laminated metal foils are also being studied as exterior materials.

The lamination film used for such lamination processing is bonded directly to a metal material, followed by heating and pressing. Therefore, there are advantages such as being able to suppress the waste of raw materials, having fewer pinholes (defects), and having excellent processability, compared with a general resin coating film in which a resin composition is applied and dried. As a material of the laminated film, polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate, and polyolefins such as polyethylene and polypropylene are generally used.

If the metal surface is not subjected to a chemical conversion treatment or the like during the lamination process, there is a problem that the laminated film is peeled off from the metal surface or the metal material is corroded. For example, for food containers or packaging materials, after adding the contents to the laminated containers or packaging materials, heat treatment for the purpose of sterilization is carried out, but the laminated film may be detached from the metal during the heat treatment. Surface peeling. Moreover, the exterior material etc. of a lithium ion secondary battery are processed with a high degree of processing in the manufacturing process. In addition, during long-term use, there is a problem that moisture in the atmosphere will infiltrate into the container, react with the electrolyte to generate hydrofluoric acid, and the hydrofluoric acid will permeate the laminated film to cause peeling of the metal surface and the laminated film. , and will corrode metal surfaces.

In view of the above problems, when the laminated film is laminated on the metal surface, in order to improve the adhesion between the laminated film and the metal surface and the corrosion resistance of the metal surface, the metal surface should be degreased and cleaned, and then usually Carry out chemical conversion treatment such as phosphate chromate, etc. However, such chemical conversion treatment requires a washing step after the treatment to remove excess treatment liquid, and waste water treatment of the washing water discharged from the washing step requires cost. In particular, chemical conversion treatment such as phosphate chromate uses a treatment solution containing hexavalent chromium, and thus its use tends to be discontinued due to concerns about the environment in recent years.

For example, Patent Document 1 proposes a surface treatment agent containing a specific amount of a water-soluble zirconium compound, a water-soluble or water-dispersible acrylic resin of a specific structure, and a water-soluble or water-dispersible thermosetting crosslinking agent. In addition, Patent Document 2 proposes a chromium-free 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. In addition, Patent Document 3 proposes a metal surface treatment agent containing an aminated phenolic polymer, a specific metal compound such as Ti and Zr, and the pH of the metal surface treatment agent is in the range of 1.5 to 6.0. In addition, Patent Document 4 proposes a resin film containing an aminated phenolic polymer, an acrylic polymer, a metal compound, and if necessary, a phosphorus compound.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2002-265821

Patent Document 2: Japanese Unexamined Patent Publication No. 2003-313680

Patent Document 3: Japanese Patent Laid-Open No. 2003-138382

Patent Document 4: Japanese Patent Laid-Open No. 2004-262143

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to provide a metal surface treatment agent for forming a surface treatment film that can be used even when a resin film is laminated on the metal material, and a metal material obtained by using the metal surface treatment agent. In the case of forming a resin coating film on the surface of a metal material, and then performing severe forming processes such as deep drawing, thinning, or stretching, it is also possible to impart High adhesion of peeling.

way of solving the problem

The metal surface treatment agent of the present invention for solving the above-mentioned problems is characterized in that it contains one or more than two kinds of transition metal compounds (a) and organic compounds (b) of Group 4, and the transition metal compounds of Group 4 ( a) Zr compounds that release zirconyl ions (ZrO ²⁺ ) in aqueous solution and Ti compounds that release titanyl ions (TiO ²⁺ ) in aqueous solution, and the organic compound (b) has two One or more functional groups selected from hydroxyl, carboxyl, phosphonate group, phosphate group and sulfonate group.

According to this invention, when the metal surface treatment agent is applied to the metal surface, the Group 4 transition metal compound (a) contained in the metal surface treatment agent is caused by zirconyl ions (ZrO ²⁺ ), titanium acyl ions (TiO ²⁺ ) and other metal oxyacyl ions (オキシ metal イオン) react with the metal surface and are strongly adsorbed on the metal surface. Then, when moisture is removed by heating and drying etc. later, a bond is formed by a condensation reaction between zirconyl ions (ZrO ²⁺ ), a bond is formed by a condensation reaction between titanium acyl ions (TiO ²⁺ ), Or the bond is formed by the condensation reaction between zirconyl ions (ZrO ²⁺ ) and titanium acyl ions (TiO ²⁺ ). As a result, by using the metal surface treatment agent of the present invention, it is possible to form a tough surface treatment film that imparts high adhesion to the metal surface.

In addition, as for the organic compound (b) contained in the metal surface treatment agent, since it will interact with the zirconyl ions (ZrO ²⁺ ) or titanyl ions (TiO ² ) released from the Group 4 transition metal compound (a), ⁺ ) and other metal oxyacyl ions form water-soluble salts or complex salts, and therefore have the effect of improving the stability of these metal oxyacyl ions. In addition, when moisture is removed by heating and drying after applying the metal surface treatment agent to the metal surface, the organic compound (b) is strongly bonded to Zr or Ti to improve the film-forming property of the film.

In the metal surface treatment agent of the present invention, it is preferable that the molecular weight of the above-mentioned organic compound (b) is 100 to 1000, and the organic compound (b) has the above-mentioned functional group in a ratio of 1 per molecular weight of 30-300. compound, thereby achieving excellent adhesion.

In the metal surface treatment agent of the present invention, it is preferable that the ratio [Mb/Ma] of the mass (Mb) of the above-mentioned organic compound (b) to the mass (Ma) of the metal in the above-mentioned Group 4 transition metal compound (a) is From 0.05 to 0.6, excellent adhesion can be realized.

In the metal surface treating agent of the present invention, it is preferable to contain one or more kinds selected from polyurethane resins, epoxy resins, acrylic resins, phenolic resins, polyester resins, polyvinyl resins, and polyolefin resins. The nonionic or anionic water-based resin (c) thereby imparts flexibility and more excellent film-forming properties to the obtained surface-treated film.

In the metal surface treatment agent of the present invention, it is preferable to contain a metal compound (d) having one or more metal elements selected from Zr, Ti, V, Mo, W, Ce, and Nb, thus, it can As a corrosion inhibitor, it exhibits a more excellent effect of improving corrosion resistance.

The metal material of the present invention for solving the above-mentioned problems is characterized in that it has a surface treatment film formed by applying the above-mentioned surface treatment agent of the present invention to a metal surface.

According to this invention, since there is a surface treatment film formed by applying the metal surface treatment agent of the present invention to the surface of a metal material, even if a resin film is further laminated on the surface treatment film or a resin coating film is formed, and then the In the case of severe forming processes such as deep drawing, thinning, or stretching, it is possible to prevent the laminated film or resin coating film from peeling off from the metal material. And, even in the case of further exposure to acid or the like, the laminated film or resin coating film can be prevented from peeling off from the metal material.

The effect of the invention

According to the metal surface treatment agent of the present invention and the metal material obtained by using the treatment agent, the adhesion between the surface of the metal material and the obtained surface treatment film and the adhesion between the laminated film and the obtained surface treatment film can be improved at the same time through the above-mentioned action. Adhesion between them, and can maintain high adhesion even when exposed to acid etc. As a result, even in the case of laminating a resin film or forming a resin coating film on a metal material with a surface treatment film, and then performing severe forming processes such as deep drawing, thinning, or stretching, and even after further exposure In the case of acids, organic solvents, etc., the laminated film or resin coating film can also be prevented from peeling off from the metal material. In particular, excellent adhesion can be maintained even in corrosive environments such as retort treatment and electrolyte solution immersion.

Description of drawings

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

Symbol Description

1 metal material

2 surface treatment film

3-layer laminated film or resin-coated film

10 Metal materials with surface treatment film

Detailed ways

Hereinafter, the metal surface treatment agent of this invention and the metal material processed with this treatment agent are demonstrated. It should be noted that the technical scope of the present invention is not limited by the following description and the embodiments in the drawings.

[Metal surface treatment agent]

As shown in FIG. 1 , the metal surface treatment agent of the present invention is used to form a laminated film or a resin coating film 3 on the surface of a metal material 1 (hereinafter referred to as "base material metal 1") as a base material. Treatment agent for treating film 2. The metal surface treatment agent is characterized in that it contains the Group 4 transition metal compound (a) and an organic compound (b), and the Group 4 transition metal compound (a) is selected from the group that releases zirconyl ions (ZrO ²⁺ ) Zr compounds and Ti compounds that release titanyl ions (TiO ²⁺ ) in aqueous solution, and the organic compound (b) has two or more compounds selected from the group consisting of hydroxyl, One or more functional groups among carboxyl, phosphonic acid, phosphoric acid and sulfonic acid groups.

The term "contains" means that the metal surface treatment agent may contain other compounds other than the above-mentioned Group 4 transition metal compound (a) and the above-mentioned organic compound (b). Examples of such compounds include surfactants, antifoaming agents, leveling agents, antibacterial and antifungal agents, coloring agents and the like. These compounds can be contained within the range which does not impair the gist of the present invention and the performance of the film. In addition, the base material metal 1 which is a surface treatment object is mentioned later.

Hereinafter, each constituent element will be described in detail.

(Group 4 transition metal compounds)

The Group 4 transition metal compound (a) is one or two selected from Zr compounds that release zirconyl ions (ZrO ²⁺ ) in aqueous solution and Ti compounds that release titanyl ions (TiO ²⁺ ) in aqueous solution above compounds. When the metal surface treatment agent is applied to the surface of the base material metal 1 (also referred to as "metal surface"), the Group 4 transition metal compound (a) is induced by zirconyl ions (ZrO ²⁺ ), titanyl ions (TiO ²⁺ ) and other metal oxyacyl ions react with the metal surface and strongly adsorb on the metal surface. When moisture is removed by subsequent heat drying, etc., the adsorbed metal oxyacyl ions can be bonded by condensation reaction between zirconyl ions (ZrO ²⁺ ), bonded by condensation reaction between titanyl ions (TiO ²⁺ ), Bonds are formed, or bonds are formed through condensation reactions between zirconyl ions (ZrO ²⁺ ) and titanium acyl ions (TiO ²⁺ ). As a result, this bond formation can form a tough surface-treated film that imparts high adhesion to the metal surface.

The zirconium compound is not particularly limited as long as it is a compound capable of releasing zirconyl ions (ZrO ²⁺ ) when dissolved in water. Examples of such zirconium compounds include zirconyl oxycarbonate (Zr ₂ (CO ₃ )(OH) ₂ O ₂ ), zirconyl oxychloride hydroxy (ZrO(OH)Cl), ammonium zirconyl carbonate (( NH ₄ ) ₂ ZrO(CO ₃ ) ₂ ), potassium zirconyl carbonate (K ₂ ZrO(CO ₃ ) ₂ K ₂ ), sodium zirconyl carbonate (Na ₂ ZrO(CO ₃ ) ₂ K ₂ ), zirconyl nitrate ( ZrO(NO ₃ ) ₂ ), zirconyl acetate (ZrO(CH ₃ COO) ₂ ), zirconyl sulfate (ZrOSO ₄ ), zirconium dihydrogen phosphate (ZrO(H ₂ PO ₄ ) ₂ ), zirconium stearate ( ZrO(C ₁₈ H ₃₅ O ₂ ) ₂ ), etc.

The titanium compound is not particularly limited as long as it is a compound capable of releasing titanyl ions (TiO ²⁺ ) in an aqueous solution. Examples of such titanium compounds include diammonium titanyl dioxalate ((NH ₄ ) ₂ [Ti(C ₂ O ₄ ) ₂ O]·nH ₂ O), titanyl sulfate (TiOSO ₄ ), diisopropyl Titanium oxybisacetylacetonate (Ti(OiC ₃ H ₇ ) ₂ (C ₅ H ₇ O ₂ ) ₂ ), titanium hydroxydilactate (Ti(OH) ₂ [OCH(CH ₃ )COOH] ₂ ), and the like.

In the metal surface treatment agent, a zirconium compound and a titanium compound may be contained individually, or both may be contained. When one of the zirconium compound and the titanium compound is contained alone, the content of the compound contained in the metal surface treatment agent is preferably 0.001% by mass to 70% by mass, more preferably 0.01% by mass to 50% by mass. By setting the content to 0.001% by mass to 70% by mass, the adhesiveness and chemical-resistant adhesiveness retention of the obtained surface treatment film can be further improved.

Although the reason is not clear, it is known that a surface treatment film formed by a metal surface treatment agent obtained by blending a titanium compound with a treatment agent based on a zirconium compound brings about higher adhesion. In the metal surface treatment agent mixed with both zirconium compound and titanium compound, the proportion of the two is based on the metal mass ratio in the compound [titanium mass in titanium compound: Mat]/[zirconium mass in zirconium compound: Maz ], preferably 0.005 to 1, more preferably 0.01 to 0.43. The metal surface treatment agent compounded with the metal mass ratio [Mat/Maz] in such a range can form a surface treatment film showing higher adhesion.

(organic compound)

The organic compound (b) is a compound having two or more functional groups selected from the group consisting of hydroxyl, carboxyl, phosphonic acid, phosphoric acid and sulfonic acid in the same molecule. The organic compound (b) reacts with metal oxyacyl ions such as zirconyl ions (ZrO ²⁺ ) and/or titanium acyl ions (TiO ²⁺ ) released from the above-mentioned Group 4 transition metal compound (a) to form a water-soluble salt or complex salt. The water-soluble salt or complex salt formed has the effect of improving the stability of these metal oxyacyl ions, so the above-mentioned effects played by the metal oxyacyl ions can be stably continued, thereby stably forming a High-adhesion tough surface treatment film. In addition, when the metal surface treatment agent is applied to the metal surface and then the moisture is removed by heating and drying, etc., the organic compound (b) is strongly combined with Zr and/or Ti constituting the metal oxyacyl ion, which has the effect of making the formed The effect of improving the film-forming property of the surface treatment film.

The functional group of the organic compound (b) is any of hydroxyl group, carboxyl group, phosphonic acid group, phosphoric acid group and sulfonic acid group, and the organic compound (b) has two or more of the above functional groups in the same molecule. When having 2 or more of the above-mentioned functional groups, the number may be 3, 4, or 4 or more. The upper limit of the number of the above-mentioned functional groups is not particularly limited, and may be, for example, ten. In addition, the two or more functional groups may be the same functional group selected from the above-mentioned hydroxyl group, carboxyl group, phosphonic acid group, phosphoric acid group, and sulfonic acid group, or may be different types of functional groups.

The molecular weight of the organic compound (b) is preferably 100 to 1000, more preferably 100 to 900. The organic compound (b) having a molecular weight within this range has a functional group in a ratio of 1 per molecular weight of 30 to 300. It should be noted that there are no special limitations on other chemical structures of the organic compound (b).

Specific examples of such an organic compound (b) include, for example: ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, dibutylene glycol, glycerin, pentaerythritol, catechol, 1, 2,3-Glycinol, catechin, glucose, pullulan and other polyvalent hydroxyl compounds; oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid and other polyvalent carboxylic acids; glycolic acid, lactic acid, glycerin Hydroxycarboxylic acids such as hydroxymalonic acid, tartaric acid, malic acid, citric acid, pantothenic acid, ascorbic acid, salicylic acid, protocatechuic acid, vanillic acid, gallic acid, mandelic acid; 1-hydroxyethane-1 ,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid), hexamethylenediamine -N,N,N',N'-tetrakis(methylenephosphonic acid), diethylenetriamine-N,N,N',N'',N''-penta(methylenephosphonic acid) , 2-phosphonobutane-1,2,4-tricarboxylic acid and other organic phosphonic acids; phytic acid, phosphate starch, monophosphate glucose and other organic phosphoric acids.

The organic compound (b) has the effect of coordinating with zirconyl ions (ZrO ²⁺ ) released from a zirconium compound in an aqueous solution and/or titanyl ions (TiO ²⁺ ) released from a titanium compound in an aqueous solution, thereby increasing the Stability in metal surface treatments. In addition, when the metal surface treatment agent is used to form a surface treatment film, the organic compound (b) also has an effect of strongly binding to zirconium ions and/or titanium ions to improve film-forming properties. As a result, the corrosion resistance of the surface treatment film and the adhesiveness with the laminated film or resin coating film provided on this surface treatment film are excellent.

The content of the organic compound (b) contained in the metal surface treatment agent is 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 Group 4 transition metal compound (a) [Mass ratio=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 this mass ratio range, the corrosion resistance of the surface treatment film and the relationship between the laminated film or the resin coating film provided on the surface treatment film can be improved. The adhesion between them becomes good. When the mass ratio [Mb/Ma] is less than 0.05, the film-forming property of the surface treatment film may be reduced, and when the mass ratio [Mb/Ma] is greater than 0.6, the surface treatment film and the laminated film installed on the surface treatment film may be damaged. Or the adhesiveness between resin coating films falls.

(water-based resin)

The water-based resin (c) is one or more nonionic or anionic resins selected from polyurethane resins, epoxy resins, acrylic resins, phenolic resins, polyester resins, polyvinyl resins, and polyolefin resins. organic compounds. The organic compound is a compound with an anionic group or a nonionic group, and can be stably present in the metal surface treatment agent of the present invention, as long as it is a compound that can obtain the desired effect, there is no limitation on the type of the organic compound. limited. It should be noted that, in terms of the water-soluble form of the organic compound, the organic compound may be water-soluble or water-dispersible (emulsion, dispersion liquid).

Examples of polyurethane resins include polyurethanes obtained from polyols such as polyester polyols, polyether polyols, and polycarbonate polyols, and aliphatic polyisocyanates, alicyclic isocyanates, and/or aromatic polyisocyanates. Polyurethane resin which is a polycondensate formed of the compound uses a polyol having a polyoxyethylene chain such as polyethylene glycol and polypropylene glycol as a part of the polyol. Such a polyurethane can be dissolved in water or dispersed in water in a nonionic form by increasing the introduction ratio of the above-mentioned polyoxyethylene chain.

In addition, an anionic water-dispersible polyurethane resin can be obtained by producing a urethane prepolymer having isocyanate groups at both ends from a polyisocyanate and a polyol, and combining the prepolymer with two or more hydroxyl groups. The carboxylic acid or its reactive derivatives are reacted to obtain derivatives with isocyanate groups at both ends, and then, triethanolamine, etc. are added to form ionomers (triethanolamine salts), and then the ionomers are added to water to form an emulsion or dispersion, and then add diamines as needed for chain extension.

The carboxylic acids and reactive derivatives used in the production of the above-mentioned anionic water-dispersible polyurethane resin are used to introduce acidic groups into the polyurethane resin and to make the polyurethane resin water-dispersible. Examples of the carboxylic acid to be used include dimethylolalkanoic acids such as dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid. In addition, examples of the reactive derivative include hydrolyzable esters such as acid anhydrides, and the like.

As the epoxy resin, can enumerate: the epoxy compound that has two or more glycidyl groups; The epoxy compound that has bisphenol A or bisphenol F as the unit in skeleton; Or make the epoxy compound that has two or more glycidyl groups Epoxy resins obtained by reacting compounds with diamines such as ethylenediamine and cationizing them; epoxy compounds having bisphenol A or bisphenol F as units in the skeleton or other epoxy resins having two or more glycidyl groups Nonionic epoxy resin obtained by adding polyethylene glycol to the side chain of the compound; and so on.

As the epoxy resin, an epoxy resin having bisphenol A or bisphenol F as a unit in the skeleton can be used. It should be noted that an epoxy resin obtained by modifying part or all of the glycidyl groups of the epoxy resin with silane or phosphoric acid may also be used.

As an epoxy resin having bisphenol A or bisphenol F as a unit in the skeleton, a resin obtained by repeated dehydrochlorination reaction and addition reaction of epichlorohydrin and bisphenol A or bisphenol F; A resin obtained by repeated addition reactions between an epoxy compound having two or more, preferably two, glycidyl groups and bisphenols (A, F).

Examples of epoxy compounds include diglycidyl ethers of bisphenols (A, F), diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, Diglycidylparaben, Diglycidyl Tetrahydrophthalate, Diglycidyl Hexahydrophthalate, Diglycidyl Succinate, Diglycidyl Adipate, Diglycidyl Sebacate Esters, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether Diglycidyl ethers, polyalkylene glycol diglycidyl ethers, triglycidyl trimellitate, triglycidyl isocyanurate, 1,4-epoxypropoxybenzene, diglycidyl Propyl urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin oxide olefin addition The triglycidyl ether of the finished product, etc. The above-mentioned epoxy compounds can be used alone or in combination, respectively.

In addition, the degree of silane modification of an epoxy resin is not specifically limited as long as the effect by these modifications can be confirmed or more. Silane modification can be performed using a known silane coupling agent.

Examples of the acrylic resin include homopolymers or copolymers of acrylic monomers, and copolymers of these acrylic monomers and addition polymerizable monomers copolymerizable with the acrylic monomers. The polymerization method of such an acrylic resin is not particularly limited as long as it can exist stably in the surface treatment agent.

Examples of acrylic monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic shrink Glycerides, glycidyl methacrylate, sulfoethyl acrylate, polyethylene glycol methacrylate, etc. Examples of addition-polymerizable monomers that can be copolymerized with acrylic acid monomers include maleic acid, itaconic acid, acrylamide, N-methylolacrylamide, diacetone acrylamide, styrene, acrylonitrile, and vinyl sulfonate. Acid etc.

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

Vinyl acetate may be a resin obtained by saponification of a polymer copolymerized with a monomer that can be copolymerized with vinyl acetate. In addition, modified polymers obtained by introducing anionic groups such as carboxylic acid, sulfonic acid, and phosphoric acid into the polymer after polymerization, or modified polymers obtained by introducing diacetone acrylamide groups, acetoacetyl groups, mercapto groups, silanol groups, etc. Modified polymers with cross-linking reactive functional groups.

It should be noted that, as monomers that can be copolymerized with vinyl acetate, for example: maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth)acrylic acid and other unsaturated carboxylic acids and their esters; α-olefins such as ethylene and propylene; olefin sulfonic acids such as (meth)propylenesulfonic acid, ethanedisulfonic acid, and sulfonic malate; sodium (meth)allylsulfonate, sodium ethylenedisulfonate, sulfonic acid Sodium (meth)acrylate, sodium sulfonate (monoalkyl malate), sodium disulfonate alkyl malate and other alkali metal olefin sulfonates; N-methylolacrylamide, acrylamide alkylsulfonate Monomers containing amide groups such as acid and alkali metal salts; N-vinylpyrrolidone, N-vinylpyrrolidone derivatives; etc.

Examples of the phenolic resin include low-molecular-weight water-soluble resins or emulsion resins that are polycondensates of phenols (phenol, naphthol, bisphenol, etc.) and formaldehyde. Among them, a methylol group-containing resole phenolic resin having self-condensability is preferable.

Examples of natural polymers include cellulose, starch, dextrin, inulin, xanthan gum, tamarind gum, tannin, lignosulfonic acid and the like.

Examples of polyolefin-based resins include polyolefins obtained by modifying polyolefins such as polypropylene, polyethylene, and copolymers of propylene or ethylene and α-olefins with unsaturated carboxylic acids (such as acrylic acid and methacrylic acid). Polyolefins, or copolymers of ethylene and acrylic acid (methacrylic acid). In addition, it may be a copolymer obtained by copolymerizing a small amount of other ethylenically unsaturated monomers. As a method of water-based conversion, a method of neutralizing the carboxylic acid introduced into the polyolefin resin with ammonia or amines is mentioned.

For these non-ionic or anionic water-based resins (c), as the adhesive effect brought by the film-forming properties of itself, including: (1) can be used by the 4th group transition metal compound (a) The surface treatment film formed with the organic compound (b) imparts flexibility; and (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), thereby firmly Stick to the surface treatment film. Therefore, the metal surface treatment agent containing the water-based resin (c) can form a tougher surface treatment film that can withstand strong processing due to the above-mentioned effects of the water-based resin (c).

Examples of these nonionic or anionic water-based resins (c) include water-soluble resins, water-based cross-linking resins such as water-based emulsions and aqueous dispersions that have undergone self-emulsification or forced emulsification with an emulsifier, or water-based high molecular resin. Among them, a monomer or oligomer with a number average molecular weight of less than 1000 can be preferably used to self-crosslink and then polymerize under the action of heat, ultraviolet rays or electron beams, etc. applied when forming the film; or several A cross-linked resin in which monomers or oligomers with an average molecular weight of less than 1000 react with other cross-linking agents to become polymerized. In addition, a polymer resin having a number average molecular weight of 1,000 to 1,000,000 and capable of forming a film under the action of heat or the like can also be used. In addition, these polymeric resins may be resins having crosslinking reactive functional groups as long as the effects of the present invention are not impaired.

The content of the water-based resin (c) contained in the metal surface treatment agent is the ratio of the quality Ma of the metal element (Zr and/or Ti) in the quality Mc of the water-based resin (c) to the 4th group transition metal compound (a) [ The mass ratio=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) in this mass ratio range, while imparting flexibility and more excellent film-forming properties to the obtained surface treatment film, it is possible to form a A stronger surface treatment coating.

(metal compound)

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

Among the metal compounds (d), the metal compound having a metal element selected from Zr and Ti is a metal compound that does not release zirconyl ions (ZrO ²⁺ ) or titanyl ions (TiO ²⁺ ) in an aqueous solution. In the above-mentioned Group 4 transition metal compound (a). Such metal compounds (d) include, for example, fluozirconic acid, ammonium fluozirconate, potassium fluozirconate, sodium fluozirconate, fluotitanic acid, and ammonium titanate hydrofluoride (Chitanic acid fluoride hydrogen acid ammonium) , potassium fluotitanate, sodium fluotitanate, etc.

Metal compounds having one or more metal elements selected from V, Mo, W, Ce, and Nb are salts, complexes, or coordination compounds of these metal elements. Specific examples include: vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, and vanadium oxychloride and other vanadium compounds with an oxidation number of 5; vanadium trioxide, vanadium dioxide, vanadyl sulfate, Vanadium acetylacetonate, vanadium acetylacetonate, vanadium trichloride, and phosphovanadium molybdic acid and other vanadium compounds whose vanadium oxidation number is 5, 4 or 3; molybdic acid, ammonium molybdate, sodium molybdate, and phosphorus Molybdenum compounds such as molybdenum acid compounds (for example, ammonium phosphomolybdate, sodium phosphomolybdate, etc.); tungsten compounds such as metatungstic acid, ammonium metatungstate, sodium metatungstate, paratungstic acid, ammonium paratungstate and sodium paratungstate; acetic acid Cerium, cerium (III) or (IV) nitrate, and cerium compounds such as cerium chloride; niobium compounds such as niobium fluoride and niobium phosphate; and the like.

A given amount of metal compound added to the metal surface treatment agent can be introduced into the surface treatment coating formed by combining the Group 4 transition metal compound (a), thereby further improving the corrosion resistance and the adhesion with the laminated film. tightness. As a result, excellent adhesion can be maintained even in corrosive environments such as retort treatment and electrolyte solution immersion.

In terms of the content of the metal compound (d) contained in the metal surface treatment agent, the mass Md of the metal compound (d) and the mass of the metal element (Zr and/or Ti) in the 4th group transition metal compound (a) The ratio of Ma [mass ratio=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 this mass ratio range, it is possible to prevent the decrease in the adhesion between the metal surface and the obtained surface treatment film, and to prevent the corrosive medium from infiltrating into the metal surface to cause corrosion resistance. reduced sex. In particular, it has the following advantages: it can prevent the reduction of the adhesion between the metal surface and the obtained surface-treated film in a high-humidity environment, thereby preventing the obtained surface-treated film from becoming brittle, improving the flexibility of the surface-treated film itself, and making it Even after subsequent processing, a reduction in the adhesiveness between the obtained surface-treated film and the laminated film does not occur.

(solvent)

In order to improve the workability when the metal surface treating agent of the present invention is applied to the surface of a metal material, various solvents may be contained as necessary. Such a solvent is mainly water, but it is also possible to use alcohols, ketones, or cellosolve-based water-soluble organic solvents in combination according to needs such as improving the dryness of the surface treatment film.

Examples of solvents include water; alkane solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; alcohol solvents such as ethanol, 1-butanol, and ethyl cellosolve; tetrahydrofuran, dioxane, etc. Ether solvents such as ethyl acetate and butoxyethyl acetate; ester solvents such as ethyl acetate and butoxyethyl acetate; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfone solvents such as dimethyl sulfoxide; hexamethylphosphoric acid Phosphate amide solvents such as triamides; etc. One of the above-mentioned solvents may be used alone, or two or more of them may be used in combination. Among these solvents, water is preferable because of its environmental and economic advantages.

(other additives)

The metal surface treatment agent of the present invention may contain surfactants, defoamers, leveling agents, antibacterial and antifungal agents, colorants, curing agents, etc. within the scope of not destroying the gist of the present invention and film properties. In addition, within the scope of not destroying the gist of the present invention and the performance of the film, organic crosslinking agents such as methylolated melamine, carbodiimide, and isocyanate can also be added to improve the corrosion resistance of the surface treatment film, and γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, and N- Silane coupling agents such as β-aminoethyl-γ-aminopropyltrimethoxysilane.

(Preparation method of metal surface treatment agent)

The method for producing the metal surface treatment agent of the present invention is not particularly limited. For example, it can be produced by mixing the Group 4 transition metal compound (a) and the organic compound (b) with optionally contained water-based resin (c), metal compound (d), other additives, solvents, etc., and using a mixer Wait for the mixer to fully mix to prepare the metal surface treatment agent.

[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 metal surface treatment agent of the present invention to the surface of the base metal 1 . In this application, the metal material 1 without the surface treatment coating 2 is called "base metal 1", and the metal material with the surface treatment coating 2 on the base metal 1 is called "metal material 10". 1 shows an example in which a surface treatment film 2 and a resin film 3 or a resin coating film 3 are formed on one side surface of a base metal 1, but it may be formed on both sides of a base metal 1. , That is, the surface treatment film 2 is also formed on the other surface, and the resin film 3 or the resin coating film 3 is further provided.

The term "having" means that it may have other configurations than the base metal 1 and the surface treatment film 2 . For example, a laminated resin film 3 or a coated resin coating film 3 may be provided on the surface treatment film 2 . The term "coating" refers to applying a metal surface treatment agent to the surface of the base metal 1 through the above-mentioned coating step. Since the surface treatment film 2 is formed by applying the metal surface treatment agent of the present invention to the base material metal 1, it has excellent adhesion and chemical-resistant adhesion retention.

The shape, structure, etc. of the base material metal 1 are not particularly limited, and examples thereof include a plate shape, a foil shape, and the like. In addition, the type of base material metal 1 is not particularly limited, and various metals can be used. For example, metal materials that can be applied to the main body or lid material of food cans, food containers, dry battery containers, secondary battery exterior materials, etc., are not limited to these materials, and metals that can be used in a wide range of applications can be used. Material. In particular, metal materials that can be used as exterior materials for lithium-ion secondary batteries that are recently used in portable batteries such as mobile phones, electronic notebooks, notebook computers, and video cameras can be cited. Exterior materials for lithium-ion secondary batteries, and exterior materials for lithium-ion secondary batteries used as driving energy for electric vehicles or hybrid vehicles. Among these metal materials, it is preferable to use a metal material that can form a surface treatment film 2 on its surface, and can laminate a resin film 3 etc. on the surface treatment film 2, and can be subjected to subsequent deep drawing, thinning, or stretching. Formed metal materials.

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

As the copper alloy, a copper alloy containing 50% by mass or more of copper is preferably used, 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. As the aluminum alloy, an aluminum alloy containing 50% by mass or more of aluminum is preferably used, 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, Ti, and the like. As the alloy steel, an alloy steel containing 50% by mass or more of iron is preferably used, 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, a nickel alloy containing 50% by mass or more of nickel is preferably used, and for example, a 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, P, and the like.

The base material metal 1 may form a film containing the above-mentioned metal elements on the surface of a metal material other than the above-mentioned metal materials, a ceramic material, or an organic material. Such a metal film can be formed, for example, by methods such as plating, vapor deposition, and cladding. In addition, the shape, structure, etc. of the base material metal 1 are not particularly limited, and a plate-shaped or foil-shaped metal material can be used, for example.

As above, according to the metal material 10 of the present invention, since it has the surface treatment film 2 as described above, even if the resin film 3 or the resin coating film 3 is formed on the surface treatment film 2 and then deep drawing, thinning or stretching is performed, It is also possible to prevent the resin film 3 or the resin coating film 3 from peeling off from the metal material 10 in the case of severe forming processing such as drawing processing, and in the case of further exposure to acid or the like.

[Surface treatment method]

The metal surface treatment method using a metal surface treatment agent is a method for obtaining a film with an adhesion amount of 10 to 3000 mg/ ^m by coating the above metal surface treatment agent on the metal surface and drying it. The method includes the following steps: A coating process in which the metal surface treatment agent is applied to the metal surface of the base material; and a drying process in which the surface treatment film is formed by drying without washing with water after the coating process.

It should be noted that the surface of the metal material may be degreased and cleaned in advance as necessary. The degreasing agent can be selected from various materials suitable for the metal matrix material. In addition, water is usually used as the washing liquid, but a water-soluble solvent, an aqueous surfactant solution, or the like may also be used. In addition, the degreasing method and cleaning method are not particularly limited, but spraying method, dipping method, etc. are preferably used.

(coating process)

The coating step is a step of applying the metal surface treatment agent to the metal surface of the base material. The coating method is not particularly limited, and for example, spray coating, dip coating, roll coating, curtain coating, spin coating, or a combination of these methods can be used. The conditions of use of the metal surface treatment agent are not particularly limited. For example, the liquid temperature of the metal surface treatment agent at the time of coating is preferably in the range of 10°C to 50°C. The contact time between the metal surface treatment agent and the metal surface is usually about 0.5 seconds to 180 seconds. The metal surface treatment agent of the present invention is a coating-type treatment agent, and therefore, after being in contact with the metal surface treatment agent, it is dried as described later without washing to form a metal surface treatment film.

(drying process)

The drying step is a step of forming a surface treatment film by drying without washing with water after the coating step. The drying temperature can be set to a temperature suitable for the solvent used. For example, when water is used as a solvent, the drying temperature is preferably in the range of 60°C to 250°C. This temperature range can be changed arbitrarily within the above range according to the type of the resin component, but is more preferably 80 to 200°C. The drying device is not particularly limited, and can be a batch type, continuous type or hot air circulation type drying furnace, a conveyor belt type hot air drying furnace, or an electromagnetic induction heating furnace using an IH heater, etc. The air volume and speed can be set arbitrarily.

For the surface treatment film thus obtained, even when severe forming processes such as deep drawing, thinning, or stretching are performed after further forming a resin film (lamination film) or a resin coating film on it, and in In the case of further exposure to acid or the like, it is also possible to prevent peeling of the resin film composed of the laminated film or the resin coating film.

The film thickness of the obtained surface treatment film is preferably 0.01 μm to 1 μm, more preferably 0.02 μm to 0.05 μm. By setting the film thickness of the surface-treated coating within this range, the adhesiveness and chemical-resistant adhesion retention of the surface-treated coating can be further improved.

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. It should be noted that the following "parts" refer to "parts by mass", "mass%" is synonymous with "weight%", and the following may be expressed as "%" unless otherwise specified. "ppm" is synonymous with "mg/L".

[metallic material]

Metal materials (base material metals) used as base materials are as follows.

Al: A1100P, thickness 0.3mm

Cu: C1020P, thickness 0.3mm

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

SUS: SUS304 board, thickness 0.3mm

Nickel-plated copper: nickel-plated copper plate (thickness 0.3mm, nickel plating thickness 2μm)

From these metal materials, the metal materials shown in the "base material" column of Tables 1 to 4 were selected, and base metals of Examples 1 to 98 and Comparative Examples 1 to 18 were prepared.

[Metal surface treatment agent]

Table 1- The metal surface treatment agents of Examples 1 to 98 shown in Table 4 and the metal surface treatment agents of Comparative Examples 1 to 13. In addition, "concentration" in a table|surface represents the non-volatile content concentration (mass %) which each said compound occupies in a metal surface treatment agent. For the Group 4 transition metal compound (a) and the metal compound (d), it is expressed as the metal concentration (mass %).

[Group 4 transition metal compound (a)]

az1: ammonium zirconium carbonate

az2: zirconyl acetate

az3: zirconyl nitrate

at1: diammonium titanyl dioxalate

at2: titanium hydroxydilactate [organic compound (b)]

b1: diethylene glycol (molecular weight: 106, functional group content: 53.1g solid/eq (g solid/eq is Unit of oxazoline equivalent))

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

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

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

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

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

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

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

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

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

[Water-soluble polymer (c)]

(c1: Polyurethane resin - anionic)

100 parts of 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 dimethylol propionic acid and 85 parts of isophorone diisocyanate were reacted in MEK (methyl ethyl ketone) to obtain a urethane prepolymer. This urethane prepolymer was mixed with 9.4 parts of triethylamine and poured into water, the above urethane prepolymer was dispersed in water, and the prepolymer was elongated by ethylenediamine to obtain a dispersion . Methyl ethyl ketone was distilled off to obtain an aqueous polyurethane resin dispersion containing 30% by mass of nonvolatile matter. The acid value of the carboxyl group-containing polyurethane dispersed in the obtained aqueous polyurethane resin dispersion was 49 (KOHmg/g).

(c2: epoxy resin - anionic)

Add 85 g of orthophosphoric acid and 140 g of propylene glycol monomethyl ether, and slowly add 425 g of bisphenol A type epoxy resin with an epoxy equivalent of 250, and react at 80° C. for 2 hours. After completion of the reaction, 150 g of 29% by mass ammonia solution was slowly added at below 50°C, and then 1150g of water was added to obtain an ammonia neutralized product of phosphoric acid-modified epoxy resin with an acid value of 35 and a solid content concentration of 25% by mass.

(c3: Acrylic resin - non-ionic)

The following monomer composition was adopted: "20 parts of methyl methacrylate (molecular weight: 100), 40 parts of butyl acrylate (molecular weight: 128), 10 parts of 2-hydroxypropyl methacrylate (molecular weight: 144), benzene 10 parts of ethylene (molecular weight: 104), 20 parts of N,N-dimethylaminopropyl methacrylate (molecular weight: 175). The acrylic resin c was synthesized as follows: 10% of the reactive emulsifier "Adeka Reasoap NE-20" (manufactured by ADEKA Co., Ltd.) The said monomer was mixed with 100 parts of mass % emulsifier aqueous solution (S-1), and it emulsified by the homogenizer at 5000 rpm for 10 minutes, and obtained the monomer emulsion (ER). Next, 150 parts of the above-mentioned emulsifier aqueous solution (S-1) was added to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a monomer supply pump, and kept at 40 to 50° C. The aqueous solution (50 parts) and the above-mentioned monomer emulsion (ER) were added to the dropping funnel respectively, and the dropping funnel was installed on the other neck of the flask, and added dropwise in about 2 hours, and the temperature was raised to 60 °C, stirring was carried out for about 1 hour. Cool to room temperature while stirring to obtain an emulsified solution of acrylic resin.

(c4: Acrylic resin - non-ionic)

An aqueous solution of an acrylamide polymer (non-volatile matter concentration: 22.0% by mass, viscosity: 90 mPa·s) was used.

(c5: phenolic resin - non-ionic)

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

(c6: polyester resin - anionic)

An anionic polyester resin (solid content (NVC.) 30%) was synthesized by the condensation reaction of the following alcohol component including ethylene glycol (90mol%) and the following acid component by the following method. Methylolpropane (10mol%), the acid components include isophthalic acid (40mol%), terephthalic acid (41mol%), dimethyl isophthalate-5-sodium sulfonate (2mol%) and Trimellitic anhydride (17 mol%). In a 1000mL round-bottomed flask equipped with a Claisen tube and an air condenser, add 1 mol of total acid components, 2 mol of total alcohol components and catalysts (calcium acetate: 0.25g, n-butyl titanate: 0.1g), to the system The interior was replaced with nitrogen, and heated to 180° C. to melt the contents. Then, the bath temperature was raised to 200° C., heating and stirring were performed for about 2 hours, and an esterification or transesterification reaction was carried out. Next, the bath temperature was raised to 260° C., and after about 15 minutes, the pressure in the system was reduced to 0.5 mmHg, and reaction was performed for about 3 hours (polycondensation reaction). After completion of the reaction, it was naturally cooled while introducing nitrogen gas, and the contents were taken out. To the resin taken out, an appropriate amount of ammonia water (in an amount such that the solid content reaches 25% for water) is added so that the final pH can reach 6 to 7, and heated and stirred in an autoclave at 100° C. for 2 hours to obtain Waterborne emulsion resin. In addition, the said "solid content" means components other than volatile components, such as a solvent, etc.

(c7: polyvinyl alcohol - nonionic)

The degree of saponification: 99%, the viscosity: 12 mPa·S, the degree of acetoacetylation: 9.8%, and the acetoacetylated polyvinyl alcohol of average molecular weight: 50000 were used.

(c8: polyolefin-anionic)

100 parts of propylene-ethylene-α-olefin copolymer (propylene component: 68 mol%, ethylene component: 8 mol%, butene component: 24 mol%, weight average molecular weight: 60,000) and maleic anhydride were put into a four-necked flask. 10 parts, 10 parts of methyl methacrylate, and 1 part of dicumyl peroxide were stirred at 180 degreeC for 2 hours, and they were made to react. 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 was obtained. Then, 100 parts of the above-mentioned modified polyolefin, 10 parts of dimethylethanolamine and 10 parts of polyoxyethylene alkyl ether sulfate were uniformly stirred in a four-necked flask at 100° C. for 2 hours by a stirring blade, and melted Then, 300 parts of ion-exchanged water at 90° C. was added, and stirring was continued for 1 hour to prepare an aqueous resin composition with pH 8.0.

[Metal compound (d)]

The water-soluble metal compound (d) used is as follows.

d1: Fluorozirconic acid

d2: Ammonium molybdate

d3: Vanadium acetylacetonate

[Production of test materials]

For each base material shown in Table 1 to Table 4, use a 3% aqueous solution of Fine cleaner 359E (alkali degreasing agent manufactured by Nihon Parkerizing Co., Ltd.) to spray degrease at 65°C for 1 minute, and then wash with water to clean the surface. Next, heat drying was performed at 80° C. for 1 minute in order to evaporate moisture on the surface of the base material. Using #3 SUS Mailer bar, the metal surface treatment agents of Examples 1 to 98 and Comparative Examples 1 to 13 shown in Table 1 to Table 4 are coated on the surface of the base material after degreasing and cleaning by bar coating method, and then heated in hot air Drying at 180° C. for 1 minute in a circulating drying oven formed a surface treatment film on the surface of the base material. In addition, tests were also conducted on base materials of Comparative Examples 14 to 18 shown in Table 4, which were degreased and washed with water in the same manner as above, and then heated and dried.

It should be noted that in Tables 1 to 4, Maz represents the mass of zirconium in the zirconium compound, Mat represents the mass of titanium in the titanium compound, and Ma represents the metal (Zr and/or Ti), Mb represents the quality of the organic compound (b), Mc represents the quality of the water-based resin (c), and Md represents the quality of the metal compound (d).

The surface treatment coatings formed using the metal surface treatment agents of Examples 1 to 98 and Comparative Examples 1 to 13, and the base materials of Comparative Examples 14 to 18 were laminated by thermal lamination or dry lamination as shown below. Polypropylene film.

(hot lamination)

Next, a dispersion of acid-modified polypropylene (manufactured by Mitsui Chemicals, Inc., "R120K", non-volatile component concentration: 20%) was coated on the formed surface of the base material by the bar coating method using a #8 SUS Meller rod. After the surface of the film was treated, it was dried at 200° C. for 1 minute in a hot air circulation drying oven to form an adhesive layer. Then, this adhesive layer and a 30-micrometer-thick PP film (manufactured by Tohcello Co., Ltd., "CPPS") were heat-compressed at 190° C. and 2 MPa for 10 minutes, thereby producing a polypropylene film-laminated base material.

(dry lamination)

A polyurethane-based dry lamination adhesive (“AD-503/CAT10” manufactured by Toyomorton Co., Ltd., non-volatile content: 25%) was applied by the bar coating method using a #8 SUS Meile rod, and then circulated with hot air. Dry at 80° C. for 1 minute in a type drying oven to form an adhesive layer. Then, the corona discharge-treated surface of the adhesive layer and a 30 μm unstretched polypropylene film (manufactured by Futimura Chemical Industry Co., Ltd., "FCZX") was pressed at 100°C and 1 MPa, and then aged at 40°C. For 4 days, a polypropylene film laminate base material was thus manufactured.

Then, each of the above-mentioned polypropylene film laminate base materials produced by thermal lamination or dry lamination was subjected to deep drawing processing by a deep drawing thinning test. The laminated base material punched out to a diameter of 160 mm was drawn (first time) to produce a cup with a diameter of 100 mm. Next, this cup was drawn again (second time) to a diameter of 75 mm, and further drawn (third time) to a diameter of 65 mm to manufacture a can as a test material. In addition, the thinning (thinned portion) ratios of the first drawing, the second drawing, and the third drawing were 5%, 15%, and 15%, respectively.

[Performance Evaluation]

The initial adhesion, durable adhesion, electrolyte-resistant adhesion retention, and liquid stability after deep-drawing of each polypropylene film-laminated base material were evaluated by the methods described below. The results are shown in Table 5-Table 8.

(initial adhesion)

Initial adhesion was evaluated for the test material after deep drawing. The case where a can can be produced, no peeling of the film occurred, and excellent initial adhesion was scored as "3 points", the case of partial film peeling was recorded as "2 points", and the case where the entire surface of the film was peeled off was rated as "3 points". Recorded as "1 point". Moreover, in 3 points, the case where peeling was not observed at all, and was especially excellent in an external appearance, and was very excellent in initial stage adhesiveness was rated as "4 points."

(durable adhesion)

With regard to the test material after the deep drawing process, the durable adhesiveness was evaluated for the material after the distillation test was carried out in the gas atmosphere of the heated and pressurized steam. In the distillation test, a commercially available sterilizer (autoclave) was used, and the treatment was performed in a heated and pressurized steam atmosphere at 125° C. for 1 hour. Then, scrape the film surface with the tip of the tweezers, and the situation where no peeling of the film takes place at all is recorded as "6 points", and the case where peeling occurs but the resistance is very high is recorded as "5 points", and the case where peeling, However, the case where the resistance is high is rated as "4 points", the case where the resistance is not so high but can reach a practical level is rated as "3 points", and the case where the film can be peeled off with very weak force is rated as "2 points". , and the case where peeling of the film had already occurred was recorded as "1 point".

(Electrolyte resistance adhesion retention)

Regarding the test material after the deep drawing process, the evaluation of the electrolyte-resistant adhesion retention was performed on the material after the immersion test in the electrolyte solution for lithium-ion secondary batteries. The details are as follows: The test material after deep drawing is immersed in the electrolyte solution for lithium ion secondary batteries (electrolyte: 1M-LiPF ₆ , solvent: EC: DMC: DEC=1:1:1 (volume%)), and then put it into a constant temperature bath at 60°C for 7 days. In addition, "EC" represents ethylene carbonate, "DMC" represents dimethyl carbonate, and "DEC" represents diethyl carbonate.

Next, the test material was taken out, immersed in ion-exchanged water for 1 minute, washed by shaking, and dried at 100° C. for 10 minutes in a hot-air circulation drying oven. Then, scrape the film surface with the tip of the tweezers, and the situation where no peeling of the film takes place at all is recorded as "6 points", and the case where peeling occurs but the resistance is very high is recorded as "5 points", and the case where peeling, However, the case where the resistance is high is rated as "4 points", the case where the resistance is not so high but can reach a practical level is rated as "3 points", and the case where the film can be peeled off with very weak force is rated as "2 points". , and the case where peeling of the film had already occurred was recorded as "1 point".

(drug stability)

For the stability of the agent, the long-term stability of the metal surface treatment agent was evaluated. The details are as follows: 200 mL of the metal surface treatment agents of Examples 1 to 98 and Comparative Examples 1 to 13 shown in Table 1 to Table 4 are respectively enclosed in a 300 mL plastic container (poly container). The state of the chemical (metal surface treatment agent) after standing still for 2 weeks was evaluated. The case where solidification, separation, and precipitation did not occur at all was recorded as "3 points", the case where only precipitation was confirmed, but no solidification and separation occurred, and could reach a practical level was recorded as "2 points", and the case where solidification and precipitation were observed The case of separation was recorded as "1 point".

[table 5]

[Table 6]

[Table 7]

[Table 8]

As shown in Tables 5 to 8, it can be confirmed that the metal material with a surface treatment coating obtained by using the metal surface treatment agent and metal base material of Examples 1 to 98, regardless of thermal lamination or dry lamination, Both have excellent initial adhesion and electrolyte-resistant adhesion retention.

Claims (6)

1. A metal surface treatment agent, which contains: 1 or more Group 4 transition metal compounds (a), and organic compound (b), The Group 4 transition metal compound (a) is selected from a Zr compound that releases zirconyl ions (ZrO ²⁺ ) in an aqueous solution and a Ti compound that releases titanyl ions (TiO ²⁺ ) in an aqueous solution, The organic compound (b) has two or more functional groups selected from the group consisting of hydroxyl, carboxyl, phosphonic acid, phosphoric acid and sulfonic acid in the same molecule. 2. The metal surface treatment agent according to claim 1, wherein the molecular weight of the organic compound (b) is more than 100 and less than 1000, and the organic compound (b) is one for every molecular weight of 30 to 300 Ratio of compounds with said functional groups. 3. The metal surface treatment agent according to claim 1 or 2, wherein the difference between the quality (Mb) of the organic compound (b) and the quality (Ma) of the metal in the Group 4 transition metal compound (a) The ratio [Mb/Ma] is 0.05 to 0.6. 4. The metal surface treatment agent according to any one of claims 1 to 3, wherein it contains polyurethane resin, epoxy resin, acrylic resin, phenolic resin, polyester resin, polyvinyl resin and polyolefin One or more nonionic or anionic water-based resins (c) among resin-like resins. 5. The metal surface treatment agent according to any one of claims 1 to 4, wherein it contains a metal having one or more metal elements selected from Zr, Ti, V, Mo, W, Ce and Nb. Compound (d). 6. A metal material having a surface treatment film formed by applying the surface treatment agent according to any one of claims 1 to 5 to a metal surface.

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