TWI537421B - An aqueous metal surface treatment agent and a metal material treated with the treatment agent - Google Patents

Description

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

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

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

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

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

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

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

For example, Patent Document 1 proposes a base treatment agent containing a specific amount of a water-soluble zirconium compound, a water-soluble or water-dispersible acrylic resin having a specific structure, and a water-soluble or water-dispersible thermosetting crosslinking agent. Further, Patent Document 2 proposes a chromium-free metal surface treatment agent composed of a specific amount of a water-soluble zirconium compound and/or a water-soluble titanium compound, an organic phosphine oxide compound, and tannin. Further, Patent Document 3 proposes a metal surface treatment agent containing an aminolated phenol polymer, a specific metal compound such as Ti or Zr, and a pH of 1.5 to 6.0. Further, Patent Document 4 proposes a resin film containing an aminated phenol polymer, an acrylic polymer, a metal compound, and a phosphorus compound further required.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Patent Publication WO2002/063703

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

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

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

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

The water-based metal surface treatment agent of the present invention for solving the above-mentioned problems is characterized in that it contains two or more carboxyl groups and/or hydroxyl groups in one molecule at a ratio of one to 30 to 300 molecular weight, and has a molecular weight of 10,000. The following organic compound (A); cross-linking with a crosslinkable organic compound (B1) having a structural unit reactive with the aforementioned carboxyl group and/or the aforementioned hydroxyl group, and an element containing an element reactive with the aforementioned carboxyl group and/or the aforementioned hydroxyl group One or two or more kinds of crosslinkable compounds (B) selected from the inorganic compound (B2).

According to the invention, since the organic compound (A) and the crosslinkable compound (B) are contained, the surface-treated film obtained by treating the aqueous metal surface treatment agent has high adhesion, and even if it is exposed to acid or the like, Can maintain a high degree of closeness. As a result, even if a resin film is laminated on a metal material or a resin coating film is formed, and then subjected to a severe forming process such as deep drawing, stretching, or drawing, and the like, even if it is further exposed to an acid or an organic solvent. The laminated film or the resin coating film can also be prevented from being peeled off from the metal material at the same time.

In the aqueous metal surface treatment agent of the present invention, the crosslinkable organic compound (B1) has one selected from the group consisting of a carbodiimide bond, an oxazoline group, a glycidyl ether group, an isocyanate group, and a hydroxymethyl group. Or more than two structural units.

According to the present invention, since the crosslinkable organic compound (B1) has the above-described structural unit, the surface-treated film obtained by treating the aqueous metal surface treating agent has better adhesion and can be exposed to an organic solvent or an acid. Maintain a more stable adhesion for a long period of time.

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

According to the invention, since the crosslinkable inorganic compound (B2) contains the above-mentioned elements, the surface-treated film obtained by treating the aqueous metal surface treatment agent is more excellent in adhesion and can be held even when exposed to an organic solvent or an acid. Maintain a more stable fit during the renewal period.

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 aqueous metal surface treatment agent of the present invention to the surface of a metal material.

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

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

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

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

[Water metal surface treatment agent]

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

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

(Organic Compound (A))

The organic compound (A) is a compound containing a carboxyl group and/or a hydroxyl group of a functional group. The organic compound (A) having the carboxyl group and/or the hydroxyl group (also referred to as "functional group") can be reacted with the crosslinkable compound (B) described later to improve the adhesion of the obtained surface treated film. Sexual and drug-resistant adhesion maintenance. The above-mentioned carboxyl group and/or hydroxyl group contained in the organic compound (A) is contained in two or more molecules in a ratio of one to three molecules per molecule. The organic compound (A) containing the above carboxyl group and/or hydroxyl group in this ratio becomes more reactive with the crosslinkable compound (B). Knot As a result, the surface-treated film obtained by treating with a water-based metal surface treatment agent becomes dense, and the adhesion resistance of the drug can be further improved. The ratio of the carboxyl group and/or the hydroxyl group is more preferably two or more in one molecule in a ratio of one to 30 to 150 in molecular weight.

The organic compound (A) is a compound having a molecular weight of 10,000 or less. When the molecular weight of the organic compound (A) is 10,000 or less, the adhesion of the obtained surface-treated film can be improved, and the drug-resistant adhesion maintaining property can be made practical. When the molecular weight of the organic compound (A) exceeds 10,000, when the surface treatment film is formed, the mobility of the aqueous metal surface treatment agent becomes low, and the carboxyl group or the hydroxyl group becomes difficult to be oriented on the surface of the base metal to be in close contact with the base metal. Sex may be lower. Further, the chance of contact between the organic compound (A) and the crosslinkable compound (B) may become low, and a portion which does not crosslink may be formed, and the crosslinking density may be lowered. As a result, the surface-treated film becomes less dense, the barrier property is lowered, and the durability of the drug-resistant adhesion is lowered. The barrier property refers to a property of preventing a drug such as an acid or an organic solvent from penetrating into a surface treatment film. When the molecular weight of the organic compound (A) is 5,000 or less, it is more preferably 3,000 or less.

Examples of the organic compound (A) include oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, itaconic acid, propane dicarboxylic acid, butane dicarboxylic acid, pentane dicarboxylic acid, and hexane. a polyvalent carboxylic acid such as a dicarboxylic acid, a heptane dicarboxylic acid, a butane tricarboxylic acid, a butane tetracarboxylic acid, a cyclohexanetetracarboxylic acid or a hexanetricarboxylic acid; ethylene glycol, propylene glycol, butylene glycol Polyvalent alcohols such as hexanediol, polyethylene glycol, thiodiethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyethylene glycol, polypropylene glycol, etc.; malic acid, citric acid, tartaric acid Polyvalent hydroxycarboxylic acid; hexahydroxybenzene, pyrogallol, 1,2,4-trihydroxybenzene, phloroglucinol, catechol, resorcinol, hydroquinone, 5-methylorthophenone Trisphenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 3-methylcatechol, 4-methylcatechol, A Hydroquinone, 2,6-dimethylhydroquinone, 5-methoxy resorcinol, 3-methoxycatechol, methoxyhydroquinone, 2,5-dihydroxy-1,4- Benzoquinone, gallic acid, pyrogallol-4-carboxylic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoin Acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2 ,6-dihydroxy-4-methylbenzoic acid, 4-hydroxy-3,5-dimethylbenzoic acid, 1,4-dihydroxy-2-naphthoic acid, methyl gallate, 2,4-dihydroxy Methyl benzoate, methyl 2,6-dihydroxybenzoate, methyl 3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate, ethyl 3,4-dihydroxybenzoate, 4 ,6- Diaminoresorcinol dihydrochloride, 4,6-diaminoresorcinol, 2-nitroresorcinol, 4-nitrocatechol, meliic acid, benzenepentacarboxylic acid, Pyromellitic acid, trimellitic acid, hemi-milic acid, symmetrical trimellitic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene Carboxylic acid, 2,6-naphthalene dicarboxylic acid, 4-methylphthalic acid, 5-methylisophthalic acid, 2,5-dimethylterephthalic acid, 4-hydroxyphthalic acid, 5-hydroxyisophthalic acid, 4-nitrophthalic acid, 5-nitroisophthalic acid, 5-aminoisophthalic acid, 4-aminosalicylic acid, 4-amino-3- a cyclic organic compound such as hydroxybenzoic acid or L-ascorbic acid; Hydrolyzable tannins such as tannic acid; condensed tannins such as persimmon tannins, theaflavins, and thearubigins.

The content of the organic compound (A) contained in the aqueous metal surface treatment agent is preferably 10% by mass to 95% by mass, and more preferably 20% by mass based on the total solid content contained in the aqueous metal surface treating agent. 80% by mass, particularly preferably 20% by mass to 70% by mass. When the content of the organic compound (A) is within this range, the denseness of the surface-treated film can be further improved, whereby the durability of the drug-resistant adhesion can be further improved. In addition, the "all solid components" means a solid component obtained by removing a volatile component such as a solvent among components of the aqueous metal surface treatment agent, specifically, an organic compound (A) and a crosslinkable organic component. The total amount of one or two or more kinds of crosslinkable compounds (B) selected from the compound (B1) and the crosslinkable inorganic compound (B2). Therefore, the organic compound (A) contained in the aqueous metal surface treatment agent is preferably 10% by mass to 95% by mass based on the total amount (all solid components) of the organic compound (A) and the crosslinkable compound (B). %, more preferably 20% by mass to 80% by mass, particularly preferably 20% by mass to 70% by mass.

(crosslinkable compound (B))

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

(crosslinkable organic compound (B1))

The crosslinkable organic compound (B1) is an organic compound having a structural unit capable of reacting with a carboxyl group and/or a hydroxyl group of the organic compound (A). "Reactive" means that it can react with either or both of a carboxyl group and a hydroxyl group which the organic compound (A) has. "Structural unit" means a functional group or a single bond unit. "Having" means that other functional groups or bonding units may be present in addition to the structural units. The crosslinkable organic compound (B1) may, for example, be organic having one or two or more structural units selected from the group consisting of a carbodiimide bond, an oxazoline group, a glycidyl ether group, an isocyanate group, and a hydroxymethyl group. Compound.

The organic compound having a carbodiimide bond is not particularly limited, and for example, a polycarbodiimide compound can be used. As the polycarbodiimide compound, a decarboxylation reaction having a decarboxylation reaction by, for example, a diisocyanate compound having an aromatic ring or a diisocyanate compound having an aromatic ring and an aliphatic or alicyclic diisocyanate compound can be used. The obtained isocyanate group at both ends of the polymer of 5 to 15 carbodiimide bonds, and a nonionic or cationic polycarbodiimide compound obtained by blocking a polyol compound or a polyamine. When the isocyanate group is blocked with a polyamine, it is preferred to further act on the acid or alkylating agent to bond the hydrogen atom or the alkyl group to at least a portion of the nitrogen atom forming the secondary amine or tertiary amine moiety from the polyamine. Cationization.

The diisocyanate compound having an aromatic ring used in the decarboxylation reaction may, for example, be 3,3'-dimethoxy-4,4'-linked phenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,5. - tetrahydronaphthalene diisocyanate, 2,4-strandyl Diisocyanate (TDI), 2,6-streptyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, phenyl diisocyanate, two Tolyl diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), and the like.

Examples of the aliphatic or alicyclic diisocyanate compound used for the decarboxylation reaction include tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate, and hydrogenated xylylene diisocyanate. 4-cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and the like.

The method for synthesizing the polycarbodiimide compound by the decarboxylation reaction is not particularly limited, and a method generally used for the synthesis of a polycarbodiimide compound can be used. For example, a method of decarbonating a plurality of the above diisocyanate compounds in an inert organic solvent in the presence of a carbodiimidation catalyst at a constant temperature. As the bismuth imidization catalyst, 1-phenyl-2-cyclophosphene-1-oxide, 3-methyl-2-cyclophosphene-1-oxide, 1-ethyl-2-ring can be used. Phosphine-1-oxide, 1-ethyl-3-methyl-2-cyclophosphene-1-oxide or 3-methyl-1-phenyl-2-cyclophosphene-1-oxide, Or a cyclophosphene oxide such as a 3-cyclophosphene isomer. As the inert organic solvent, for example, an ether solvent such as tetrahydrofuran or 1,4-dioxane; a ketone solvent such as cyclohexanone or acetone; a hydrocarbon solvent such as hexane or benzene; or the like can be used.

The number of the carbon diimine bond in the molecule of the polycarbodiimide compound obtained by the above decarboxylation reaction is preferably 5 to 15, more preferably 7 to 13. By making the number of carbodiimide bonds in the range of 5 to 15, The adhesion of the surface treatment film obtained by the treatment with the metal surface treatment agent can be further improved, and the resin film or the like can be strongly adhered to the base metal. Further, since the structure of the polycarbodiimide compound becomes soft, the obtained surface-treated film has flexibility, and even if it is subjected to severe molding, the resin film or the like is difficult to be peeled off.

When the number of carbodiimide bonds is less than 5, the reactivity of the polycarbodiimide compound increases, and the cross-linking is excessively promoted, so that the obtained surface-treated film easily becomes a hard and brittle surface-treated film. . Further, when the number of the carbodiimide bonds exceeds 15, the reactivity is excessively lowered, the crosslinking becomes insufficient, and the water dispersibility is also lowered. When the crosslinking becomes insufficient, the obtained surface treated film becomes dense, and the chemical adhesion maintaining property is lowered.

Further, a solution of a polycarbodiimide compound or a polyamine is further added to the solution of the polycarbodiimide compound obtained by the above decarboxylation reaction to block the isocyanate groups at both ends. The polyhydric alcohol-based compound may, for example, be a poly(alkylene glycol) represented by the following chemical formula (1) or a monoalkyl ether thereof, and the polyamine may be a polyamine represented by the following chemical formula (2) or a chemical formula (3) a poly(alkylenediamine) N-alkyl derivative represented by . Further, in the chemical formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 2 to 30; in the chemical formula (2) R ³ to R ⁶ represent an alkyl group having 1 to 4 carbon atoms, and R ⁷ represents an alkanetriyl group having 2 to 4 carbon atoms; in the chemical formula (3), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ⁹ represents an alkyl group having 1 to 4 carbon atoms, R ¹⁰ represents an alkylene group having 2 to 4 carbon atoms, and m represents an integer of 2 to 30.

[1] R ¹ O(R ² O) _n H (1)

[Chemical 3] R ⁸ R ⁹ N(R ¹⁰ NH) _m H (3)

In the chemical formulae (1) to (3), the alkyl group having 1 to 4 carbon atoms in the definition of R ¹ , R ³ to R ⁶ , R ⁸ and R ⁹ may, for example, be a methyl group, an ethyl group, a propyl group or an isopropyl group. A base, a butyl group or the like, among which a methyl group and an ethyl group are particularly preferred. R ² and R ¹⁰ may, for example, be an ethyl group, a propyl group or a n-butyl group, and particularly preferably an ethyl group and a propyl group. Examples of R ⁷ include an ethane triyl group, a propane triyl group, a butane triyl group, and the like.

The poly(alkylene glycol) represented by the formula (1) or a monoalkyl ether thereof, specifically, a poly(ethylene glycol) having n of 2 to 30, a monomethyl group thereof or a monoethyl group thereof Ether, or n is a poly(propylene glycol) of 2 to 30, a monomethyl group thereof or a monoethyl ether thereof. Specific examples of the polyamine represented by the chemical formula (2) include 3,3-bis(dimethylamino)propylamine and 3,3-bis(diethylamino)propylamine. The poly(alkylenediamine) N-alkyl derivative represented by the chemical formula (3), specifically, one of the terminal amine groups of m (ethylenediamine) having m of 2 to 30 is monomethyl Base or dimethylation, or monoethylated or diethylated.

When the polyisocyanate group of the polycarbodiimide compound is blocked by the polyamine of the chemical formula (2) or the chemical formula (3), the acid is further added to the reaction solution containing the polycarbodiimide compound. Or an alkylating agent which bonds a hydrogen atom or an alkyl group to at least a portion of a nitrogen atom forming a secondary or tertiary amine moiety of the chemical formula (2) or the chemical formula (3) to be cationized.

The acid used for the cationization may be an inorganic acid or an organic acid, and examples thereof include sulfuric acid, hydrogen halide acid (hydrogen chloride gas, hydrochloric acid, hydrofluoric acid, etc.), phosphorous acid, phosphoric acid, and alkyl sulfuric acid (methyl sulfuric acid, Ethyl sulfuric acid, etc.), formic acid, acetic acid, and the like. Examples of the alkylating agent used for the cationization include halogenation of dialkylsulfuric acid such as dimethylsulfuric acid or diethylsulfonic acid, methyl chloride, ethyl chloride, propyl chloride, and chlorobutyl. Alkyl and the like.

The polycarbodiimide compound is usually used in the form of an aqueous solution or a water-dispersed form. The water dispersion form may be in the form of an emulsion or a colloidal dispersion. The method of the aqueous solution form or the water dispersion form is not particularly limited. For example, a method in which the cationization is carried out by an acid or an alkylating agent as described above, followed by addition of water, followed by distillation of an inactive organic solvent or the like to obtain an aqueous solution form or an aqueous emulsion form can be employed. The dissolution or dispersion of water can be achieved based on either self-solubility or self-dispersibility, or by a cationic surfactant (for example, a tetraalkylammonium salt, etc.) and a nonionic interface. It is achieved in the presence of one or more selected from the group consisting of active agents (for example, polyoxyalkylene alkylphenyl ethers). From the viewpoint of maintaining the adhesion of the surface-treated film treated with the aqueous metal surface treatment agent and maintaining the adhesion of the drug, it is preferred to use a polycarbodiimide compound without using a surfactant. It has the action of a hydrophilic group and dissolves or disperses water in terms of self-solubility or self-dispersibility.

The organic compound containing an oxazoline group is not particularly limited, and a conventionally known emulsion type or water-soluble type oxazoline group-containing resin can be used. Both an emulsion type and a water soluble type can also be used. The emulsion type means the type of water dispersion formed in water, and the water soluble type means the formation of an aqueous solution in water or the like. type. For the oxazoline group-containing resin, for example, a copolymer obtained by polymerizing one or more selected ones of the addition polymerizable oxazoline compound and another monomer may be mentioned.

The addition polymerizable oxazoline compound, specifically, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl -2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxo As the oxazoline, one or a mixture of two or more selected from the group can be used. Among these, 2-isopropenyl-2-oxazoline is industrially easy to obtain and suitable.

The amount of the addition-polymerizable oxazoline compound to be used is not particularly limited, but is preferably 5% by mass or more based on the total mass of the mixture of the addition polymerizable oxazoline compound and another monomer. When the amount is less than 5% by mass, the degree of crosslinking with the upper layer tends to be insufficient, and the resistance to drug adhesion is insufficient.

The other monomer is not particularly limited as long as it is a monomer which does not react with the oxazoline group and can be copolymerized with the addition polymerizable oxazoline compound, and examples thereof include methyl (meth)acrylate and (methyl). Ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-aminoethyl (meth)acrylate and (meth)acrylates such as these salts; unsaturated nitriles such as (meth)acrylonitrile; (meth)acrylamide, N-hydroxyl An unsaturated decylamine such as methyl (meth) acrylamide or N-(2-hydroxyethyl) (meth) acrylamide; a vinyl ester of vinyl acetate or vinyl propionate; Vinyl ether, ethyl vinyl a vinyl ether such as an ether; an α-olefin such as ethylene or propylene; a halogen-containing α,β-unsaturated monomer such as a vinyl chloride, a vinylidene chloride or a fluorinated vinyl; styrene; An α,β-unsaturated aromatic monomer such as α-methylstyrene or sodium styrenesulfonate. One or a mixture of two or more selected from the group may be used.

In the method for producing an oxazoline group-containing resin of the emulsion type, one or two or more selected from the above-mentioned other monomers may be used, and a conventionally known polymerization method can be used. The method of polymerization. Among the conventionally known polymerization methods, an emulsion polymerization method is particularly preferably used.

As the emulsion polymerization method, a conventionally known polymerization initiator, a surfactant, a solvent, or the like can be used, and a method such as a so-called monomer titration method, a multistage polymerization method, or a pre-emulsion method can be used. Specifically, a mixture of an addition-polymerizable oxazoline compound and one or a mixture of two or more selected from the above-mentioned other monomers may be dispersed in an aqueous solvent containing a conventionally known surfactant. A polymerization initiator is then added to polymerize.

The surfactant is not particularly limited, and examples thereof include an anionic surfactant such as sodium n-dodecylbenzenesulfonate or sodium laurate; and a nonionic surfactant such as nonylphenol ether of polyethylene glycol. . The polymerization initiator is not particularly limited, and examples thereof include hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, benzammonium peroxide, lauryl peroxide, and diisopropylphenyl. a peroxide such as an oxide, di-tert-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide or diisopropylbenzene hydroperoxide; 2,2'-azobis Isobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), azobiscyanovaleric acid, 2,2'-azobis-(2-methylpropanylpropane) An azo compound such as a dihydrochloride salt.

An aqueous solvent, either water or a mixture of water and an organic solvent. The organic solvent is not particularly limited as long as it can be mixed with water. Examples of such an organic solvent include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol. Alcohol, acetone, methyl ethyl ketone, and the like.

When the structure of the oxazoline group-containing resin of the emulsion type is a core-shell structure, the core portion may be selected from the above-mentioned other monomers without containing an addition polymerizable oxazoline compound as a monomer. One or two types of acrylic emulsions, and the shell portion contains an addition polymerizable oxazoline compound and one or two or more kinds of oxazoline group-containing polymer layers selected from the other monomers described above. A resin containing an oxazoline group. As a method for producing the oxazoline group-containing resin having such a shell structure, a known method such as a multi-stage feeding method or a motor feeding method can be used.

A conventionally known polymerization method can be used as the method for producing the water-soluble oxazoline group-containing resin. For example, one or two kinds of the addition polymerizable oxazoline compound and the other monomer described above can be used. Above, a method of solution polymerization in an aqueous solvent. Specifically, for example, one or a mixture of two or more kinds of the addition-polymerizable oxazoline compound and the other monomer may be dispersed in an aqueous solvent, followed by addition of a polymerization initiator. polymerization. The polymerization initiator and the aqueous solvent are not particularly limited, and the same ones as those used in the production of the oxazoline group-containing resin of the above emulsion type can be used.

In order to become "water soluble", one of the other monomers mentioned above Or two or more types, and it is preferable to contain a hydrophilic monomer. The hydrophilic monomer may, for example, be exemplified by 2-hydroxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, or 2-amino(meth)acrylate among the other monomers mentioned above. Ethyl ester and its salt, (meth) acrylamide, N-methylol (meth) acrylamide, N-(2-hydroxyethyl) (meth) acrylamide, (meth) acrylonitrile , sodium styrene sulfonate, and the like.

The ratio of the hydrophilic monomer contained in the water-soluble oxazoline group-containing resin is preferably 50% by mass or more, based on the total mass of the addition polymerization oxazoline compound and other monomer mixture. Good is 70% by mass or more. When the hydrophilic monomer is contained in an amount of 50% by mass, the oxazoline group-containing resin can be easily made water-soluble.

The organic compound having a glycidyl ether group is not particularly limited, and a conventionally known polyvalent glycidyl ether compound can be used. Specific examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl ether. And diglycerin glycidyl ether, polyglyceryl triglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, and the like.

Examples of the organic compound having an isocyanate group include an isomer of tolyl diisocyanate; an aromatic diisocyanate such as 4,4'-diphenylmethane diisocyanate; and an aromatic aliphatic group such as xylylene diisocyanate. Diisocyanate; alicyclic diisocyanate such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate; hexamethylene diisocyanate An aliphatic diisocyanate such as an ester or 2,2,4-trimethylhexamethylene diisocyanate. The organic compound having an isocyanate group is not particularly limited, but from the viewpoint of the stability of the aqueous metal surface treatment agent, it is preferred to use an isocyanate compound which is blocked by various blocking agents. Examples of the blocking agent include various blocking agents such as a phenol type, an alcohol type, an anthraquinone type, an active methylene type, an acid amide type, an aminoformate type, and a sulfite type.

The organic compound which has a methylol group, for example, one or two or more selected from the group consisting of a soluble phenol resin, methylol melamine, and N-methylol acrylamide monomer may be used as a constituent unit for homopolymerization or Copolymer.

(crosslinkable inorganic compound (B2))

The crosslinkable inorganic compound (B2) is a compound containing an element which can react with a carboxyl group and/or a hydroxyl group of a functional group which the organic compound (A) has. "Reactive" means that it can be reacted with either or both of a carboxyl group and a hydroxyl group. "Include" means that there may be other elements in addition to those elements.

As the crosslinkable inorganic compound (B2), a conventionally known inorganic substance containing an element capable of reacting with a carboxyl group and/or a hydroxyl group which the organic compound (A) has can be used can be used. For example, it may be composed of Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, An inorganic compound of one or more elements selected from the group consisting of In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La. Among them, it contains Mg, Al, Ca, Mn, Cr(III), Zn, Fe, An inorganic compound of one or more selected from the group consisting of Zr, Ti, Si, Ce, Te, and Hf is more preferable, and one selected from the group consisting of Cr(III), Zr, Ti, Si, Ce, and Te or The inorganic compound of two or more elements is more preferable.

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

More specifically, bis(ethylmercaptopyruvate) magnesium dihydrate (II), magnesium aluminate, magnesium benzoate, magnesium formate, magnesium oxalate, magnesium tungstate, magnesium metasilicate, magnesium borate, molybdic acid Magnesium salt of magnesium, magnesium iodide, magnesium pyrophosphate, magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, magnesium ammonium phosphate, magnesium hydrogen phosphate, magnesium oxide, etc.; aluminum nitrate, aluminum sulfate, sulfuric acid Potassium aluminum, aluminum sulfate aluminum, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum oxide, aluminum fluoride, aluminum iodide, aluminum acetate, aluminum benzoate, aluminum citrate, aluminum gluconate, Aluminum salts of aluminum selenate, aluminum oxalate, aluminum tartrate, aluminum lactate, aluminum palmitate, etc.; bis(acetylthiopyruvate) calcium (II) dihydrate, calcium benzoate, calcium citrate, calcium metastannate, Calcium selenate, calcium tungstate, calcium carbonate, calcium tetraborate, calcium molybdate, calcium maleate, calcium malate, calcium pyrophosphate, calcium fluoride, calcium hypophosphite, calcium nitrate, calcium hydroxide, calcium oxide, Calcium salt of calcium oxalate, calcium oxide, calcium acetate, etc.; bis(acetylthiopyruvate) manganese (II) dihydrate, trimanganese tetraoxide, Manganese (II) oxide, manganese (III) oxide, manganese (IV) oxide, manganese (II) bromide, manganese (II) oxalate, permanganic acid (VII), potassium permanganate (VII), sodium permanganate (VII), manganese dihydrogen phosphate (II), manganese nitrate (II), manganese (II) sulfate, manganese (III) sulfate, manganese (IV) sulfate, manganese (II) fluoride, manganese (III) fluoride, Manganese salts such as manganese (II) carbonate, manganese (II) acetate, manganese (III) acetate, manganese (II) sulfate, manganese (II) oxide, manganese (II) oxide, etc. or manganeseate; (Ethyl pyruvic acid) cobalt (II) dihydrate, cobalt (III) ginsengyl pyruvate, cobalt (II) amine sulfonate, cobalt (II) chloride, chloropentachlorocobalt chloride (III ), hexaammine cobalt chloride (III), diammonium tetranitrocobalt (III) acid ammonium, cobalt sulfate (II), ammonium sulfate cobalt, cobalt (II) nitrate, cobalt aluminum oxide, cobalt hydroxide (II) Cobalt (II) oxide, cobalt phosphate, cobalt (II) acetate, cobalt (II) formate, cobalt trioxide, cobalt (II) bromide, cobalt (II) oxalate, cobalt (II) selenate, cobalt (II) sulphate a cobalt salt of cobalt (II) hydroxycarbonate, cobalt (II) molybdate, cobalt (II) iodide, cobalt (II) phosphate, etc.; nickel (II) diamine sulfonate, nickel (II) benzoate, nitric acid Nickel (II), nickel (II) sulfate, nickel (II) carbonate, acetone Nickel ruthenium (II), nickel (II) chloride, hexachloronickel chloride, nickel oxide, nickel (II) hydroxide, nickel (II) oxide, nickel acetate, nickel (II) citrate, succinic acid Nickel (II), nickel (II) bromide, nickel (II) oxalate, nickel (II) tartrate, nickel (II) sulphate, nickel (II) hydroxycarbonate, nickel (II) lactate, nickel (II) molybdate a nickel salt such as nickel (II) iodide or nickel (II) diphosphate; Chromium (III), chromium (III), chromium (III), chromium (III) sulfate, chromium (III) oxalate, chromium (III) acetate, chromium (III) phosphate, chromium (III) , chromium (III) oxide, chromium (III) bromide, chromium (III) and other chromium salts; bis(ethylmercaptopyruvate) zinc (II), zinc benzoate (II), zinc hydroxychloride (II), zinc (II) hydride, zinc (II) citrate, zinc (II) bromide, zinc (II) oxalate, zinc (II) tartrate, zinc (II) bis stannate, zinc (II) selenate , zinc tungstate (II), zinc (II) fluoride, zinc (II) molybdate, zinc (II) butyrate, zinc (II) pyrophosphate, zinc (II) sulfate, zinc (II) carbonate, zinc chloride (II), zinc salt of zinc iodide (II), zinc (II) hydroxide, zinc oxide (II), etc.; bis(ethylmercaptopyruvate) iron (II) dihydrate, ginseng (acetonitrile) Acid) iron (III), tripotassium trioxalate, iron (II) formate, iron (III) tetravanadate, iron (III) bromide, iron (III) tartrate, iron (II) lactate, iron fluoride ( II), iron (III) fluoride, iron (II) chloride, iron (III) chloride, iron (II) iodide, iron (III) iodide, iron (II) sulfate, iron (III) sulfate, Iron (II) nitrate, iron (III) nitrate, iron (II) acetate, iron (III) acetate, iron citrate II) Iron (III) citrate, iron (II) glycinate, iron (III) glycinate, iron (II) oxalate, iron (III) oxalate, iron (II) pyridinecarboxylate, iron (III) picolinate , L-phenylalanine iron (II), L-phenylalanine iron (III), iron (II) malonate, iron (III) malonate, iron (II) hydroxide, iron hydroxide ( III), iron oxides such as iron oxide (II), iron oxide (III), and triiron tetroxide; Bis(acetylthiopyruvate) ruthenium (II) dihydrate, ruthenium (II) ruthenate, ruthenium ruthenate (II) bismuth tungstate, bismuth metasilicate, ruthenium oxide (IV), ruthenium (II) oxide, bismuth oxalate , bismuth citrate, bismuth molybdate, cesium iodide, cerium nitrate, cerium sulfate, cerium carbonate, cerium acetate, cerium chloride, cerium phosphate, cerium lactate, etc.; oxadioxalate titanium diammonium, oxygen Titanium oxalate, titanium oxide (II), titanium oxide (III), titanium oxide (IV), titanium (IV) oxysulfate, alkaline titanium phosphate, titanium (IV) bromide, metatitanic acid, zinc metasilicate (II), aluminum titanate (III), potassium metatitadate, cobalt (II) metasilicate, zirconium titanate, barium titanate, iron (III) titanate, copper (II) metasilicate, titanium Sodium, barium (III) dititanate, barium metasilicate barium, barium (III) metasilicate, magnesium metatitadate, magnesium titanate, manganese (II) metasilicate, barium (III) dititanate, partial Lithium titanate, ammonium hexafluorotitanium (IV), potassium hexafluorotitanate (IV), titanium (IV) iodide, titanium (III) sulfate, titanium (IV) sulfate, titanium chloride, titanium nitrate, sulfuric acid Titanium, titanium (III) fluoride, titanium (IV) fluoride, hexafluorotitanate, titanium lactate, peroxotitanic acid, titanium laurate, titanium pyridinium acetate, titanium hydroxide (IV), etc. Titanium salt or the like or titanate; zirconium (IV), cerium (acetyl) pyruvate, zirconium (IV) chloride, zirconium (IV) chloride, zirconium silicate, zirconium (IV) acetate, zirconia (IV), nitric acid zirconia (IV), meta-zirconium zirconate, lithium meta-zirconate, zinc meta-zirconate (II), aluminum meta-zirconate (III), calcium metachromate, cobalt meta-zirconate (II), Bismuth zirconate, copper (II) meta-zirconate, sodium meta-zirconate, nickel (II) meta-zirconate, bismuth meta-zirconate, bismuth zirconate (III), magnesium meta-zirconate, zirconium oxycarbonate, hexafluoro Zirconium (IV) acid, potassium hexafluorozirconate (IV), zirconium iodide, Zirconium dihydrogen phosphate (IV), basic zirconium carbonate, ammonium zirconium carbonate, ammonium hydrogen carbonate, zirconium nitrate, zirconyl nitrate, zirconium sulfate (IV), zirconyl sulfate, hexafluorozirconic acid, zirconyl oxyphosphate, coke a zirconium salt such as zirconium phosphate, zirconium oxyhydroxide, zirconium oxychloride, zirconium fluoride, zirconyl acetate, zirconium oxide or zirconium hydroxide; a ceric acid salt such as hexafluoroantimonic acid or cerium oxide; Tungsten (VI), iron (III) oxide, tungsten (VI), tungsten dichloride, tungsten dioxide, tungsten trioxide, metatungstic acid, ammonium metatungstate, sodium metatungstate, secondary Tungstic acid, ammonium paratungstate, sodium paratungstate, zinc (II) tungstate, potassium tungstate, calcium tungstate, cobalt (II) tungstate, barium tungstate, barium tungstate, copper (II) tungstate, nickel tungstate , tungstate tungstate, magnesium tungstate, manganese (II) tungstate, lithium tungstate, phosphotungstic acid, ammonium phosphotungstate, sodium tungstate, etc. or tungstate; ginseng Acid) cerium (III), cerium (III) chloride, cerium (III) oxide, cerium (IV) oxide, cerium (III) bromide, cerium (III) oxalate, cerium (IV) hydroxide, ammonium cerium sulfate ( IV), Ammonium sulphate (III), cerium (III) carbonate, barium sulfate, cerium (III) acetate, cerium (III) nitrate, sulfur Barium salts of cerium (IV), cerium (III) fluoride, cerium (III) iodide, cerium (III) phosphate, etc.; molybdenum chloride (V), molybdenum oxide (IV), molybdenum oxide (VI), molybdenum Zinc (II), potassium molybdate, calcium molybdate, cobalt (II) molybdate, bismuth molybdate, nickel (II) molybdate, bismuth molybdate, bismuth molybdate (III), magnesium molybdate, lithium molybdate , molybdenum molybdate, bismuth molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium molybdate, molybdic acid, ammonium molybdate, ammonium paramolybdate, molybdate, etc. or molybdate; Oxygen vanadium dichloride, oxygen vanadium trichloride, vanadium trichloride, vanadium oxide, tetravanado Iron (III), vanadium (III) bromide, vanadium oxalate, vanadium (II) iodide, vanadium pentoxide, metavanadic acid, sodium metavanadate, sodium vanadate, ammonium metavanadate, sodium metavanadate , vanadate vanadate, oxygen vanadium trichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyethanoacetate, vanadium acetoxy acetate, vanadium molybdate, etc. Or vanadate, etc.; tin (II) chloride, tin (II) acetate, tin (II) oxalate, tin (II) tartrate, tin (IV) oxide, tin nitrate, tin sulfate, tin (II) fluoride, Tin (II) iodide, tin (IV) iodide, tin (II) pyrophosphate, metastannic acid, zinc metastannate, calcium metastannate, barium metastannate, barium metastannate, magnesium metastannate, etc. Tin salt or stannate; bismuth benzoate (III), cerium (III) chloride, cerium (III) citrate, cerium (III) oxychloride, cerium (III) oxidized tartrate, cerium (III) oxide , bismuth oxysulfate, cerium (III) bromide, cerium (III) tartrate, cerium (III) hydroxide, cerium oxycarbonate, cerium (III) hydride, cerium oxynitrate, cerium (III) tetratitanate, Barium strontium trititanate (III), cerium (III) hydride, cerium (III) molybdate, cerium (III) iodide, cerium (III) nitrate, cerium (III) chloride, cerium sulfate (III) ), cerium (III) acetate, cerium (III) phosphate, etc.; cerium chloride (V), cerium oxide (V), cerium bromide (V), citric acid, potassium hexanoate, hexamic acid锶, sodium metasilicate, lithium metasilicate, cesium iodide (V), pyruvate oxime oxime, bismuth citrate, ammonium hexanoate, potassium hexafluoroantimonate, etc. or citrate Etc.; citric acid, ammonium bismuth citrate, potassium metasilicate, sodium metasilicate, cesium iodide (IV), potassium citrate, sodium citrate, sulfonic acid, potassium citrate, sulfonic acid Sodium, bismuth subruthenate, lithium niobate, ruthenium (IV) chloride, ruthenium (IV) oxide, ruthenium (IV) bromide, ruthenium hydroxide, antimony trioxide, zinc ruthenate, etc. Phthalate, etc.; indium (III) (acetyl) pyruvate, indium (III) guanamine, indium dichloride, indium (I) chloride, indium (III) chloride, indium (III) acetate Indium salts of indium (III) bromide, indium (III) iodide, indium (III) nitrate, indium (III) sulfate, indium (III) fluoride, indium (III) oxide, and indium (III) hydroxide Etc.; bis(ethylmercaptopyruvate) ruthenium (II) dihydrate, bismuth selenite, bismuth citrate, bismuth benzoate, strontium aluminate, cesium chloride, cesium formate, bismuth citrate, bismuth oxide, bromine Antimony, bismuth oxalate, barium tartrate, barium zirconate, barium hydroxide, barium metasilicate, barium tungstate, barium metasilicate, barium metasilicate, barium lactate, barium metaborate, barium molybdate, iodide Barium salts such as barium, strontium hydrogen phosphate, barium carbonate, barium fluoride, etc.; barium (IV) pyridinium (IV), barium chloride (IV), barium oxide (IV), barium iodide (IV) , barium sulfate (IV), cerium (IV) nitrate, cerium (IV) oxide, fluoroantimonic acid, fluoroantimonate, barium fluoride, etc. Potassium selenite, potassium hydrogen selenite, trihydroanthracene selenite, sodium hydrogen selenite, lithium hydrogen selenite, copper (II) selenite, sodium selenite, barium selenite, oxygen Selenium chloride, selenium chloride (I), selenium (IV) chloride, selenium (IV) oxide, aluminum selenate, selenate, zinc selenite, potassium selenate, ammonium selenate, calcium selenate, selenic acid Selenium salts such as cerium, cobalt selenate, copper (II) selenate, nickel selenate, sodium selenate, strontium selenate, zinc selenate, etc. or selenate; Barium (III) chloride, barium (III) carboxylate, barium (III) acetate, barium (III) nitrate, barium (III) oxide, barium (III) fluoride, barium (III) iodide, barium (III) sulfate Such as strontium salt, etc.; cerium (II) oxide, cerium oxide (V), bismuth (hydrogen oxalate) strontium, strontium hydroxide (V), pyruvate oxime oxime Bismuth citrate, bismuth citrate, magnesium metasilicate, lithium metasilicate, ammonium metamonate, sodium metasilicate, cesium pentachloride, etc. or citrate; guanamine sulphate (II) ), copper benzoate (II), copper (II) nitrate, copper (II) citrate, copper (I) oxide, copper (I) bromide, copper (II) oxalate, copper (II) formate, Copper (II) acetate, copper (II) propionate, copper (II) pentoxide, copper (II) gluconate, copper (II) tartrate, copper (II) chloride, copper (II) bromide, copper hydroxide (II), copper (II) acetate, copper (II) nitrate, copper (II) sulfate, copper (II) carbonate, copper (II) oxide, copper (II) hydroxy nitrate, copper (II) tungstate, hydrogen carbonate Copper (II) oxide, copper (II) lactate, copper (II) fluoride, copper (I) and other copper salts; ginsengylpyruvate ruthenium (III), ruthenium chloride (III) , cerium (III) formate, cerium (III) citrate, B钇(III), cerium (III) oxide, cerium (III) oxalate, cerium (III) nitrate, cerium (III) carbonate, cerium (III) fluoride, cerium (III) hydride, cerium (III) sulfate, phosphoric acid Barium salts such as cerium (III); cerium (III), cerium (III) chloride, cerium (III) carboxylic acid, cerium (III) acetate, cerium (III) oxide, cerium oxalate (III), cerium (III) nitrate, cerium (III) carbonate, cesium fluoride (III), barium (III) dititanate, barium (III) sulfate, barium (III) phosphate, barium (III) iodide, etc.; ginsylpyruvate, ruthenium (III), chlorine Antimony (III), antimony (III) formate, antimony (III) acetate, antimony (III), antimony (III) bromide, antimony (III) oxalate, antimony (III) nitrate, antimony (III) carbonate, Barium salts such as barium (III) titanate, cerium (III) fluoride, cerium (III) iodide, cerium (III) sulfate, cerium (III) phosphate, and the like. These compounds may be anhydrous or hydrated. Further, these may be used alone or in combination of two or more. Further, it may be dissolved in the aqueous metal surface treatment solvent or may be dispersed.

The total of the content of the crosslinkable compound (B) selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) (B=B1+B2) is preferably relative to The total solid content is from 5% by mass to 90% by mass, more preferably from 10% by mass to 80% by mass, even more preferably from 20% by mass to 80% by mass. When the content of the crosslinkable compound (B) is in the range of 5% by mass to 90% by mass, the adhesion of the surface-treated film and the durability of the drug-resistant adhesion are further improved.

(solvent)

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

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

(other additives)

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

(Modulation method of water metal surface treatment agent)

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

[metallic material]

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

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

Further, in FIG. 1, although the surface treatment film 2, the resin film 3, or the resin coating film 3 is formed on the surface on one side of the base metal 1, it may be on both sides of the base metal 1, that is, The surface treatment film 2 is also formed on the surface on the other side, and the resin film 3 or the resin coating film 3 is further provided.

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

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

As the copper alloy, it is preferable to contain 50% by mass or more of copper, and for example, brass or the like can be used. Examples of the alloy component other than copper in the copper alloy include Zn, P, Al, Fe, Ni, and the like. As the aluminum alloy, those containing 50% by mass or more of aluminum are preferable, and for example, an Al-Mg-based alloy or the like can be used. Examples of the alloy component other than aluminum in the aluminum alloy include Si, Fe, Cu, Mn, Cr, Zn, Ti, and the like. As the alloy steel, those containing 50% by mass or more of iron are preferable, and for example, stainless steel or the like can be used. Examples of the alloy component other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr, Mo, and the like. As the nickel alloy, those containing 50% by mass or more of nickel are preferable, and for example, a Ni-P alloy or the like can be used. Examples of the alloy component other than nickel in the nickel alloy include Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, and P.

The base metal 1 may be formed on the surface of a metal material, a ceramic material or an organic material other than the above-mentioned metal material to form a film containing the above metal element. Such a metal film can be formed, for example, by a method such as plating, vapor deposition, or coating. Further, the shape, structure, and the like of the base metal 1 are not particularly limited, and for example, a plate-shaped or foil-shaped metal material can be used.

As described above, the aqueous metal surface treatment agent according to the present invention contains the organic compound (A) and one selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2). Further, since the cross-linking compound (B) is used, the surface-treated film obtained by treating the aqueous metal surface treatment agent has high adhesion, and can maintain high adhesion even when exposed to an acid or the like. The result, even if it is formed The surface of the surface-treated metal film is laminated with a resin film or a resin coating film, and then subjected to a severe forming process such as deep drawing, stretching, or drawing, and further exposed to an acid or an organic solvent. It is also possible to prevent the laminated film or the resin coating film from being peeled off from the metal material.

[Surface treatment method]

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

(coating step)

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

(drying step)

The drying step is a step of drying the surface after the coating step without water washing to form a surface-treated film. Drying temperature can be set to match the solvent used temperature. For example, when water is used as the solvent, it is preferably in the range of 50 ° C to 250 ° C. Although the drying apparatus is not particularly limited, an electromagnetic induction heating furnace using a batch type, a continuous type or a hot air circulation type drying furnace, a conveying type hot air drying furnace or an IH heater can be used, and the air volume and the wind speed can be arbitrarily set. .

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

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

[Examples]

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

[Organic Compound (A)]

The organic compound (A) used is as follows. Again, functional The base content means a value obtained by dividing the molecular weight of the organic compound (A) by the total content of the carboxyl group and/or the hydroxyl group contained in one molecule.

Aa: polymaleic acid (molecular weight 3000, functional group content 58)

Ab: L-ascorbic acid (molecular weight 175, functional group content 43.8)

Ac: tartaric acid (molecular weight 150, functional group content 37.5)

Ad: pyromellitic acid (molecular weight 254, functional group content 63.5)

Ae: butane tetracarboxylic acid (molecular weight 234, functional group content 58.5)

Af: pentaerythritol (molecular weight 136, functional group content 34)

Ag: gallic acid (molecular weight 188, functional group content 47)

Ah: polyethylene glycol (molecular weight 4000, functional group content 2000)

Ai: polyacrylic acid (molecular weight 15000, functional group content 72)

Aj: polymaleic acid (molecular weight 20000, functional group content 58)

[Crosslinking organic compound (B1)]

(Organic compound I having a carbodiimide bond: symbol B1a)

700 parts (2.87 mol) of m-methylmethyl xylylene diisocyanate, 14 parts of 3-methyl-1-phenyl-2-cyclophosphene-1-oxide (carbodiimide catalyst) In the presence of the mixture, the mixture was reacted at 180 ° C for 32 hours to obtain a polycarbodiimide compound having a degree of condensation 12 of isocyanate groups at both ends. To 224 parts of the obtained polycarbodiimide compound, 115 parts of polyoxyethylene monomethyl ether having a polymerization degree of 12 was added, and the mixture was reacted at 100 ° C for 48 hours to terminate the isocyanate groups at both ends. Then, 509 parts by mass of distilled water was gradually added thereto at 50 ° C to obtain a polycarbodiimide compound aqueous solution B1a.

(Organic compound II having a carbodiimide bond: symbol B1b)

338 parts (1.35 mol) of diphenylmethane diisocyanate and 354 parts (1.35 mol) of 4,4'-dicyclohexylmethane diisocyanate in 3-methyl-1-phenyl-2-cyclophosphene- The 1-oxide (carbodiimide catalyst) was reacted at 180 ° C for 32 hours in the presence of 2.9 parts to obtain a polycarbodiimide compound having a degree of condensation 12 of an isocyanate group at both ends. To 224 parts of the obtained polycarbodiimide compound, 115 parts of polyoxyethylene monomethyl ether having a polymerization degree of 12 was added, and the mixture was reacted at 100 ° C for 48 hours to terminate the isocyanate groups at both ends. Next, 509 parts of distilled water was slowly added at 50 ° C to obtain a polycarbodiimide compound aqueous solution B1b.

(Organic compound III having a carbodiimide bond: symbol B1c)

700 parts of m-tetramethylxylylene diisocyanate was present in 14 parts of 3-methyl-1-phenyl-2-cyclophosphene-1-oxide (carbodiimide catalyst) The reaction was carried out at 180 ° C for 32 hours to obtain a polycarbodiimide compound having a degree of condensation 12 of an isocyanate group at both ends. 224.4 parts of the obtained polycarbodiimide compound and 10.2 parts of 3,3-bis(dimethylamino)propylamine were reacted at 80 ° C for 1 hour, and then 12.6 g of dimethylsulfuric acid was added, and the mixture was stirred. hour. Next, 509.1 g of distilled water of distilled water was slowly added at 50 ° C to obtain an aqueous solution B1c of a polycarbodiimide compound.

(Organic compound I having oxazoline group: symbol B1d)

In a flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 220 parts of deionized water and 380 parts of 1-methoxy-2-propanol were fed. 5 parts of sodium persulfate, 200 parts of 2-isopropenyl-2-oxazoline, and 200 parts of ethyl acrylate were slowly introduced into the nitrogen gas while heating to 50 °C. The temperature in the flask was maintained at 50 ± 1 ° C, stirring was continued for 10 hours, and after completion of the reaction, the mixture was cooled to obtain a water-soluble oxazoline group-containing resin B1d having a nonvolatile content of 40.0%. The number average molecular weight of the polymer was about 20,000, and the oxazoline group content per 1 g of the polymer was 4.5 mmol/g.

(Organic compound II with oxazoline group: symbol B1e)

In a separation flask with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer with a capacity of 1 liter, 228.1 parts of deionized water was fed, and the surfactant nonylphenol polyethoxyl alcohol (ethylene oxide 6 mola) 1.25 parts of a 25% aqueous solution of ammonium sulfate and 1.9 parts of a 7% aqueous ammonia solution were introduced, and nitrogen gas was slowly introduced while raising the temperature to 70 °C. Thereafter, in the separation flask, 283.5 parts of butyl (meth)acrylate, 211.4 parts of styrene, 0.6 parts of divinylbenzene, and 55.1 parts of 2-isopropenyl-2-oxazoline were added as initial feed. Pre-formed emulsion composed of 158.4 parts of deionized water, 21.0 parts of 25% aqueous solution of surfactant ammonium nonylphenol polyethoxy alcohol (ethylene oxide 6 molar addition) and 7% ammonia water 10% by mass. Thereafter, an aqueous solution of 4.4 parts of potassium persulfate dissolved in 34.4 parts of pure water was further added to the separation flask to start polymerization. Further, the remaining pre-formed emulsion was dropped for 2.5 hours, reacted while stirring, and then dripped at 80 ° C for 2.5 hours. After completion of the reaction, 1.4 parts of 7% aqueous ammonia was added, and the pH was adjusted to 8.8 to obtain an oxazoline group-containing aqueous dispersion of acrylic acid B1e having a nonvolatile content of 55.6 mass%. The theoretical oxazoline group equivalent is 0.90 mmol/g.

(Organic compound III with oxazoline group: symbol B1f)

In a separation flask with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer with a capacity of 1 liter, 228.1 parts of deionized water was fed, and the surfactant nonylphenol polyethoxyl alcohol (ethylene oxide 6 mola) 1.25 parts of a 25% aqueous solution of ammonium sulfate salt and 1.9 parts of a 7% aqueous ammonia solution were added, and nitrogen gas was gradually introduced while raising the temperature to 70 °C. After the temperature was raised to 70 ° C, the flask was placed in the separation flask, and 170.1 parts of butyl (meth)acrylate, 159.9 parts of styrene, and 0.4 parts of divinylbenzene were added as a material for the first-stage polymerization reaction as initial feed. Pre-formed emulsion composed of deionized water 95.0 parts, surfactant nonylphenol polyethoxy alcohol (ethylene oxide 6 molar addition) ammonium sulfate salt 25% aqueous solution 18.6 parts and 7% ammonia water 0.4 parts (hereinafter referred to as "pre-made emulsion of the first stage") is 10% by mass. Thereafter, an aqueous solution of 4.4 parts of potassium persulfate dissolved in 34.4 parts of pure water was added to the separation flask to start polymerization. Further, the remaining pre-formed emulsion of the first stage was dropped for 1.3 hours, and reacted while stirring.

10 minutes after the end of the dropwise addition, 113.4 parts of butyl (meth)acrylate, 62.5 parts of styrene, 0.2 parts of divinylbenzene, 2-isopropenyl-2-oxo were dropped from the above separation flask for 1.3 hours. 44.1 parts of oxazoline, 63.4 parts of deionized water, 12.4 parts of a 25% aqueous solution of a surfactant ammonium nonylphenol polyethoxy alcohol (ethylene oxide 6 molar addition), and 0.2 parts of 7% ammonia water The pre-formed emulsion (hereinafter referred to as "second stage pre-formed emulsion") is reacted as a second-stage polymerization reaction while stirring. After the completion of the second stage of the pre-formed emulsified droplets, it was aged at 80 ° C for 2.5 hours. reaction After completion, 1.4 parts of 7% ammonia water was added, and the pH was adjusted to 8.9 to obtain an oxazoline group-containing aqueous acrylic acid dispersion B1f having a nonvolatile content of 55.6 mass% and a core-shell ratio = 6/4. The theoretical oxazoline group equivalent is 0.72 mmol/g.

(Organic compound with glycidyl ether group: symbol B1g)

Glycerol polyglycidyl ether (3 functional, epoxy equivalent 144, viscosity 170 mPa.S) was used.

(Organic compound having isocyanate group: symbol B1h)

A hexamethylene diisocyanate-acetonitrile ethyl acetate block was used.

(organic compound with methylol; symbol B1i)

Use methylol melamine.

[Crosslinking inorganic compound (B2)]

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

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

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

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

B2d: titanium lactate (concentration 44.0% by mass)

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

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

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

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

B2i: Selenium oxide (IV)

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

B2k: chromium (III) acetate

[Water metal surface treatment agent]

One or two or more kinds selected from the group consisting of the organic compounds Aa to Aj, the crosslinkable organic compounds B1a to B1i, and the crosslinkable inorganic compounds B2a to B2k are used in combination with water, and water is used as a solvent to prepare Tables 1 to 6. The aqueous metal surface treatment agents of Examples 1 to 91 and Comparative Examples 1 to 20 are shown. In addition, the "concentration" in Tables 1 to 6 indicates the concentration (% by mass) of the nonvolatile component of each compound contained in the aqueous metal surface treatment agent. In addition, the "A concentration" indicates the content (% by mass) of the total solid content of the organic compound (A) with respect to the aqueous metal surface treatment agent; "B1 + B2 concentration" is the crosslinkable compound (B) relative to the aqueous metal The content of all the solid components in the surface treatment agent is a total content (% by mass) of the crosslinkable organic compound B1 and the crosslinkable inorganic compound B2.

[metallic material]

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

Al: A1100P, thickness 0.3mm

Cu: C1020P, thickness 0.3mm

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

SUS: SUS304 plate, thickness 0.3mm

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

From the metal materials, the metal materials shown in the "substrate" column of Tables 1 to 6 were selected, and the base metals of Examples 1 to 91 and Comparative Examples 1 to 24 were prepared.

[Manufacture of test materials]

(surface treatment)

The substrate metals of Examples 1 to 91 and Comparative Examples 1 to 20 shown in Tables 1 to 6 were sprayed at 65 ° C with a 3% aqueous solution of FINE CLEANER 359E (alkali degreaser manufactured by Nippon Parkerizing Co., Ltd.). After degreasing for a minute, wash with water to clean the surface. Next, in order to evaporate the water on the surface of the metal material, it was dried by heating at 80 ° C for 1 minute. On the surface of the base metal which was degreased and washed, the water-based metal surface treatments of Examples 1 to 90 and Comparative Examples 1 to 20 shown in Tables 1 to 6 were respectively applied by bar coating using #3SUS Mayer bar. The agent (coating step) was dried in a hot air circulating type drying oven at 200 ° C for 1 minute (drying step) to obtain a metal material having a surface-treated film. Further, two metal materials which were surface-treated with the same aqueous metal surface treatment agent were prepared, and the lamination processing was applied to the surface treatment film by a different method as described below.

In addition, the metal materials described in Comparative Examples 21 to 24 were prepared, and the water-based metal surface treatment agent was applied, and the mixture was degreased, washed with water, and dried by heating to obtain a metal material having no surface treatment film. Further, two metal materials of the same kind were prepared, and lamination processing was applied to the surface in different ways as shown below.

(lamination processing)

One of the two metal materials having the surface-treated coatings prepared thereon was subjected to a lamination process of thermal lamination on the surface-treated coating. A lamination process of dry lamination is applied to the other surface treatment film. For not having The metal material of the surface treatment film is also subjected to thermal lamination to one of the two side surfaces and dry lamination to the other one side surface.

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

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

(forming processing)

The polypropylene film laminated metal material obtained by thermal lamination and the polypropylene film laminated metal material obtained by dry lamination were respectively subjected to deep drawing processing by a draw extension processing test. For stamping a coated gold with a diameter of 160mm The plate was subjected to drawing (first time) to produce a cup having a diameter of 100 mm. Next, the cup was again drawn to a diameter of 75 mm (second time), and further drawn to a diameter of 65 mm (third time) to produce a can for the test material. In addition, the ironing rate (thinning fraction) in the first drawing process, the second drawing process, and the third drawing process is 5%, 15%, and 15%, respectively. .

[Performance Evaluation]

(adhesion)

The presence or absence of peeling of the polypropylene film (hereinafter referred to as "initial adhesion") was evaluated for the can after the forming process. It is possible to produce a can, and the film is not peeled off, and the initial adhesion is "3 points"; the part of the film is "2 points"; the film peeling is "1 point". The results of the evaluation test are shown in Tables 7 to 9.

(drug tightness maintenance)

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

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

Thereafter, the test piece was taken out, immersed in ion-exchanged water for 1 minute, washed by shaking, and then dried in a hot air circulating type drying oven at 100 ° C for 10 minutes. Then, the film surface is gripped by the tip of the tweezers, and the film is peeled off without any film peeling, and the electrolyte retention resistance is excellent, and the film is "3 points", and the film peeling is "2 points", and the film peeling is "1 point." To evaluate. The results of the evaluation test are shown in Tables 7 to 9.

As shown in Tables 7 to 9, the metal materials having the surface-treated coatings formed by applying the aqueous metal surface treatment agents described in Examples 1 to 91 confirmed the initial adhesion regardless of the thermal lamination and the dry lamination. The properties and resistance to electrolyte adhesion are very good.

1‧‧‧Substrate metal

2‧‧‧Surface treatment film

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

10‧‧‧Metal materials with surface treated film

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

Claims (4)

An aqueous metal surface treatment agent for treating a surface treatment film for a substrate of a laminate film or a resin coating film on the surface of a metal material, which comprises: a molecular weight of from 30 to 300 The ratio of an organic compound (A) having two or more carboxyl groups and/or hydroxyl groups in one molecule and having a molecular weight of 10,000 or less, and a crosslinkable organic compound having a structural unit capable of reacting with the carboxyl group and/or the hydroxyl group One or two or more kinds of crosslinkable compounds (B) selected from the group consisting of the compound (B1) and the crosslinkable inorganic compound (B2) which can react with the carboxyl group and/or the hydroxyl group. The aqueous metal surface treatment agent according to claim 1, wherein the crosslinkable organic compound (B1) has a carbodiimide bond, an oxazoline group, a glycidyl ether group, an isocyanate group, and a hydroxymethyl group. One or more structural units selected from the above. The aqueous metal surface treatment agent according to claim 1 or 2, wherein the crosslinkable inorganic compound (B2) contains Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, One or two selected from Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La More than one element. A metal material characterized by having a surface treatment film formed by applying an aqueous metal surface treatment agent according to any one of claims 1 to 3 to a surface of a metal material.