TWI558849B - Water metal surface treatment agent and metal film with surface coating - Google Patents

Description

Water metal surface treatment agent and metal material with surface film

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 water-based metal having no hexavalent chromium surface treatment film which is excellent in adhesion resistance maintenance of high adhesion and adhesion, even if it is further exposed to an acid or the like. Surface treatment agent, etc.

The laminating process is a processing method in which a film made of a resin (hereinafter referred to as "resin film" or "laminated film") is heat-pressure-bonded to the surface of a metal material (hereinafter, simply referred to as "metal surface"). One of the coating methods for protecting a metal surface or imparting design to a metal surface is used in various fields. This laminating process is a method in which a resin composition is dried or dispersed in a solvent to form a resin coating film, and a solvent or a waste gas such as carbon dioxide or a warm gas generated during drying is produced as compared with a method in which a resin composition is dissolved or dispersed in a solvent. Less. Therefore, it is preferably applied to an environmentally friendly surface, and its use is expanded, for example, for use in a body or a lid of a food can, which is made of an aluminum thin plate, a steel thin plate, a packaging aluminum foil, or a stainless steel foil. food 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 treatment, it is necessary to carry out a washing step for removing the excess treatment liquid after the treatment, and the waste water treatment of the washing water discharged from the washing step is costly. In particular, since a treatment liquid containing a hexavalent chromium is used in the chemical conversion treatment such as chromate phosphate, it is tend to be 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.

However, when the aluminum foil with the surface treatment film described in Patent Documents 2 to 4 is used for a laminated outer casing of a lithium ion secondary battery, as described above, in a highly corrosive environment in an electrolytic solution, it is impossible. The high adhesion maintainability between the metal surface and the laminated film is satisfied.

[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 laminated metal film or the resin coating film is not adhered to the high-adhesive property, and the metal-based surface treatment of the hexavalent chromium-free surface treatment film which is excellent in the adhesion resistance maintenance of the high-adhesion resistance even when exposed to an acid or the like is maintained. And a metal material treated with the metal surface treatment agent.

The aqueous metal surface treatment agent of the present invention for solving the above problems is characterized in that it contains a polyisocyanate compound (A) containing two or more blocked isocyanate groups.

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

In the aqueous metal surface treatment agent of the present invention, it is preferred to contain a crosslinkable organic compound (B1) having a functional group reactive with the above isocyanate group and a crosslinkable inorganic compound having an element reactive with the aforementioned isocyanate group. One or two or more kinds of crosslinkable compounds (B) selected from (B2).

According to the present invention, since the crosslinkable compound (B) is further contained, the surface-treated film obtained by treating the aqueous metal surface treatment agent has higher adhesion and can be maintained even higher even when exposed to an acid or the like. Adhesion.

In the aqueous metal surface treatment agent of the present invention, the functional group of the crosslinkable organic compound (B1) is preferably one selected from the group consisting of a carboxyl group, a hydroxyl group, a carbodiimide group and a glycidyl ether group. 2 or more types.

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

In the aqueous metal surface treatment agent of the present invention, the cross-linking organication The compound (B1) is preferably tannin.

In the aqueous metal surface treatment agent of the present invention, the crosslinkable inorganic compound (B2) preferably contains Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, Ti, Si. One or two or more elements selected from the group consisting of Sr, 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 sustained even when 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 polyisocyanate compound (A) is preferably a bisulfite-terminated urethane prepolymer.

In the aqueous metal surface treatment agent of the present invention, when the solid content of the polyisocyanate compound (A) is M _A and the solid content of the crosslinkable compound (B) is M _B , the polyisocyanate compound (A) The solid content mass ratio [M _A / (M _A + M _B )] is preferably 0.5.

According to the present invention, since the solid content ratio of the polyisocyanate compound (A) is 0.5 or more, the surface-treated film treated with such an aqueous metal surface treatment agent, the isocyanate which is active by the polyisocyanate compound (A) is mutually active. In the case where the crosslinkable compound (B) is used in combination, the cross-linking reaction between the isocyanate having the activity of the polyisocyanate compound (A) and the functional group of the crosslinkable compound is obtained. It is dense and has excellent barrier properties. Result, the surface treatment The film has excellent adhesion and, even when exposed to an organic solvent or an acid, maintains a more stable adhesion for a long period of time.

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 water-based metal surface treatment agent of the present invention, the surface-treated film obtained by treating the aqueous metal surface treatment agent containing at least the polyisocyanate compound (A) has high adhesion, and can maintain high adhesion even when exposed to an acid or the like. Sex. 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.

The metal material according to the present invention has 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. When a severe molding process such as elongation processing or stretch drawing processing 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.

Hereinafter, the aqueous metal surface treatment agent of the present invention will be described and have A metal surface treatment agent is applied to a metal material of a surface treatment film formed on the surface of a metal material. 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 used to form 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 by containing a polyisocyanate compound (A) containing two or more blocked isocyanate groups. "Contained" means that a compound other than the polyisocyanate compound (A) may be contained in the aqueous metal surface treatment agent. Such a compound is preferably one or two or more kinds of crosslinkable compounds (B) selected from the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2), and may further contain an interface as needed. Active agent, antifoaming agent, leveling agent, antibacterial and antifungal agent, coloring agent, and the like. 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.

(polyisocyanate compound (A))

The polyisocyanate compound (A) is a compound containing two or more blocked isocyanate groups. The "polyisocyanate compound containing a blocked isocyanate group" is a compound in which an active isocyanate group present in an aqueous metal surface treatment agent is not activated by a blocking agent, and is a water-based metal which can utilize thermal reactivity. A compound of a surface treatment agent. Contains this The aqueous metal surface treatment agent of the polyisocyanate compound is also preferable from the viewpoint of stability.

In addition, the polyisocyanate compound contains "two or more blocked isocyanate groups", and after applying an aqueous water-based metal surface treatment agent and heating and drying to form a surface-treated film, (1) removal of the capping And the reaction of the decarburized amine group with the isocyanate group or the crosslinking reaction of the functional group and the isocyanate group of (2) a carboxyl group, a hydroxyl group, a carbodiimide group, a glycidyl ether group, etc. which can react with an isocyanate It has the effect of being polymerizable to form a dense surface treatment film.

Since the surface-treated film formed of the aqueous metal surface treatment agent containing the polyisocyanate compound (A) has polarity, it can not only obtain initial adhesion, but also exhibits poor solubility in substances existing in a drug such as an electrolytic solution. Therefore, it is possible to exhibit drug-resistant adhesion maintenance.

As the polyisocyanate compound, an aromatic, aliphatic or alicyclic organic polyisocyanate which has been conventionally used can be used. Specific examples thereof include naphthalene diisocyanate, isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), and tetramethyl xylylene diisocyanate (TMXDI). Organic polyisocyanate such as dicyclohexylmethane diisocyanate (H12MDI), hydrogen added diphenylmethane diisocyanate (hydrogenated MDI), diphenylmethane diisocyanate (MDI), tolyl diisocyanate (TDI), or the like A diurea compound, a trimeric isocyanate compound, a carbodiimide modified body, or a mixture thereof.

The polyisocyanate compound is preferably such that an excess of polyisocyanate is A urethane prepolymer obtained by reacting a polyhydric alcohol having at least two or more hydroxyl groups per molecule to form a prepolymer containing two or more terminal isocyanate groups and then reacting with a blocking agent.

The number of terminal isocyanate groups of the urethane prepolymer is preferably from 3 to 4, particularly preferably three. The number of terminal isocyanate groups is three or more urethane polymers, and a three-dimensional mesh structure can be adopted to form a dense film, which is insoluble in a drug such as an electrolytic solution, and improves drug adhesion maintaining property.

Examples of the polyhydric alcohol include a divalent alcohol such as 1,3-butanediol, 1,4-cyclohexanedimethanol, 1,4-butanediol, and 1,6-hexanediol; Either or a mixture of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, pentaerythritol, trimethylolpropane, mono-, di- or triethanolamine, diglycerin, sorbitol, sucrose, etc.; Polyol, castor oil, etc. obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide. Further, a dibasic acid such as adipic acid or phthalic anhydride; or a dehydration condensation reaction with a glycol or a triol of ethylene glycol, diethylene glycol or trimethylolpropane may be mentioned. Various polyester polyols; lactone polyester polyols obtained by ring-opening polymerization of ε-caprolactam; phosgene of polyols, polycarbonates synthesized by transesterification of diphenyl carbonate Ester diol; other acrylic polyol, polybutadiene polyol, and the like.

The NCO content of the terminal isocyanate group present in the polyisocyanate compound is usually preferably from 1 to 10% by mass, more preferably from 2 to 5% by mass. In this range, a poorly soluble, surface-treated film can be formed by the reaction of isocyanate groups or the reaction of an isocyanate group with a compound. membrane. When the content of the NCO group is less than 1% by mass, the reaction position is insufficient, so that it is difficult to form a dense surface-treated film, and it is difficult to obtain a drug-resistant adhesion maintaining property. When the content of the NCO group exceeds 10% by mass and further has more than four isocyanate groups, the crosslinking site may be excessive, and the surface-treated film formed may become brittle, the film strength may be lowered, and the initial adhesion may be lowered.

The blocking agent to be introduced for the purpose of blocking the isocyanate group is preferably selected from the viewpoints of safety, reactivity, and the like. Examples of the blocking agent include phenols such as phenol, butyl phenol, chlorophenol, and phenylphenol; oximes such as methyl ethyl ketone oxime, cyclohexane hydrazine, and acetone oxime; imidazole, 2-methylimidazole, and 2-ethyl b. Imidazoles such as imidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole; sodium bisulfite, and the like. Among these, it is preferable to use sodium bisulfite as a blocking agent from the viewpoint of being easy to be relatively low temperature and dissociating in a short time.

For the method of imparting water solubility to the polyisocyanate, a method of binding a bisulfite, a sodium taurate, an alkyl halide, a diethylsulfate, a polyethylene glycol, or the like to a polyisocyanate, or a nonionic active agent may be used. A commonly known method such as a method of emulsification. When a nonionic active agent is used, it must be an amount that does not impair the effects of the present invention.

The ratio of the terminal isocyanate to the blocking agent of the polyisocyanate is preferably from 1.0 to 1.5 moles per terminal isocyanate group (i.e., free isocyanate group) of the polyisocyanate.

In addition, when the water-based metal surface treatment agent of the present invention further contains a crosslinkable compound (B) to be described later, the solid content of the polyisocyanate compound (A) is M _A , and a crosslinkable compound (B) will be described later. When the mass of the solid component is M _B , the solid content ratio [M _A /(M _A + M _B )] of the polyisocyanate compound (A) is preferably 0.5 or more. When the solid content ratio of the polyisocyanate compound (A) is 0.5 or more, the surface-treated film treated with the aqueous metal surface treatment agent is self-crossed by the isocyanate having the activity of the polyisocyanate compound (A). In the case where the crosslinkable compound (B) is used in combination, the crosslinking reaction between the isocyanate having the activity of the polyisocyanate compound (A) and the functional group of the crosslinkable compound becomes dense and Those with good barrier properties. The solid content mass ratio is more preferably 0.6 or more, and particularly preferably 0.7 or more. When the mass ratio of the solid content of the polyisocyanate compound (A) is less than 0.5, the surface treatment film obtained by the aqueous metal surface treatment agent may become brittle, and the strength of the surface treatment film may be lowered to maintain the adhesion resistance of the drug. Reduced situation.

(crosslinkable compound (B))

Although the crosslinkable compound (B) is a compound which can be arbitrarily contained in the aqueous metal surface treatment agent of the present invention, it can achieve higher adhesion and chemical adhesion maintenance.

The crosslinkable compound (B) is selected from a crosslinkable organic compound (B1) having a functional group reactive with an isocyanate group, and a crosslinkable inorganic compound (B2) having an element reactive with an isocyanate group. One or two or more compounds. The "isocyanate group" is a two or more blocked isocyanate groups of the polyisocyanate compound (A). "Reactive" means a reaction which can be reacted with an isocyanate group.

"Yes" means that in addition to functional groups or elements that are reactive with isocyanate groups, In addition, other functional groups, elements or bonding units may be aggregated.

(crosslinkable organic compound (B1))

The crosslinkable organic compound (B1) has one or two or more functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, a carbodiimide group, and a glycidyl ether group. "Having" means that the crosslinkable organic compound may have other functional groups or bonding units in addition to the functional groups.

Examples of the organic compound having a carboxyl group and/or a hydroxyl group include oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, itaconic acid, propane dicarboxylic acid, butane dicarboxylic acid, and pentane dicarboxylic acid. Acid, hexane dicarboxylic acid, heptane dicarboxylic acid, butane tricarboxylic acid, butane tetracarboxylic acid, cyclohexane tetracarboxylic acid, and hexane tricarboxylic acid, and the like, a polycarboxylic acid; ethylene glycol, Polyhydric alcohols such as propylene glycol, butylene glycol, hexanediol, polyethylene glycol, thiodiethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyethylene glycol, polypropylene glycol, etc.; malic acid, Citric acid, tartaric acid, etc. polyvalent hydroxycarboxylic acid; hexahydroxybenzene, pyrogallol, 1,2,4-trihydroxybenzene, phloroglucinol, catechol, resorcinol, hydroquinone, 5 -methyl pyrogallol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 3-methylcatechol, 4-methyl Catechol, methylhydroquinone, 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-dihydroxybenzoic 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-methylbenzoin Acid, 4-hydroxy-3,5-dimethylbenzoic acid, 1,4-dihydroxy-2-naphthoic acid, methyl gallate, methyl 2,4-dihydroxybenzoate, 2,6-dihydroxy Methyl benzoate, methyl 3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate, ethyl 3,4-dihydroxybenzoate, 4,6-diaminoresorcinol Hydrochloride, 4,6-diaminoresorcinol, 2-nitroresorcinol, 4-nitrocatechol, meliic acid, phenylpentacarboxylic acid, pyromellitic acid, trimellitic acid Formic acid, half methic acid, symmetrical trimellitic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic 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-hydroxybenzoic acid, L-resistant Ring-like organic compounds such as acid; tannic acid, witch hazel tannin, gallnut tannin, gallnut tannin, tannin of medlar, tannin of medlar fruit, tannin of tannin, persimmon Tannin, theaflavin, thearubigin, the tannin of the cyanobacteria, the tannin of the tea, the tannin of the condensed tannin, and the like. Among these crosslinkable organic compounds (B1), tannic acid is preferred in order to exhibit drug-resistant adhesion maintenance.

The carboxyl group and/or the hydroxyl group are preferably contained in two or more molecules in a ratio of one to three molecules per molecule.

The molecular weight of the crosslinkable organic compound (B1) is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less. Cross-linking organic When the molecular weight of the compound (B1) exceeds 10,000, the crosslinkable organic compound may become difficult to move in the aqueous metal surface treatment agent, and thus the carboxyl group or the hydroxyl group may be difficult to be oriented on the metal surface when forming the surface treatment film, and the metal surface The adhesion is low. Further, the crosslinkable organic compound (B1) is hard to move, and the chance of contact with the polyisocyanate compound (A) having a blocked isocyanate group is reduced, so that the uncrosslinked portion is likely to be generated and the crosslinking density is lowered. As a result, there is a possibility that the density of the surface-treated film is lowered and the durability of the drug-resistant adhesion is lowered.

The crosslinkable organic compound (B1) having a carbodiimide is not particularly limited, and a conventionally known polycarbodiimide compound is exemplified.

The polycarbodiimide compound can be obtained by a decarboxylation reaction of a diisocyanate compound having an aromatic ring or a decarboxylation reaction of an aliphatic or alicyclic diisocyanate compound having an aromatic ring. The polycarbodiimide compound thus obtained is a polymer compound having 5 to 15 carbodiimide bonds, and is obtained by capping the isocyanate groups at both ends thereof with a polyol compound or a polyamine. A nonionic or cationic polycarbodiimide compound. In the case where the isocyanate groups at both ends are blocked with a polyamine, the hydrogen atom or the alkyl group is bonded to at least a part of the nitrogen atom forming the secondary or tertiary amine moiety by further action of an acid or an alkylating agent. It can be a cationic polycarbodiimide compound.

The polyhydric alcohol compound may, for example, be a poly(alkylene glycol) represented by the formula (1) or a monoalkyl ether thereof.

[1] R ¹ O(R ² O) _n H (1)

In the 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.

The polyamine may, for example, be a polyamine represented by the formula (2) or a poly(alkylenediamine) N-alkyl derivative represented by the formula (3).

In the 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.

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

In the 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 2 to 2; An integer of 30.

The number of the carbon diimine bond in the molecule of the polycarbodiimide compound obtained by the decarboxylation reaction must be 5 to 15, preferably 7 to 13. When the number of carbodiimide bonds is maintained in the above range, not only the adhesion between the coating surface and the deep-drawing property and the metal surface or the upper coating material is improved, but also the structure of the polycarbodiimide compound becomes soft. Therefore, the processing adhesion is improved. When the number of carbodiimide bonds is less than 5, the reactivity of the polycarbodiimide compound itself increases, and it becomes easy to become a hard and brittle surface treatment film. another On the other hand, when the number of the carbodiimide bonds exceeds 15, the reactivity of the polycarbodiimide compound itself is lowered too low, and not only the crosslinking becomes insufficient, but also the water dispersibility is lowered.

The diisocyanate having an aromatic ring used in the production of the polycarbodiimide compound can be used as the compound exemplified in the "isocyanate compound" described in the column of the "polyisocyanate compound (A)".

As a method for synthesizing a polycarbodiimide compound, a usual synthesis method of decarbonation of a diisocyanate can be used. For example, a method of synthesizing deisocyanate at a certain temperature in the presence of a diisocyanate in an inert organic solvent or a carbodiimide catalyst can be mentioned. For the bismuth imidization catalyst, 1-phenyl-2-cyclophosphene-1-oxide, 3-methyl-2-cyclophosphene-1-oxide, 1-ethyl-2- can be used. Cyclophosphene-1-oxide, 1-ethyl-3-methyl-2-cyclophosphene-1-oxide, 3-methyl-1-phenyl-2-cyclophosphene-1-oxide Or a cyclophosphene oxide such as a 3-cyclophosphene isomer. In addition, the inactive organic solvent may, for example, be an ether solvent such as tetrahydrofuran or 1,4-dioxane, a ketone solvent such as cyclohexanone or acetone, or a hydrocarbon solvent such as hexane or benzene.

To the solution of the polycarbodiimide compound obtained in this manner, a polyol compound or a polyamine is added to carry out a reaction, and the isocyanate groups at both terminals are blocked. Further, as the polyol compound or polyamine, a poly(alkylene glycol) represented by the above formula (1) or a monoalkyl ether thereof, a polyamine represented by the above formula (2), or A poly(alkylenediamine) N-alkyl derivative represented by the above formula (3). Further, in the 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 or a propyl group. , isopropyl, butyl, etc., but methyl or ethyl is preferred. R ² and R ¹⁰ may, for example, be an ethyl group, a propyl group or a n-butyl group, but an ethyl group and a propyl group are preferred. Examples of R ⁷ include an ethane triyl group, a propane triyl group, a butane triyl group, and the like.

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

When the polyamine of the formula (2) or the formula (3) is used to terminate the terminal isocyanate group, an acid or an alkylating agent is further added to the reaction solution containing the polycarbodiimide compound to cause a hydrogen atom or The alkyl group is cationized by forming at least a portion of a nitrogen atom derived from the secondary or tertiary amine moiety of formula (2) or formula (3). This can be a cationic polycarbodiimide compound. The acid here is not particularly limited, and 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 (A). Base sulfuric acid, ethyl sulfuric acid, etc.), formic acid, acetic acid, and the like. The alkylating agent is not particularly limited, and examples thereof include dialkyl sulfuric acid such as dimethylsulfuric acid and diethylsulfonic acid; or halogenation of methyl chloride, ethyl chloride, propyl chloride, chlorobutyl or the like. Alkyl and the like.

Polycarbodiimide compound, usually in the form of an aqueous solution or water dispersion Form to use. The carbodiimide compound in the form of an aqueous solution or an aqueous emulsion can be obtained by adding water to the cationized polycarbodiimide compound, followed by removing the inactive organic solvent by distillation or the like. The water dispersion form may be in the form of an emulsion or a colloidal dispersion. The dissolution or dispersion of the carbodiimide compound in water can be achieved based on either self-solubility or self-dispersibility, or by a cationic surfactant (for example, a tetraalkylammonium salt, etc.). And/or the presence of a nonionic surfactant (eg, polyoxyalkylene alkylphenyl ether, etc.) is achieved. However, the use of such surfactants adversely affects performance. Therefore, it is preferred not to use a surfactant or to inhibit the amount of use even when used.

The crosslinkable organic compound (B1) 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.

The effect of each of the crosslinkable organic compounds (B1) differs depending on the properties possessed by the polyisocyanate compound (A), and the isocyanate and the crosslinkable compound (B) which are active by the polyisocyanate compound (A) The crosslinking reaction of the functional group can improve the density and barrier properties, and improve the adhesion or the adhesion resistance of the drug.

(crosslinkable inorganic compound (B2))

The crosslinkable inorganic compound (B2) is an inorganic compound having an element reactive with the blocked isocyanate group of the polyisocyanate compound (A). "Having" means that the crosslinkable inorganic compound may have other elements or bonding units in addition to the elements.

As the crosslinkable inorganic compound (B2), a conventionally known inorganic substance containing an element which can react with the blocked isocyanate group of the polyisocyanate compound (A) 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. In particular, an inorganic compound containing one or more elements selected from the group consisting of Mg, Al, Ca, Mn, Cr(III), Zn, Fe, Zr, Ti, Si, Ce, Te, and Hf is more preferable; An inorganic compound containing one or two or more elements selected from the group consisting of Cr(III), Zr, Ti, Si, Ce, and Te is more preferable.

Specifically, it includes Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta. a salt, a wrong compound or a metal hydrated oxide of one or more elements selected from the group consisting of Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and La (hereinafter also referred to as " Salt, 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, magnesium iodide, magnesium pyrophosphate, magnesium nitrate , magnesium sulfate such as magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, magnesium ammonium phosphate, magnesium hydrogen phosphate, magnesium oxide, etc.; aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, aluminum sulfate, aluminum ammonium sulfate, phosphoric acid Aluminum, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum oxide, aluminum fluoride, aluminum iodide, aluminum acetate, aluminum benzoate, aluminum citrate, aluminum gluconate, aluminum selenate, aluminum oxalate, aluminum tartrate, aluminum lactate Aluminum salt of aluminum palmitate, etc.; bis(acetylthiopyruvate) calcium (II) dihydrate, calcium benzoate, calcium citrate, calcium metastannate, calcium selenate, calcium tungstate, calcium carbonate, four Calcium borate, calcium molybdate, calcium maleate, calcium malate, calcium pyrophosphate, calcium fluoride, calcium hypophosphite, calcium nitrate, calcium hydroxide, calcium oxide, calcium oxalate, calcium acetate, etc.; (Ethyl pyruvic acid) 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, sulfuric acid Manganese (IV), Manganese (II), manganese (III) fluoride, manganese (II) carbonate, manganese (II) acetate, manganese (III) acetate, manganese (II) ammonium sulfate, manganese (II) iodide, manganese hydroxide (II) a manganese salt or the like, or a manganate or the like; bis(acetylthiopyruvate) cobalt (II) dihydrate, cobalt (III) ginsyl pyruvate, cobalt (II) amine sulfonate, chlorination Cobalt (II), chloropentaamine cobalt chloride (III), hexaammine cobalt chloride (III), ammonium diammonium tetranitrocobalt (III) acid, cobalt (II) sulfate, cobalt ammonium sulfate, cobalt nitrate (II ) , cobalt aluminum oxide, cobalt (II) hydroxide, cobalt (II) oxide, cobalt phosphate, cobalt (II) acetate, cobalt (II) formate, cobalt trioxide, cobalt (II) bromide, cobalt (II) oxalate, selenium Cobalt acid (II), cobalt (II) tungstate, cobalt (II) hydroxycarbonate, cobalt (II) molybdate, cobalt (II) chloride, cobalt (II) phosphate, etc.; nickel diamine sulfonate (II), nickel benzoate (II), nickel (II) nitrate, nickel (II) sulfate, nickel (II) carbonate, nickel pyridinium (II) pyruvate, nickel (II) chloride, hexachloro nickel chloride Compound, nickel oxide, nickel (II) hydroxide, nickel (II) oxide, nickel acetate, nickel (II) citrate, nickel (II) succinate, nickel (II) bromide, nickel (II) oxalate, nickel tartrate (II) nickel salt of nickel (II) selenate, nickel (II) hydroxycarbonate, nickel (II) lactate, nickel (II) molybdate, nickel (II) iodide, nickel (II) diphosphate, etc.; 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 formate (II), lemon Zinc (II), zinc (II) bromide, zinc (II) oxalate, zinc (II) tartrate, zinc (II) metastannate, zinc (II) selenate, zinc (II) sulphate, zinc fluoride (II), zinc molybdate (II), zinc (II) butyrate, zinc (II) pyrophosphate, zinc (II) sulfate, zinc (II) carbonate, zinc (II) chloride, zinc iodide (II), a zinc salt such as zinc hydroxide (II) or zinc oxide (II); Bis(acetylthiopyruvate) iron (II) dihydrate, iron (III) ginsengyl pyruvate, iron tripotassium trioxalate, iron (II) formate, iron (III) tetravanadate, bromination Iron (III), iron (III) tartrate, iron (II) lactate, iron (II) fluoride, iron (III) fluoride, iron (II) chloride, iron (III) chloride, iron iodide (II) ), 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) pyridinecarboxylate, Iron (II) L-phenylalanine, iron (III) L-phenylalanine, 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(ethylmercaptopyruvate) ruthenium (II) dihydrate, ruthenium (II) ruthenate, ruthenium citrate (II) ) barium tungstate, barium metastannate, barium (IV) oxide, barium (II) oxide, barium oxalate, barium metasilicate, barium molybdate, barium iodide, barium nitrate, barium sulfate, barium carbonate, barium acetate, Barium chloride, barium phosphate, lactic acid Such as strontium salt, etc.; diammonium diammonium dioxalate, dipotassium oxydioxalate, titanium oxide (II), titanium oxide (III), titanium oxide (IV), titanium (IV) oxysulfate, alkaline titanium phosphate, Titanium (IV) bromide, metatitanic acid, zinc (II) metasilicate, aluminum (III) titanate, potassium metatitadate, cobalt (II) metasilicate, zirconium titanate, barium titanate, titanium Iron (III), copper (II) metasilicate, sodium titanate, barium (III) dititanate, barium metasilicate barium, barium titanate (III), magnesium metatrate, titanium Magnesium oxide, manganese (II) meta-titanate, bismuth (III) dititanate, lithium metatitanate, ammonium hexafluorotitanium (IV), potassium hexafluorotitanate (IV), titanium (IV) iodide, sulfuric acid Titanium (III), titanium (IV) sulfate, titanium chloride, titanium nitrate, titanium oxysulfate, titanium (III) fluoride, titanium (IV) fluoride, hexafluorotitanate, titanium lactate, peroxotitanic acid, laurel Titanium salt of titanium titanate, pyruvic acid titanium hydride group, titanium hydroxide (IV), etc. or titanate; cerium (acetyl acetonate) zirconium (IV), zirconia (IV) chloride, chlorination Zirconium (IV), zirconium silicate, zirconium (IV) acetate, zirconium oxide (IV), zirconium oxide (IV) nitrate, barium zirconate, lithium meta-zirconate, zinc (II) meta-zirconate, meta-zirconic acid Aluminum (III), calcium meta-zirconate, cobalt (II) meta-zirconate, bismuth zirconate, copper (II) meta-zirconate, sodium meta-zirconium, nickel (II) meta-zirconate, bismuth zirconate, partial Cerium (III) zirconate, magnesium meta-zirconate, zirconium oxycarbonate, ammonium hexafluorozirconate (IV), potassium hexafluorozirconate (IV), zirconium iodide, zirconium hydroxide zirconium hydroxide (IV), basic carbonic acid Zirconium, ammonium zirconium carbonate, ammonium zirconium carbonate, zirconium nitrate, zirconium nitrate, zirconium sulfate (IV), zirconyl sulfate, hexafluorozirconate, zirconium oxyphosphate, zirconium pyrophosphate, zirconium dihydrogen phosphate, a zirconium salt such as zirconium chloride, zirconium fluoride, zirconyl acetate, zirconium oxide or zirconium hydroxide; a ceric acid salt such as hexafluoroantimonic acid or cerium oxide; tungsten (VI) chloride and iron oxytungstate (III), tungsten (VI) chloride, tungsten dichloride, tungsten dioxide, tungsten trioxide, metatungstic acid, ammonium metatungstate, sodium metatungstate, paratungstic acid, ammonium paratungstate, sodium paratungstate, Zinc tungstate (II), potassium tungstate, calcium tungstate, cobalt (II) tungstate, barium tungstate, barium tungstate, copper (II) tungstate, nickel tungstate, barium tungstate, magnesium tungstate, tungsten Tungsten salt of manganese manganate (II), lithium tungstate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, etc. or tungsten Acid salt; ginseng (III) pyridinium (III), cerium (III) chloride, cerium (III) oxide, cerium (IV) oxide, cerium (III) bromide, cerium (III) oxalate, hydrogen Cerium (IV) oxide, ammonium cerium (IV) sulfate, ammonium cerium (III) sulfate, cerium (III) carbonate, cerium sulfate, cerium (III) acetate, cerium (III) nitrate, cerium (IV) sulfate, fluorinated Barium salts such as cerium (III), cerium (III) iodide, cerium (III) phosphate, etc.; molybdenum chloride (V), molybdenum oxide (IV), molybdenum oxide (VI), zinc molybdate (II), molybdenum Potassium acid, calcium molybdate, cobalt (II) molybdate, bismuth molybdate, nickel (II) molybdate, bismuth molybdate, bismuth molybdate (III), magnesium molybdate, lithium molybdate, lithium paramolybdate, molybdenum Acid bismuth, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, molybdic acid, ammonium molybdate, ammonium paramolybdate, molybdate salts such as sodium molybdate, etc. or molybdate; oxygen vanadium dichloride, oxygen Vanadium trichloride, vanadium trichloride, vanadium oxide, iron (III) tetravanadate, vanadium (III) bromide, vanadium oxalate, vanadium (II) iodide, vanadium pentoxide, metavanadic acid, pyrovanaic acid Sodium, sodium vanadate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium trichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetate, vanadium Base a vanadium salt such as an acid ester or a phosphorus vanadium molybdate or a vanadate; tin (II) chloride, tin (II) acetate, tin (II) oxalate, tin (II) tartrate, tin (IV) oxide, and nitric acid Tin, tin sulfate, tin (II) fluoride, tin (II) iodide, tin (IV) iodide, tin (II) pyrophosphate, metastannic acid, zinc metastannate, calcium metastannate, metastannic acid a tin salt or a stannate such as barium, barium stannate or magnesium metastannate; barium benzoate (III), barium chloride (III), barium citrate (III), cerium (III) oxyacetate, cerium (III) oxidized tartrate, cerium (III) oxide, cerium oxysulfate, cerium (III) bromide, cerium (III) tartrate, cerium (III) hydroxide, oxygen Dicerium carbonate, cerium (III) zirconate, cerium oxynitrate, cerium (III) tetratitanate, cerium (III) trititanate, cerium (III) fluoride, cerium (III) molybdate, cerium iodide (III) ), cerium (III) nitrate, cerium (III) chloride, cerium (III) sulfate, cerium (III) acetate, cerium (III) phosphate, etc.; cerium chloride (V), cerium oxide (V) , bismuth bromide (V), citric acid, potassium hexasilicate, bismuth citrate, sodium metasilicate, lithium metasilicate, cesium iodide (V), pyruvate oxime, abietic acid, Ammonium citrate, potassium hexafluoroantimonate or the like, or citrate; citric acid, ammonium hexanoate, potassium metasilicate, sodium metasilicate, cerium iodide (IV), potassium citrate, Sodium citrate, decanoic acid, potassium citrate, sodium citrate, bismuth citrate, lithium niobate, cerium (IV) chloride, cerium (IV) oxide, cerium (IV) bromide, hydrogen peroxide碲 硝酸 硝酸 碲 碲 碲 碲 碲 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸 硝酸(I), Indium (III) chloride, indium (III) acetate, indium (III) bromide, indium (III) iodide, indium (III) nitrate, indium (III) sulfate, indium (III) fluoride, indium oxide (III) ), indium salts such as indium (III) hydroxide, etc.; bis(ethylmercaptopyruvate) ruthenium (II) dihydrate, bismuth selenite, bismuth citrate, bismuth benzoate, bismuth aluminate, ruthenium chloride , cesium formate, barium citrate, barium oxide, barium bromide, barium oxalate, barium tartrate, barium zirconate, hydrogen Barium oxide, barium metastannate, barium tungstate, barium titanate, barium metasilicate, barium lactate, barium metaborate, barium molybdate, barium iodide, barium hydrogen phosphate, barium carbonate, barium fluoride, etc. Salt, etc.; cerium (ethionylpyruvate) cerium (IV), cerium (IV) chloride, cerium (IV) oxide, cerium (IV) iodide, cerium (IV) sulfate, cerium (IV) nitrate, oxalic acid铪(IV), fluoroantimonic acid, fluoroantimonate, cesium fluoride, etc. or bismuth salt; potassium sulfite, potassium hydrogen selenite, trihydroindrene selenite, hydrogen selenite Sodium, lithium hydrogen selenite, copper (II) selenite, sodium selenite, barium selenite, selenium oxychloride, selenium chloride (I), selenium chloride (IV), selenium oxide (IV) , aluminum selenate, selenate, zinc selenite, potassium selenate, ammonium selenate, calcium selenate, strontium selenate, cobalt selenate, copper selenate (II), nickel selenate, sodium selenate, selenate Selenium salts such as strontium, zinc selenate, etc. or selenate; cerium (III) chloride, cerium (III) carboxylic acid, cerium (III) acetate, cerium (III) nitrate, cerium (III) oxide, cerium fluoride (III), barium salts of cerium (III) iodide, barium sulphate (III), etc.; cerium (II) oxide, cerium oxide (V), cerium (hydrogen oxalate), cerium hydroxide (V), pyruvic acid Oxyethyl sulfonate, bismuth citrate, calcium metasilicate, bismuth citrate, bismuth bismuth citrate, magnesium metasilicate, lithium metasilicate, ammonium metamonate, sodium metasilicate, ruthenium pentachloride, etc.铌 salt or the like or citrate; copper amide sulfate (II), copper (II) benzoate, copper (II) nitrate, copper (II) citrate, copper (I) oxide, copper bromide ( I), copper (II) oxalate, copper (II) formate, copper (II) acetate, copper (II) propionate, copper (II) pentoxide, copper (II) gluconate, copper tartrate (II) ), copper (II) chloride, copper (II) bromide, copper (II) hydroxide, copper (II) acetate, copper (II) nitrate, copper (II) sulfate, copper (II) carbonate, copper oxide ( II) copper hydroxy nitrate (II), copper (II) tungstate, copper (II) carbonate, copper (II) lactate, copper (II) fluoride, copper (I) copper, etc.; Paracetamol (III), cerium (III) chloride, cerium (III) formate, cerium (III) citrate, cerium (III) acetate, cerium (III) oxide, cerium (III) oxalate , barium nitrate (III), barium (III) carbonate, barium (III) fluoride, barium iodide (III), barium sulfate (III), barium (III) phosphate, etc.; Acid) cerium (III), cerium (III) chloride, cerium (III) carboxylic acid, cerium (III) acetate, cerium (III) oxide, cerium (III) oxalate, cerium (III) nitrate, cerium (III) carbonate, Barium salts of cerium (III) fluoride, cerium (III) dibasic acid, cerium (III) sulfate, cerium (III) phosphate, cerium (III) hydride, etc.; cerium (ethyl thiopyruvate) cerium (III) ), cerium (III) chloride, cerium (III) carboxylic acid, cerium (III) acetate, cerium (III) oxide, cerium (III) bromide, cerium (III) oxalate, cerium (III) nitrate, cerium carbonate (III) ), barium (III) dititanate, barium (III) fluoride, barium (III) iodide, sulfur Neodymium (III), neodymium (III) phosphate and other salts of neodymium. 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 a water-based metal surface treatment solvent or may be dispersed.

From a crosslinkable organic compound (B1) and a crosslinkable inorganic compound ( The total content of the crosslinkable compound (B) selected in B2) (B=B1+B2) is preferably 5% by mass to 90% by mass, more preferably 5% by mass to 90% by mass based on the total solid content. 10% by mass to 80% by mass, particularly preferably 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.

The effects of the respective crosslinkable inorganic compounds (B2) vary depending on the properties of the respective inorganic compounds (B2), and can cause passivation of a metal surface, formation of a hardly soluble salt, and insolubilization of a surface-treated film. Maintenance improvement.

The crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) constituting the crosslinkable compound (B) have been described above, but the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) are described. Any one may be contained in the aqueous metal surface treatment agent as the crosslinkable compound (B), and does not necessarily contain both of the compounds (A) and (B).

However, when both the crosslinkable organic compound (B1) and the crosslinkable inorganic compound (B2) are contained, the content ratio (mass ratio) of both is preferably M _B1 /(M _B1 +M _B2 ) Range of 0.2~0.8. When the content ratio of the crosslinkable organic compound (B1) is within this range, the denseness of the surface treated film obtained by the aqueous metal surface treatment agent can be further improved, whereby the chemical adhesion maintaining property can be further improved.

(solvent)

The water-based metal surface treatment agent of the present invention is used for coating a metal surface The workability at the time of cloth becomes better, and various solvents can be contained as needed.

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

(other additives)

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

(Modulation method of water metal surface treatment agent)

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

[metallic material]

As shown in FIG. 1, the metal material 10 of the present invention has a base metal 1 and is coated with a water-based metal surface treatment agent of the present invention on the surface thereof. Surface treatment of the film 2. "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, the resin film 3 formed by lamination processing or the resin coating film 3 formed by coating may be provided on the surface treatment film 2. 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, after the resin film 3 or the resin coating film 3 is formed on the surface treatment film 2, even if it is subjected to severe drawing such as deep drawing, stretching, or drawing, In addition, it is possible to prevent the resin film 3 or the resin coating film 3 from being peeled off from the metal material 10 even if it is further exposed to a drug (chemical liquid) such as an acid such as a battery electrolyte.

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

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

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

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

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

As described above, the aqueous metal surface treatment agent of the present invention contains a polyisocyanate compound (A) containing two or more blocked isocyanate groups, and thus the surface-treated film obtained by treating the aqueous metal surface treatment agent, It has high adhesion and maintains high adhesion even when exposed to acid or the like. In particular, when the isocyanate group is three or more, the surface-treated film formed has a three-dimensional mesh structure and is a film which is insoluble in an acid or an organic solvent. As a result, the resin film 3 is laminated on the base metal 1 on which the surface treatment film 2 is formed or the resin coating film 3 is formed, and even after the severe forming process such as deep drawing, stretching, or drawing, is performed, Even if it is further exposed to an acid or an organic solvent, etc., the laminated film 3 or the resin coating film 3 can be prevented from being peeled off from the base metal 1. Moreover, it exhibits high adhesion maintenance to a drug such as an electrolyte.

Moreover, the metal material according to the present invention can be a metal material having a surface-treated film excellent in adhesion and chemical resistance.

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

(drying step)

The drying step is a step of drying the surface after the coating step without water washing to form a surface-treated film. The drying temperature can be set to match the temperature of the solvent used. For example, when water is used as the solvent, it is preferably in the range of 50 ° C to 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 can be further improved and It is resistant to drug adhesion and maintenance.

[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 addition, the following "parts" are "mass parts" and "% by mass" are synonymous with "% by weight". Unless otherwise specified, the following is also expressed as "%". [ppm] is synonymous with "mg/L".

[Polyisocyanate compound (A)]

The polyisocyanate compound (A) used is as follows.

(Aa: polyisocyanate A)

486 parts by mass of a polyol having a molecular weight of 3,000 and a molecular weight of 3,000 parts by weight of ethylene oxide added to propylene oxide in a manner of adding 15% of the total molecular weight to the terminal, and 26.1 parts by mass of dipropylene glycol (average 0.02 parts by mass of dioctyltin dilaurate was added to the molecular weight of 2,854 and the average functional group number was 2.46. Further, 139 parts by mass of hexamethylene diisocyanate (NCO/OH equivalent ratio: 1.85) was further added, and the reaction was carried out at 80 ° C for 1 hour. Thereby, a urethane prepolymer containing a terminal isocyanate group having an NCO content of 4.9% by mass was obtained. Next, 183 parts by mass of DINP (diisononyl phthalate) was added as a solvent. In the urethane prepolymer containing a terminal isocyanate group, 1.25 equivalents of sodium bisulfite was added to the NCO group, and the reaction was carried out at 60 ° C for 1 hour to obtain a capping. The isocyanate group contains a urethane prepolymer A.

(Ab: polyisocyanate B)

486 parts by mass of a polyol having a molecular weight of 3,000 and a molecular weight of 3,000 parts by weight of ethylene oxide added to propylene oxide in a manner of adding 15% of the total molecular weight to the terminal, and 26.1 parts by mass of dipropylene glycol (average 0.02 parts by mass of dioctyltin dilaurate was added to the molecular weight of 2,854 and the average number of functional groups was 2.46. Further, 183 parts by mass of isophorone diisocyanate (NCO/OH equivalent ratio: 1.85) was further added, and the reaction was carried out at 80 ° C for 1 hour. Thereby, a urethane prepolymer containing a terminal isocyanate group having an NCO content of 4.6% by mass was obtained. Next, 194 parts by mass of DINP (diisononyl phthalate) was added as a solvent. In the urethane prepolymer containing a terminal isocyanate group, 1.25 equivalents of methyl ethyl ketone oxime was added to the NCO group, and the reaction was carried out at 60 ° C for 1 hour to obtain a blocked isocyanate group-containing urethane pre-prepared. Polymer B.

(Ac: polyisocyanate C)

486 parts by mass of a polyol having a molecular weight of 3,000 and a molecular weight of 3,000 parts by weight of ethylene oxide added to propylene oxide in a manner of adding 15% of the total molecular weight to the terminal, and 26.1 parts by mass of dipropylene glycol (average 0.02 parts by mass of dioctyltin dilaurate was added to the molecular weight of 2,854 and the average number of functional groups was 2.46. Further, 183 parts by mass of isophorone diisocyanate (NCO/OH equivalent ratio: 1.85) was further added, and the reaction was carried out at 80 ° C for 1 hour. Thereby, a terminal isocyanate having an NCO of 4.6% by mass was obtained. A urethane prepolymer. Next, 194 parts by mass of DINP (diisononyl phthalate) was added as a solvent. In the urethane prepolymer containing a terminal isocyanate group, 1.25 equivalents of methyl ethyl ketone oxime was added to the NCO group, and the reaction was carried out at 60 ° C for 1 hour to obtain a blocked isocyanate group-containing urethane pre-prepared. Polymer C.

(Ad: polyisocyanate D)

486 parts by mass of a polyol having a molecular weight of 3,000 in which ethylene glycol is added to the terminal, and 6.2 parts by mass of dipropylene glycol, in which bisphenol A ethylene oxide is added to glycerin and further added to 15% of the total molecular weight. 0.02 parts by mass of dioctyltin dilaurate was added to the polyol (average molecular weight 2854 and average functional group number 2.46), and 139 parts by mass of hexamethylene diisocyanate (NCO/OH equivalent ratio 1.85) was further added, and the reaction was carried out at 80 ° C. 1 hour. Thereby, a urethane prepolymer containing a terminal isocyanate group having an NCO content of 4.9% by mass was obtained. Next, 183 parts by mass of DINP (diisononyl phthalate) was added as a solvent. In the urethane prepolymer containing a terminal isocyanate group, 1.25 equivalents of sodium bisulfite was added to the NCO group, and the reaction was carried out at 60 ° C for 1 hour to obtain a blocked isocyanate group-containing urethane. Prepolymer D.

[Crosslinking organic compound (B1)]

B1a: 1,2,3,4-butane tetracarboxylic acid

B1b: an organic compound having carbodiimide [will be 700 parts by weight of m-tetramethylxylylene diisocyanate in 3-methyl-1-phenyl-2-cyclophosphorus The presence of 14 parts by mass of an ene-1-oxide (carbodiimide catalyst) was carried out at 180 ° C for 32 hours to obtain a polycarbodiimide compound having an isocyanate group at both ends and a condensation degree of 12. 115 parts by mass of polyoxyethylene monomethyl ether having a polymerization degree of 12 was added to 224 parts by mass of the obtained polycarbodiimide compound, and the isocyanate groups at both terminals were blocked by reacting at 100 ° C for 48 hours, followed by 50 ° C. 509 parts by mass of distilled water was slowly added to obtain an aqueous solution of a polycarbodiimide compound]

B1c: an organic compound having a glycidyl group [using glycerol polyglycidyl ether (3 functional, epoxy equivalent 144, viscosity 170 mPa. S)]

B1d: Tannin C ₇₆ H ₅₂ O ₄₆

B1e: gallic acid C ₆ H ₂ (OH) ₃ COOH

[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]

The organic compound Aa~Ad and the crosslinkable organic compound B1a to B1e and the crosslinkable inorganic compound B2a to B2k are one or more selected in the specified amount, and water is used as a solvent. The aqueous metal surface treatment agents of Examples 1 to 30 are shown. In addition, the "concentration" in Table 1 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, and the "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.

On the other hand, in Comparative Example 1, the water-soluble acrylic resin A aqueous solution (see below) described in JP-A-2002-265821 is referred to as a metal surface treatment agent; and Comparative Example 2 is disclosed in JP-A-2003-313680 The treatment agent (refer to the following) described in the publication is a metal surface treatment agent.

[Metal surface treatment agent of Comparative Example 1: JP-A-2002-265821]

The monomer composition of the acrylic resin is 160 parts by mass of acrylic acid. 20 parts by mass of ethyl acrylate and 20 parts by mass of 2-hydroxyethyl methacrylate. To the mixed monomer liquid, a mixed liquid of 1.6 parts by mass of ammonium sulfate and 23.4 parts by mass of ion-exchanged water was dropped for 3 hours using a dropping funnel. After the completion of the dropwise addition, heating, stirring, and nitrogen reflux were continued for 2 hours. Heating and nitrogen reflux were stopped, and the solution was stirred while cooling to 30 ° C, and filtered through a 200 mesh sieve to obtain a colorless transparent water-soluble acrylic resin A aqueous solution. It was confirmed that the nonvolatile content concentration was 20%, the resin solid content acid value was 623, and the resin solid content hydroxyl group value was 43. Further, SHOWNOL BRL-157 (manufactured by Showa Polymer Co., Ltd., a nonvolatile content concentration of 43%) was used as the water-soluble phenol resin, and zirconium hydrofluoric acid (nonvolatile content: 40%) was used as the zirconium compound.

[Metal surface treatment agent of Comparative Example 2: JP-A-2003-313680]

970.2 parts by mass of ion-exchanged water was placed in a 1 L plastic beaker. While stirring at normal temperature, zirconium hydrofluoric acid (pre-adjusted to 17.6% in terms of Zr concentration) was slowly added in an amount of 2.8 parts by mass. Further, 3 parts by mass of 1-hydroxyethylidene-1,1-diphosphonic acid was slowly added. Next, 24 parts by mass of tannic acid (pre-adjusted to a non-volatile content of 50% concentration) was slowly added. While stirring, while adding hydrofluoric acid to adjust the free fluorine concentration of the treating agent to 12 ppm, ammonia was added to adjust the pH of the treating agent to 2.6. Thereafter, the mixture was stirred for 10 minutes to obtain a treating agent. With respect to the component composition of the treating agent, an aqueous solution containing zirconium hydride at 500 ppm in terms of zirconium, 1-hydroxyethylidene-1,1-diphosphonic acid in an amount of 100 ppm in terms of phosphorus, and 1200 ppm of tannin was obtained.

[metallic material]

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

Al: A1100P, thickness 0.3mm

Cu: C1020P, thickness 0.3mm

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

SUS: SUS304 plate, thickness 0.3mm

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

The base materials of Examples 1 to 30 and Comparative Examples 1 to 6 were prepared from these metal materials by selecting the metal materials shown in the "Substrate" column of Table 1.

[Manufacture of test materials] (surface treatment)

The base metals of Examples 1 to 30 and Comparative Examples 1 to 6 shown in Table 1 were sprayed and degreased at 65 ° C in a 3% aqueous solution of FINE CLEANER 359E (alkali degreaser manufactured by Nippon Parkerizing Co., Ltd.). After a minute, wash with water to clean the surface. Next, in order to evaporate the water on the surface of the base metal, it was dried by heating at 80 ° C for 1 minute. On the surface of the base metal which was degreased and washed, a wet weight of 5 mL was applied by bar coating using #3SUS Mayer bar. m ² of the embodiment as shown in Example 1 of tables 1 to 30 and Comparative Examples 1 and 2 of the aqueous metal surface treatment agent (coating step), dried in a hot air circulation type drying oven at 180 [deg.] C 1 min (drying step), A metal material having a surface treated film is obtained.

In Comparative Example 1, the above-described Al material was used in the same manner as in Examples 1 to 30 until the pretreatment. A metal surface treatment agent used for a wet amount of 10 mL/m ² was applied onto the base metal using a #6SUS Mayer bar, and dried by heating at 80 °C. Further, in Comparative Example 2, the Al material was used for alkali degreasing in the same manner as in Examples 1 to 30 until the pretreatment, and then washed with water, further immersed in 1% dilute sulfuric acid at 65 ° C for 3 seconds, and washed with water. Further, the metal surface treatment agent was spray-treated at 55 ° C for 5 seconds using a spray device, and dried by heating at 80 ° C for 30 seconds.

In the comparative examples 3 to 6, the base metal described in Table 1 was prepared, and the water-based metal surface treatment agent was applied, and the mixture was degreased, washed with water, and dried by heating to obtain a metal material having no surface-treated film.

In each of Examples 1 to 30 and Comparative Examples 1 and 2, 2 The metal material surface-treated with the same aqueous metal surface treatment agent is subjected to lamination processing by a different method on the surface treatment film as shown below. Further, in Comparative Examples 3 to 6, two substrates of the same kind without the surface treatment film were prepared, and as shown below, the laminate metal was applied to the base metal by a different method.

(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 the metal material which does not have the surface treatment film, one of the two side surfaces is also thermally laminated, and the other one side surface is subjected to dry lamination. By the lamination processing, a polypropylene film laminated metal material is obtained.

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. was applied by bar coating. After the concentration of the non-volatile component was 25% by mass, it was dried in a hot air circulating drying oven at 80 ° C for 1 minute, and then the adhesive layer and a 30 μm unstretched polypropylene film (manufactured by Nakamura Chemical Co., Ltd., "FCZX"). The corona discharge treated surface was cured at 100 ° C and 1 MPa, and then cured at 40 ° C for 4 days, thereby performing lamination processing of dry lamination to obtain a metal material laminated with a polypropylene film.

(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. The coated metal sheet having a diameter of 160 mm was subjected to drawing (first time) to produce a cup having a diameter of 100 mm. Next, the cup was again drawn to a diameter of 75 mm (second time), and further drawn to a diameter of 65 mm (third time) to produce a can for the test material. In addition, the ironing rate (thinning fraction) in the first drawing process, the second drawing process, and the third drawing process is 5%, 15%, and 15%, respectively. .

[Performance Evaluation] (initial adhesion)

For the test materials after deep drawing, the presence or absence of peeling of the polypropylene film (referred to as "initial adhesion") was evaluated. 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 Table 2. Shown.

(drug tightness maintenance)

The test material after the deep drawing process was immersed in an electrolyte solution for a lithium ion battery in which 1000 ppm of ion-exchanged water was filled in a sealed container (electrolyte; 1 M-LiPF ₆ , solvent; EC: DMC: DEC = 1:1) After 1 (vol%), it was placed in a thermostat at 60 ° C for 7 days. Further, "EC" is ethyl carbonate, "DMC" is dimethyl carbonate, and "DEC" is diethyl carbonate. Thereafter, the test piece was taken out, immersed in ion-exchanged water for 1 minute, washed by shaking, and then dried in a hot air circulating type drying oven at 100 ° C for 10 minutes. When the film is not peeled off and the adhesion resistance of the film is excellent, it is "3 points", and when the film is not peeled off, it is "2.5 points" when the nail is strongly scraped, and "2 points" when the film is partially peeled off. The film peeling off the entire surface is "1 point." The rating is judged to be a practical level with a score of "2.5 points" or more. The results of the evaluation test are shown in Table 2.

As is apparent from the results shown in Table 2, the metal materials surface-treated with the aqueous metal surface treatment agent containing the urethane prepolymer containing the blocked isocyanate group as in Examples 1 to 5, regardless of the thermal lamination In the dry lamination, the initial adhesion and the resistance to drug adhesion were all good. Further, as shown in Examples 6 to 30, the metal material surface-treated with the aqueous metal surface treatment agent of the crosslinkable organic compound (B1) or the crosslinkable inorganic compound (B2) is used to obtain the drug-resistant adhesion further. Improve the results.

On the other hand, as the metal materials treated by the conventional metal surface treatment agents of Comparative Examples 1 and 2, or the metal materials which are not provided with the surface treatment film of Comparative Examples 3 to 6, regardless of the initial adhesion and resistance Satisfactory results were not obtained with the tightness of drug adhesion.

1‧‧‧Stainless steel substrate

2‧‧‧Surface treatment film

3‧‧‧Laminated materials (resin film or resin coating film)

10‧‧‧Metal materials

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 (7)

An aqueous metal surface treatment agent for treating a surface treatment film for forming a laminate film or a resin coating film on a surface of a metal material, characterized by comprising: two or more blocked isocyanate groups; The polyisocyanate compound (A) is selected from a crosslinkable organic compound (B1) having a functional group reactive with the above-mentioned isocyanate group and a crosslinkable inorganic compound (B2) having an element capable of reacting with the aforementioned isocyanate group. One type or two or more types of crosslinkable compounds (B). The aqueous metal surface treatment agent according to the first aspect of the invention, wherein the functional group of the crosslinkable organic compound (B1) is selected from the group consisting of a carboxyl group, a hydroxyl group, a carbodiimide group and a glycidyl ether group. One or two or more. The aqueous metal surface treatment agent according to claim 2, wherein the crosslinkable organic compound (B1) is tannin. The aqueous metal surface treatment agent according to claim 1, wherein the crosslinkable inorganic compound (B2) contains Mg, Al, Ca, Mn, Co, Ni, Cr(III), Zn, Fe, Zr, One or more selected from the group consisting of Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La Elements. The aqueous metal surface treatment agent according to any one of claims 1 to 4, wherein the polyisocyanate compound (A) is a bisulfite-terminated urethane prepolymer. The aqueous metal surface treatment agent according to any one of the first to fourth aspects of the present invention, wherein the solid content of the polyisocyanate compound (A) is M _A and the solid content of the crosslinkable compound (B) When the mass is M _B , the solid content ratio [M _A /(M _A +M _B )] of the polyisocyanate compound (A) is 0.5 or more. 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 6 to a surface of a metal material.