KR20130009679A - Aqueous metal-surface treatment agent and metal material - Google Patents

Abstract

PURPOSE: A water-based metal surface treatment agent for forming hexa-valent chrome-free surface treatment coating layer and a metal material formed by being treated with a processing agent are provided to prevent metal material, laminate film or resin coated layer from being exfoliated. CONSTITUTION: A water-based metal surface treatment agent comprises organic compound having the molecular weight of 10000 or less and contains two or more carboxyl groups and hydroxyl group, and a crosslinkable compound. The cross-linkable compounds are one or two kinds selected from crosslinking inorganic compound and crosslinking organic compound. The water-based metal surface treatment agent is an agent which forms a surface treating film(2) of resin coated film(3) or laminate film on a metal material(1).

Description

Aqueous metal surface treatment agent and a metal material which is processed by the treatment agent {AQUEOUS METAL-SURFACE TREATMENT AGENT AND METAL MATERIAL}

The present invention relates to a metal material formed by treating with a water-based metal surface treatment agent and a metal surface treatment agent for forming a surface treatment film excellent in adhesion and chemical resistance retention resistance which can prevent the metal material and the laminate film or resin coating film from peeling off. It is about. Specifically, even when laminating a resin film or forming a resin coating film on a metal material, and then performing a strict molding process such as a deep drawing process, ironing process or stretch draw process, the laminated film or the like does not peel off. The present invention relates to an aqueous metal surface treatment agent for forming a hexavalent chromium-free surface treatment film that can provide high adhesion and, moreover, has excellent chemical adhesion retention properties that can maintain high adhesion even when exposed to an acid or an organic solvent.

Lamination processing is a processing means which heat-presses a resin film (hereinafter referred to as a "resin film" or a "laminate film") to the surface of a metal material (hereinafter also simply referred to as a "metal surface"), and protects the metal surface. It is one of the coating | covering methods of the metal surface for the purpose of imparting or giving designability, and is used in various fields. This lamination process has less generation | occurrence | production amount of waste gas or warming gas, such as a solvent and carbon dioxide which generate | occur | produce at the time of drying, compared with the method of forming a resin coating film by apply | coating and drying what melt | dissolved or disperse | distributed the resin composition in the solvent to the metal surface. Therefore, it is applied suitably from the surface of environmental conservation, The use is expanded, For example, the body or lid | cover material of the can for foodstuffs which consists of aluminum foil material, steel foil material, aluminum foil for packaging, stainless steel foil, etc., foodstuff Used for containers for batteries or batteries.

In particular, metal foils such as aluminum foil or stainless steel foil, which are lightweight and have high barrier properties, are preferably used as exterior materials and tab lead materials for mobile lithium ion secondary batteries used in cellular phones, electronic notebooks, notebook computers, video cameras, and the like. Laminating is applied to the surface of this metal foil. Moreover, although the lithium ion secondary battery is examined as a driving energy of an electric vehicle or a hybrid vehicle, the laminated metal foil is also examined as the exterior material.

The laminate film used for such a lamination process is heat-compression crimped after bonding directly to a metal material. Therefore, compared with the general resin coating film which apply | coats and dries a resin composition, waste of a raw material can be suppressed, there are few pinholes (defect part), and there exists an advantage that it is excellent in workability. Generally as a material of a laminate film, polyester-based resins, such as polyethylene terephthalate and polyethylene naphthalate, and polyolefins, such as polyethylene and a polypropylene, are used.

If lamination processing is performed on the metal surface without treatment such as chemical conversion treatment, there is a problem that the laminate film is peeled off from the metal surface or corrosion occurs on the metal material. For example, in a food container or packaging material, after the contents are added to the container or packaging material after the laminating process, heat treatment for sterilization is performed, but the laminate film is peeled from the metal surface during the heating treatment. have. Moreover, in the exterior material etc. of a lithium ion secondary battery, processing with high workability is received in the manufacturing process. In addition, after long-term use, moisture in the atmosphere penetrates into the container, which reacts with the electrolyte to produce hydrofluoric acid, which penetrates the laminate film, causing peeling of the metal surface and the laminate film, and corroding the metal surface. There is a problem.

In response to such a problem, when laminating a laminate film on a metal surface, in order to improve the adhesion between the laminate film and the metal surface and the corrosion resistance of the metal surface, after degreasing and cleaning the metal surface, chemical conversion treatment such as phosphate chromate or the like is usually performed. This is carried out. However, such chemical conversion treatment requires a washing step for removing excess treatment liquid after the treatment, and it is costly to treat waste water of the washing water discharged from the washing step. In particular, for chemical conversion treatment such as phosphate chromate, a treatment liquid containing hexavalent chromium is used, but it tends to be saved from recent environmental considerations.

For example, Patent Document 1 proposes a ground treatment agent containing a specific amount of a water-soluble zirconium compound, a water-soluble or water-dispersible acrylic resin having a specific structure, and a water-soluble or water-dispersible thermosetting crosslinking agent. Moreover, in patent document 2, the nonchromium metal surface treating agent which consists of a specific amount of water-soluble zirconium compound and / or water-soluble titanium compound, an organic phosphonic acid compound, and tannin is proposed. Moreover, in patent document 3, the metal surface treatment agent containing the amination phenol polymer and specific metal compounds, such as Ti and Zr, and whose pH is 1.5-6.0 is proposed. Moreover, in patent document 4, the resin film containing an amination phenol polymer, an acryl-type polymer, a metal compound, and the phosphorus compound as needed is proposed.

International patent publication WO2002 / 063703 Japanese Unexamined Patent Publication No. 2002-265821 Japanese Laid-Open Patent Publication 2003-313680 Japanese Unexamined Patent Publication No. 2004-262143

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous metal surface treatment agent for forming a surface treatment film which is excellent in adhesion and chemical-resistance adhesion retention which can prevent the metal material and the laminate film or resin coating film from peeling off, and the metal surface treatment agent as the metal surface treatment agent. It is to provide a metal material formed by treatment. Specifically, even when a resin film is laminated on a metal material or a resin coating film is formed, and then strict molding processing such as deep drawing processing, ironing processing or stretch draw processing is performed, the laminated film or resin coating film is peeled off. Providing a metal surface treatment agent for forming a hexavalent chromium-free surface treatment film having excellent adhesion and resistance to chemicals that can maintain high adhesion even when exposed to an acid or the like, while not being exposed to an acid or the like, and treating with the metal surface treatment agent It is to provide a metal material formed by.

The aqueous metal surface treating agent which concerns on this invention for solving the said subject contains two or more carboxyl groups and / or hydroxyl groups in 1 molecule by the ratio of 30-300 in molecular weight, and the organic compound (A) whose molecular weight is 10000 or less, and Selected from a crosslinkable organic compound (B1) having a structural unit capable of reacting with the carboxyl group and / or the hydroxyl group, and a crosslinkable inorganic compound (B2) containing an element capable of reacting with the carboxyl group and / or the hydroxyl group. It is characterized by containing 1 type, or 2 or more types of crosslinking | crosslinked compound (B).

According to this invention, since the said organic compound (A) and said crosslinking | crosslinked compound (B) are contained, even if it is exposed to an acid etc., the surface treatment film obtained by processing with this aqueous metal surface treating agent has high adhesiveness. High adhesiveness can be maintained. As a result, even when a resin film is laminated to a metal material or a resin coating film is formed, and then strict molding processing such as deep drawing processing, ironing processing, or stretch draw processing is performed, further exposure to acid, organic solvent, etc. Even if it is, the laminated film or the resin coating film can be prevented from being peeled from the metal material.

In the water-based metal surface treatment agent according to the present invention, the crosslinkable organic compound (B1) is one or two or more structures selected from carbodiimide bonds, oxazoline groups, glycidyl ether groups, isocyanate groups and methylol groups. Has units.

According to this invention, since a crosslinkable organic compound (B1) has the above-mentioned structural unit, the surface treatment film obtained by processing with this aqueous metal surface treatment agent is more excellent in adhesiveness, and it is long term even if it exposes to an organic solvent or an acid. The more stable adhesiveness can be maintained over.

In the water-based metal surface treatment agent according to the present invention, the crosslinkable inorganic compound (B2) is Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W It contains one or two or more elements selected from Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and La.

According to this invention, since a crosslinkable inorganic compound (B2) contains the said element, the surface treatment film obtained by processing with this aqueous metal surface treating agent is more excellent in adhesiveness, and it is long term even if exposed to the organic solvent or an acid. The more stable adhesiveness can be maintained over.

The metal material which concerns on this invention for solving the said subject is characterized by having the surface treatment film formed by apply | coating the water-based metal surface treatment agent which concerns on the said invention on the metal material surface.

According to this invention, since it has the surface treatment film formed by apply | coating the water-based metal surface treatment agent which concerns on the said invention, it laminates to the metal material which has this surface treatment film, and after that, deep drawing process, ironing process, or Even when strict molding processing such as stretch draw processing or the like is carried out, even when exposed to acid or the like, it is possible to prevent the laminate film or the resin coating film formed on the surface of the metal material from peeling off.

According to the aqueous metal surface treatment agent which concerns on this invention, the water-based metal surface treatment agent for forming the surface treatment film excellent in the adhesiveness and chemical-resistance adhesive-resistance property which can prevent peeling of a metal material, a laminated film, or a resin coating film can be provided. have.

According to the metal material which concerns on this invention, the metal material which has such a surface treatment film can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows an example of the metal material which has a surface treatment film formed by apply | coating the water-based metal surface treatment agent concerning this invention.

EMBODIMENT OF THE INVENTION Hereinafter, the metal material which has a surface treatment film formed by apply | coating the water-based metal surface treatment agent concerning this invention and this metal surface treatment agent to the surface of a metal material is demonstrated. In addition, the technical scope of this invention is not limited by the following description and the form of drawing.

[Aqueous Metal Surface Treatment Agent]

As shown in FIG. 1, the water-based metal surface treating agent which concerns on this invention is a laminated film or resin coating film 3 on the surface of the metal material 1 (henceforth a "base metal 1") which is a base material. It is a processing agent for forming the surface treatment film 2 for base materials of the base material. The characteristic is that it contains an organic compound (A), 1 type (s) or 2 or more types of crosslinkable compounds (B) chosen from a crosslinkable organic compound (B1) and a crosslinkable inorganic compound (B2). "Containing" means that the compounds other than the organic compound (A) and the crosslinkable compound (B) may be contained in the aqueous metal surface treatment agent. As such a compound, surfactant, an antifoamer, a leveling agent, an antibacterial fungicide, a coloring agent, etc. are mentioned, for example. These compounds can be contained in the range which does not impair the meaning and film | membrane performance of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, the structure of this invention is demonstrated in detail.

(Organic Compound (A))

An organic compound (A) is a compound containing the carboxyl group and / or the hydroxyl group which is a functional group. The organic compound (A) having these carboxyl groups and / or hydroxyl groups (also referred to as "functional groups") can be reacted with the crosslinking compound (B) described later to improve the adhesion and the chemical-resistance adhesion-resistance of the surface-treated film obtained. . Two or more said carboxyl groups and / or hydroxyl groups which an organic compound (A) contains are contained in 1 molecule by the ratio of molecular weight 30-300 in one ratio. In this ratio, the organic compound (A) containing the carboxyl group and / or the hydroxyl group is more likely to react with the crosslinkable compound (B). As a result, the surface treatment film obtained by processing with an aqueous metal surface treatment agent becomes dense, and chemical-resistance adhesion retention can be improved more. As for the content rate of a carboxyl group and / or a hydroxyl group, it is more preferable to have two or more in 1 molecule by 1 ratio by molecular weight 30-150.

An organic compound (A) is a compound whose molecular weight is 10000 or less. When the molecular weight of an organic compound (A) is 10000 or less, the adhesiveness of the surface treatment film obtained can be improved, and chemical-resistance adhesiveness retention can be made into a practical level. When the molecular weight of an organic compound (A) exceeds 10000, when a surface treatment film is formed, the mobility of an aqueous metal surface treating agent will become low, it becomes difficult to orientate a carboxyl group and a hydroxyl group on the surface of a base metal, and adhesiveness with a base metal It may be lowered. Moreover, the contact chance of an organic compound (A) and a crosslinkable compound (B) becomes low, a site which does not crosslink arises, and crosslinking density may fall. As a result, the surface treatment film is not dense, the barrier property is lowered, and the chemical-resistance adhesion retention property is lowered. Barrier property means the property which prevents chemicals, such as an acid and an organic solvent, from penetrating into a surface treatment film. The molecular weight of an organic compound (A) is more preferable in it being 5000 or less, and especially preferable in it being 3000 or less.

As the organic compound (A), for example, oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, itaconic acid, propanedicarboxylic acid, butanedicarboxylic acid, pentanedicarboxylic acid, hexanedicarboxylic acid, Polyhydric carboxylic acids such as heptanedicarboxylic acid, butanetricarboxylic acid, butanetetracarboxylic acid, cyclohexanetetracarboxylic acid and hexanetricarboxylic acid; ethylene glycol, propylene glycol, butylene glycol, hexanediol, Polyhydric alcohols such as polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyethylene glycol, and polypropylene glycol; polyhydric hydroxycarboxylic acids such as malic acid, citric acid and tartaric acid;

Hexahydroxybenzene, pyrogallol, 1,2,4-trihydroxybenzene, phloroglycinol, catechol, resorcinol, hydroquinone, 5-methylpyrogallol, 2-methylresorcinol, 5- Methylresorcinol, 2,5-dimethylresorcinol, 3-methylcatechol, 4-methylcatechol, methylhydroquinone, 2,6-dimethylhydroquinone, 5-methoxyresorcinol, 3-methoxy Catechol, methoxyhydroquinone, 2,5-dihydroxy-1,4-benzoquinone, gallic acid, pyrogallol-4-carboxylic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxy Benzoic 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-methylbenzoic acid, 4-hydroxy-3,5-dimethylbenzoic acid, 1,4-dihydroxy- 2-naphthoic acid, methyl gallate, 2,4-dihydroxybenzoic acid Methyl 2,6-dihydroxybenzoate, methyl 3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate, ethyl 3,4-dihydroxybenzoate, 4,6-diaminoresorcinol Hydrochloride, 4,6-diaminoresorcinol, 2-nitroresorcinol, 4-nitrocatechol, melic acid, benzenepentacarboxylic acid, pyromellitic acid, trimellitic acid, hemimelic acid, trimesic acid, Phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic 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, Cyclic organic compounds such as L-ascorbic acid;

Hydrolyzable tannins, such as tannic acid; condensed tannins, such as persimmon tannin, theaflavin, and thearubizin, etc. are mentioned.

It is preferable that content of the organic compound (A) contained in an aqueous metal surface treating agent is 10 mass%-95 mass% with respect to the total solid contained in an aqueous metal surface treatment agent, and it is more preferable that it is 20 mass%-80 mass%. It is preferable and it is especially preferable that they are 20 mass%-70 mass%. When content of an organic compound (A) exists in this range, the density of a surface treatment film can be made higher, and chemical-resistance adhesive-resistance improves further by this. In addition, "total solid content" means solid content except the volatile components, such as a solvent, among the components which comprise an aqueous metal surface treating agent, and specifically, an organic compound (A), a crosslinkable organic compound (B1), and a crosslinking. It is the total amount of 1 type, or 2 or more types of crosslinking | crosslinked compound (B) chosen from an acidic inorganic compound (B2). Therefore, it is preferable that the organic compound (A) contained in an aqueous metal surface treating agent is 10 mass%-95 mass% with respect to the total amount (total solid content) of an organic compound (A) and a crosslinkable compound (B), 20 It is more preferable that it is mass%-80 mass%, and it is especially preferable that it is 20 mass%-70 mass%.

(Crosslinkable Compound (B))

The crosslinkable compound (B) is one or two or more compounds selected from a crosslinkable organic compound (B1) and a crosslinkable inorganic compound (B2). When an aqueous metal surface treating agent contains a crosslinkable compound (B), the adhesiveness and chemical-resistance adhesive-resistance of the surface treatment film obtained by processing this aqueous metal surface treating agent can be improved.

(Crosslinkable Organic Compound (B1))

A crosslinkable organic compound (B1) is an organic compound which has a structural unit which can react with the carboxyl group and / or the hydroxyl group which the organic compound (A) has. "Reactable" means that both or either one of the carboxyl group and the hydroxyl group which the organic compound (A) has can be contacted, and can react with them. A "structural unit" is a functional group or a single bond unit. "Have" means that you may have other functional groups and coupling units other than these structural units. As a crosslinkable organic compound (B1), the organic compound which has 1 type, or 2 or more types of structural units chosen from a carbodiimide bond, an oxazoline group, glycidyl ether group, an isocyanate group, and a methylol group is mentioned, for example. Can be.

Although it does not specifically limit as an organic compound which has a carbodiimide bond, For example, a polycarbodiimide compound can be used. The polycarbodiimide compound is, for example, five to one obtained by decarboxylation reaction of a diisocyanate compound having an aromatic ring or decarboxylation reaction of a diisocyanate compound having an aromatic ring and an aliphatic or alicyclic diisocyanate compound. Nonionic or cationic polycarbodiimide compounds in which both terminal isocyanate groups of a polymer having 15 carbodiimide bonds are sealed with a polyol compound or a polyamine can be used. In the case where the isocyanate group is sealed with a polyamine, an acid or alkylating agent is further acted to form a cation by bonding a hydrogen atom or an alkyl group to at least a part of the nitrogen atom forming the secondary amine or tertiary amine moiety derived from the polyamine. It is desirable to.

As a diisocyanate compound which has an aromatic ring used for decarbonation reaction, 3,3'- dimethoxy-4,4'-biphenylene diisocyanate, 1, 5- naphthalene diisocyanate, 1, 5-, for example Tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, Phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), etc. are mentioned.

As an aliphatic or alicyclic diisocyanate compound used for a decarboxylation reaction, it is tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1, 4- cyclo, for example. sildi hexyl isocyanate, and the like can be mentioned 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 2,4'- dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI).

The synthesis | combining method of the polycarbodiimide compound by a decarboxylation reaction is not specifically limited, The method normally used for the synthesis | combination of a polycarbodiimide compound can be used. For example, the above-mentioned various diisocyanate compounds can be mentioned in the presence of a carbodiimidation catalyst in an inert organic solvent, and a decarbonation is performed by adding a fixed temperature. Examples of the carbodiimidation catalyst include 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 1-ethyl-2-phosphorene-1-oxide, and 1-ethyl. Phosphorene oxides such as 3-methyl-2-phosphorene-1-oxide or 3-methyl-1-phenyl-2-phosphorene-1-oxide or 3-phosphorene isomers thereof can be used. As an inert organic solvent, ether solvents, such as tetrahydrofuran and 1, 4- dioxane, ketone solvents, such as cyclohexanone and acetone, or hydrocarbon solvents, such as hexane and benzene, can be used, for example. .

It is preferable that it is 5-15, and, as for the number of the carbodiimide bond in 1 molecule of polycarbodiimide compounds obtained by said decarbonation reaction, it is more preferable that it is 7-13. By making the number of carbodiimide bonds into the range of 5-15, the adhesiveness of the surface treatment film obtained by processing with an aqueous metal surface treating agent can be improved more, and a resin film etc. can be strongly adhered to a base metal. Moreover, since the structure of a polycarbodiimide compound becomes flexible, even if the surface treatment film obtained has flexibility and strict molding process is performed, a resin film etc. becomes difficult to peel more.

When the number of carbodiimide bonds is less than 5, since the reactivity of the polycarbodiimide compound rises and crosslinking is promoted too much, the surface treatment film obtained tends to be a hard and soft surface treatment film. Moreover, when the number of carbodiimide bonds exceeds 15, reactivity will fall too much and a crosslinking will become inadequate, and water dispersibility will also fall. When crosslinking becomes inadequate, the surface treatment film obtained will become dense and chemical-resistance adhesive-resistance will fall.

A polyol compound or a polyamine is further added and reacted with the solution of the polycarbodiimide compound obtained by the above-mentioned decarbonation reaction, and the isocyanate group of both terminals is sealed. As a polyol type compound, the poly (alkylene glycol) represented by following General formula (1) or its monoalkyl ether is mentioned, As a polyamine, the polyamine represented by following General formula (2) or the poly represented by following General formula (3) (Alkylenediamine) N-alkyl derivatives are mentioned. 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, n represents an integer of 2 to 30, and formula (2) In the above, R ³ to R ⁶ represent an alkyl group having 1 to 4 carbon atoms, R ⁷ represents an alkantriyl group having 2 to 4 carbon atoms, and R ⁸ in formula (3) 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.

[Formula 1]

[Formula 2]

(3)

In the formulas (1) to (3), examples of 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 include methyl group, ethyl group, propyl group, isopropyl group, Butyl group etc. are mentioned, Especially, a methyl group and an ethyl group are preferable. As R <^2> and R <^10> , an ethylene group, a propylene group, n-butylene group, etc. are mentioned, Especially, an ethylene group and a propylene group are preferable. As R <^7> , an ethane triyl group, a propane triyl group, a butane triyl group, etc. are mentioned.

Specifically as poly (alkylene glycol) represented by General formula (1) or its monoalkyl ether, Poly (ethylene glycol) whose n is 2-30, its monomethyl, or its monoethyl ether, n is 2- 30 phosphorus poly (propylene glycol), its monomethyl, or its monoethyl ether, etc. are mentioned. Specific examples of the polyamine represented by the general formula (2) include 3,3-bis (dimethylamino) propylamine, 3,3-bis (diethylamino) propylamine, and the like. Specifically as a poly (alkylenediamine) N-alkyl derivative represented by General formula (3), the terminal amino group of the poly (ethylenediamine) whose m is 2-30 is monomethylated or dimethylated, or, Monoethylated or diethylated, etc. may be mentioned.

When sealing of both terminal isocyanate groups of a polycarbodiimide compound is performed using the polyamine of Formula (2) or Formula (3), an acid or an alkylating agent is further added to the reaction solution containing the polycarbodiimide compound. A hydrogen atom or an alkyl group is bonded and cationized to at least a part of the nitrogen atom which forms the secondary or tertiary amine moiety derived from general formula (2) or general formula (3).

The acid used for the cationization may be either an inorganic acid or an organic acid. For example, sulfuric acid, hydrofluoric acid (hydrogen chloride gas, hydrochloric acid, hydrofluoric acid, etc.), phosphorous acid, phosphoric acid, alkylsulfuric acid (methyl sulfate, ethyl sulfuric acid, etc.), formic acid, acetic acid Etc. can be mentioned. As an alkylating agent used for cationization, halogenated alkyls, such as dialkyl sulfuric acid, such as dimethyl sulfuric acid and diethyl sulfuric acid, methyl chloride, ethyl chloride, a propyl chloride, and butyl chloride, etc. are mentioned, for example.

The polycarbodiimide compound is usually used in the form of aqueous solution or water dispersion. The aqueous dispersion may be in the form of an emulsion or may be in the form of a colloidal dispersion. The method of making it into an aqueous solution form or a water dispersion form is not specifically limited. For example, after cationic with an acid or an alkylating agent as described above, water is added, and then an inert organic solvent is removed by distillation or the like to form an aqueous solution or an aqueous emulsion. Dissolution or dispersion in water may be achieved based on either self solubility or self dispersibility, and may also be cationic surfactants (eg, tetraalkylammonium salts, etc.) and nonionic surfactants (eg, Polyoxyalkylene alkylphenyl ether, etc.) may be achieved by the 1 type (s) or 2 or more types selected from them. From the viewpoint of maintaining the adhesion of the surface-treated film obtained by treatment with an aqueous metal surface treatment agent and the chemical-resistance-resistance retention property, no surfactant is used, and self-solubility or self-dispersibility is caused by the action of the hydrophilic group of the polycarbodiimide compound. It is preferable to dissolve or disperse in water.

It does not specifically limit as an organic compound containing an oxazoline group, Conventionally well-known emulsion type or water-soluble type oxazoline group containing resin can be used. You may use both an emulsion type and a water-soluble type. An emulsion type means the type which forms an aqueous dispersion in water, and a water-soluble type means the type which forms an aqueous solution in water. As such oxazoline group containing resin, the copolymer which superposed | polymerized 1 type (s) or 2 or more types chosen from an addition polymeric oxazoline compound and another monomer is mentioned, for example.

Specifically as an addition polymeric oxazoline compound, 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-oxazoline, and 1 selected from the group thereof Species or mixtures of two or more thereof may be used. Among these, 2-isopropenyl-2-oxazoline is preferable because it is easy to obtain industrially.

Although the usage-amount of an addition polymeric oxazoline compound is not specifically limited, It is preferable that it is 5 mass% or more with respect to the gross mass of the mixture of an addition polymeric oxazoline compound and another monomer. When the amount is less than 5% by mass, the degree of crosslinking with the upper layer is insufficient, and there is a tendency that the chemical-resistance adhesion retention is insufficient.

It will not specifically limit, if it is a monomer which does not react with an oxazoline group and can copolymerize with an addition polymeric oxazoline compound as another monomer, For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate (Meth) acrylic acid esters such as 2-ethylhexyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and salts thereof; Unsaturated nitriles such as meth) acrylonitrile; unsaturated amides such as (meth) acrylamide, N-methylol (meth) acrylamide and N- (2-hydroxyethyl) (meth) acrylamide; vinyl acetate, propionic acid Vinyl esters such as vinyl; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α, β-fire such as vinyl chloride, vinylidene chloride and vinyl fluoride Saturated monomers; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene and sodium styrene sulfonate. 1 type, or 2 or more types of mixtures chosen from these group can be used.

As the method for producing an emulsion type oxazoline group-containing resin, a method of polymerizing one or two or more selected from an addition polymerizable oxazoline compound and the other monomers described above can be used by a conventionally known polymerization method. Of the conventionally known polymerization methods, in particular, emulsion polymerization can be preferably used.

As an emulsion polymerization method, methods, such as a monomer titration method, a multistage polymerization method, or a preemulsion method, can be used using a conventionally well-known polymerization initiator, surfactant, a solvent, etc. Specifically, a mixture containing an addition polymerizable oxazoline compound and one or two or more kinds selected from the other monomers described above is dispersed in an aqueous solvent containing a conventionally known surfactant under stirring conditions, followed by a polymerization initiator. It can superpose | polymerize by adding.

Although it does not specifically limit as surfactant, For example, Anionic surfactant, such as n-dodecylbenzenesulfonate sodium and sodium laurate; Nonionic surfactant, such as nonylphenol ether of polyethyleneglycol, is mentioned. . Although it does not specifically limit as a polymerization initiator, For example, hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-t- butyl peroxide, cumenehydride Peroxides such as loperoxide, t-butylhydroperoxide and diisopropylbenzenehydroperoxide; 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile And azo compounds such as azobiscyano valeric acid and 2,2'-azobis- (2-amidinopropane) dihydrochloride.

The aqueous solvent is 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 organic solvents include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, acetone, methyl ethyl ketone, and the like. Can be mentioned.

When making the structure of emulsion type oxazoline group containing resin into a core-shell-type structure, the acryl-type which a core part does not contain an addition polymeric oxazoline compound as a monomer, and contains 1 type or 2 types chosen from the other monomers mentioned above. It is an emulsion and it can be set as the oxazoline group containing resin which is an oxazoline group containing polymer layer in which a shell part contains an addition polymerizable oxazoline compound as a monomer and 1 type (s) or 2 or more types chosen from the above-mentioned other monomer. As the method for producing an oxazoline group-containing resin having such a core-shell structure, a known method such as a multistage feed method or a power feed method can be used.

As a manufacturing method of the water-soluble oxazoline group containing resin, a conventionally well-known polymerization method can be used, For example, 1 type (s) or 2 or more types chosen from an addition polymerizable oxazoline compound and the other monomer mentioned above are aqueous solvents. Solution polymerization may be used. Specifically, the polymerization is carried out by, for example, dispersing an addition polymerizable oxazoline compound and a mixture containing one or two or more selected from the other monomers described above under stirring conditions in an aqueous solvent and then adding a polymerization initiator. You can. There is no restriction | limiting in particular as a polymerization initiator and an aqueous solvent, The substance similar to the case of manufacturing the above-mentioned emulsion type oxazoline group containing resin can be used.

In order to make it "water-soluble", it is preferable that 1 type (s) or 2 or more types chosen from said other monomer contain a hydrophilic monomer. As a hydrophilic monomer, For example, (meth) acrylic-acid 2-hydroxyethyl, (meth) acrylic-acid methoxy polyethyleneglycol, (meth) acrylic-acid 2-aminoethyl, its salt, (meth) Acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, (meth) acrylonitrile, sodium styrene sulfonate, etc. are mentioned.

It is preferable that it is 50 mass% or more with respect to the gross mass of the mixture of an addition polymeric oxazoline compound and another monomer, and, as for the ratio of the hydrophilic monomer contained in water-soluble oxazoline group containing resin, it is more preferable that it is 70 mass% or more. By containing 50 mass% of hydrophilic monomers, oxazoline group containing resin can be made water-soluble easily.

Although it does not specifically limit as an organic compound which has a glycidyl ether group, A conventionally well-known polyhydric glycidyl ether compound can be used. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether Diglycerol diglycidyl ether, polyglycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylol propane diglycidyl ether, trimethylol propane triglycidyl ether, sorbitol polyglycidyl ether, and the like. Can be mentioned.

Examples of the organic compound having an isocyanate group include isomers of tolylene diisocyanate; aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate; aromatic aliphatic diisocyanates such as xylylene diisocyanate; isophorone Alicyclic diisocyanates such as diisocyanate and 4,4'-dicyclohexyl methane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate. Although the organic compound which has these isocyanate groups is not specifically limited, It is preferable to use the isocyanate compound blocked by various blocking agents from the viewpoint of the stability of an aqueous metal surface treating agent. As a blocking agent, various blocking agents, such as a phenol type, alcohol type, an oxime type, an active methylene type, an acid amide type, a carbamate type, a sulfite type, are mentioned, for example.

As an organic compound which has a methylol group, the sole or copolymer which makes 1 type, or 2 or more types chosen from a resor type | mold phenol resin, methylol melamine, and N-methylol acrylamide monomer as a structural unit is mentioned, for example. have.

(Crosslinkable inorganic compound (B2))

A crosslinkable inorganic compound (B2) is a compound containing an element which can react with the carboxyl group and / or the hydroxyl group which is a functional group which the organic compound (A) has. "Reactable" means that both or either of the carboxyl group and the hydroxyl group can be contacted and react with them. "Contains" means that you may have other elements besides these elements.

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

Specifically, Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, In Salts, complex compounds or metal hydride oxides (hereinafter also referred to as "salts") containing one or more elements selected from Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and La; Can be.

More specifically, bis (acetylacetonato) diaqua magnesium (II), magnesium aluminate, magnesium benzoate, magnesium formate, magnesium oxalate, magnesium tungstate, magnesium borate, magnesium molybdate, magnesium iodide, and iodide Magnesium salts such as magnesium diphosphate, magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, magnesium ammonium phosphate, magnesium hydrogen phosphate and magnesium oxide;

Aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum fluoride, aluminum iodide, aluminum acetate, aluminum benzoate, aluminum citrate, aluminum gluconate, selenic acid Aluminum salts such as aluminum, aluminum oxalate, aluminum tartarate, aluminum lactate and aluminum palmitate;

Bis (acetylacetonato) diaqua calcium (II), calcium benzoate, calcium citrate, calcium metatartrate, calcium selenate, calcium tungstate, calcium carbonate, calcium tetraborate, calcium molybdate, calcium maleate, calcium malate Calcium salts such as calcium phosphate, calcium fluoride, calcium phosphate, calcium nitrate, calcium hydroxide, calcium oxide, calcium oxalate, calcium oxide and calcium acetate;

Bis (acetylacetonato) diaquamanganese (II), trimanganese tetraoxide, manganese oxide (II), manganese oxide (III), manganese oxide (IV), manganese bromide (II), manganese oxalate (II), permanganic acid (Ⅶ) , Potassium permanganate (Ⅶ), sodium permanganate (Ⅶ), manganese dihydrogen phosphate (II), manganese nitrate (II), manganese sulfate (II), manganese sulfate (III), manganese sulfate (IV), manganese fluoride (II) Manganese salts such as manganese fluoride (III), manganese carbonate (II), manganese acetate (II), manganese acetate (III), ammonium manganese sulfate (II), manganese iodide (II), and manganese hydroxide (II); Acid salts;

Bis (acetylacetonato) diaquacobalt (II), tris (acetylacetonato) cobalt (III), sulfamate cobalt (II), cobalt chloride (II), chloropentamincobalt chloride (III), hexaammine cobalt chloride (III), diammine tetranitrocobalt (III) ammonium, cobalt sulfate (II), ammonium cobalt sulfate, cobalt nitrate (II), cobalt dialuminum oxide, cobalt (II), cobalt oxide (II), cobalt phosphate, Cobalt acetate (II), cobalt formate (II), tricobalt tetraoxide, cobalt bromide (II), cobalt oxalate (II), cobalt selenate (II), cobalt tungstate (II), hydroxycobalt carbonate (II), Cobalt salts such as cobalt molybdate (II), cobalt iodide (II), and cobalt phosphate (II);

Nickel sulfamate (II), nickel benzoate (II), nickel nitrate (II), nickel sulfate (II), nickel carbonate (II), nickel acetylacetonate (II), nickel chloride (II), hexaammine nickel chloride, Nickel oxide, nickel hydroxide (II), nickel oxide (II), nickel acetate, nickel citrate (II), nickel succinate (II), nickel bromide (II), nickel oxalate (II), nickel tartarate (II), selenic acid Nickel salts such as nickel (II), nickel hydroxy carbonate (II), nickel lactate (II), nickel molybdate (II), nickel iodide (II) and nickel diphosphate (II);

Chromium formate (III), chromium fluoride (III), chromium nitrate (III), chromium sulfate (III), chromium oxalate (III), chromium acetate (III), chromium acetate (III), chromium hydroxide (III), oxidation Chromium salts such as chromium (III), chromium bromide (III), and chromium iodide (III);

Bis (acetylacetonato) zinc (II), zinc benzoate (II), hydroxy zinc chloride (II), zinc formate (II), zinc citrate (II), zinc bromide (II), zinc oxalate (II), tartaric acid Zinc (II), Meta metatartrate (II), Zinc selenite (II), Zinc tungsten (II), Zinc fluoride (II), Zinc molybdate (II), Zinc butyrate (II), Zinc diphosphate (II) Zinc salts such as zinc sulfate (II), zinc carbonate (II), zinc chloride (II), zinc iodide (II), zinc hydroxide (II) and zinc (II);

Bis (acetylacetonato) diaqua iron (II), tris (acetylacetonato) iron (III), tripotassium iron trioxalate, iron formate (II), iron savanadiate (III), iron bromide (III), iron tartarate (III), iron (l), iron fluoride (II), iron fluoride (III), iron chloride (II), iron chloride (III), iron iodide (II), iron iodide (III), iron sulfate (II), Iron (III) sulfate, iron nitrate (II), iron nitrate (III), iron acetate (II), iron acetate (III), iron citrate (II), iron citrate (III), glycine iron (II), glycine iron (III), iron oxalate (II), iron oxalate (III), iron picolate (II), iron picolate (III), L-phenylalanine iron (II), L-phenylalanine iron (III), iron malonate ( Iron salts such as II), iron malonate (III), iron hydroxide (II), iron hydroxide (III), iron oxide (II), iron oxide (III), and triiron tetraoxide;

Bis (acetylacetonato) diaquastrontium (II), strontium formate (II), strontium citrate (II), strontium tungstate, strontium metastannate, strontium oxide (IV), strontium oxide (II), strontium oxalate, metaniob Strontium salts such as strontium oxide, strontium molybdate, strontium iodide, strontium nitrate, strontium sulfate, strontium carbonate, strontium acetate, strontium chloride, strontium phosphate, and strontium lactate;

Titanium dioxyammonium oxalate, dipotassium titanium oxyoxalate, titanium (II) oxide, titanium (III) oxide, titanium oxide (IV), titanium oxysulfate, basic titanium phosphate, titanium bromide (IV), metatitanic acid, metatitanic acid Zinc (II), aluminum titanate (III), potassium meta titanate, metatitanium tricobalt (II), zirconium titanate, strontium titanate, triiron titanate (III), copper meta titanate (II), sodium titanate, neodymium titanate (III), barium meta titanate, bismuth meta titanate (III), magnesium metatitanate, magnesium titanate, manganese titanate (II), lanthanum titanate (III), lithium titanate, ammonium hexafluorotitanium (IV), Potassium hexafluorotitanium (IV), titanium iodide (IV), titanium sulfate (III), titanium sulfate (IV), titanium chloride, titanium nitrate, titanium sulfate, titanium fluoride (III), titanium fluoride (IV), Hexafluorotitanic acid, titanium lactic acid, peroxotitanic acid, titanium laurate, titanium Titanium salts such as cetyl acetonate, titanium hydroxide (IV) and the like or titanates;

Tetrakis (acetylacetonato) zirconium (IV), zirconium chloride (IV), zirconium chloride (IV), zirconium silicate, zirconium acetate (IV), zirconium oxide (IV), zirconium oxide (IV), metazirconium Cesium Oxide, Lithium Metazirconate, Zinc Metazirconate (II), Aluminum Metazirconate (III), Calcium Zirconate, Cobalt (II) Metabolite, Strontium Metazirconate, Copper Zirconate (II), Sodium metazirconate, nickel metazirconate (II), barium metazirconate, bismuth metazirconate (III), magnesium metazirconate, zirconium oxycarbonate, ammonium hexafluorozirconium (IV), hexafluorozirconium ( (IV) Potassium acid, zirconium iodide, zirconium dihydrogen phosphate (IV), basic zirconium carbonate, ammonium zirconium carbonate, zirconyl ammonium carbonate, zirconium nitrate, zirconyl nitrate, zirconium sulfate ( IV), zirconium salts such as zirconyl sulfate, hexafluorozirconium acid, zirconium oxyphosphate, zirconium pyrophosphate, zirconium dihydrogen zirconate, zirconium oxychloride, zirconium oxychloride, zirconyl acetate, zirconium oxide, zirconium hydroxide and the like;

Silicates such as hexafluorosilicic acid and silica;

Tungsten chloride (VI), iron tungsten oxide (III), tungsten chloride (VI), tungsten oxychloride, tungsten dioxide, tungsten trioxide, metatungstic acid, ammonium metatungstate, sodium metatungstate, paratungstic acid, paratungstic acid Ammonium, sodium paratungstate, zinc tungstate (II), potassium tungstate, calcium tungstate, cobalt tungstate (II), strontium tungsten, cesium tungstate, copper tungstate (II), nickel tungstate, tungstic acid Tungsten salts such as barium, magnesium tungstate, manganese tungstate (II), lithium tungstate, phosphotungstic acid, ammonium phosphate tungsten and sodium phosphotungate;

Tris (acetylacetonato) cerium (III), cerium chloride (III), cerium oxide (III), cerium oxide (IV), cerium bromide (III), cerium oxalate (III), cerium hydroxide (IV), cesium sulfate Ammonium (IV), cerium sulfate ammonium (III), cerium carbonate (III), cerium sulfate, cerium acetate (III), cerium nitrate (III), cerium sulfate (IV), cerium fluoride (III), cerium iodide (III) ), Cerium salts, such as cerium (III) phosphate;

Molybdenum chloride (V), molybdenum oxide (IV), molybdenum oxide (VI), zinc molybdate (II), potassium molybdate, calcium molybdate, cobalt molybdate (II), cesium molybdate, nickel molybdate (II) , Barium molybdate, bismuth molybdate (III), magnesium molybdate, lithium molybdate, lithium paramolybdate, strontium molybdate, phosphomolybdate, ammonium phosphate, sodium phosphate, ammonium molybdate, ammonium molybdate, Molybdenum salts such as ammonium paramolybdate and sodium molybdate or the like;

Vanadium oxydichloride, vanadium oxytrichloride, vanadium trichloride, vanadium oxide, iron vanadate (III), vanadium bromide (III), vanadium oxyoxalate, vanadium iodide (II), vanadium pentoxide, metavanadine, sodium pyrovanadate Sodium vanadate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetylacetate, vanadium acetylacetate, invanad molybdenum Vanadium salts such as acids or vanadate salts;

Tin chloride (II), tin acetate (II), tin oxalate (II), tin tartarate (II), tin oxide (IV), tin nitrate, tin sulfate, tin fluoride (II), tin iodide (II), tin iodide (IV), tin salts or tartarate salts such as tin pyrolate (II), meta-tartrate, zinc meta-tartrate, calcium meta-stannate, strontium meta-stannate, barium meta-stannate, and magnesium meta-stannate;

Bismuth benzoate (III), bismuth chloride (III), bismuth citrate (III), bismuth oxyacetate (III), bismuth oxide tartrate (III), bismuth oxide (III), bismuth oxysulfate, bismuth bromide (III), Bismuth tartarate (III), bismuth hydroxide (III), bismuth oxycarbonate, bismuth zirconate (III), bismuth oxynitrate, bismuth titanate (III), bismuth tricarbonate (III), bismuth fluoride (III), molybdate Bismuth salts such as bismuth (III), bismuth iodide (III), bismuth nitrate (III), bismuth chloride (III), bismuth sulfate (III), bismuth acetate (III) and bismuth phosphate (III);

Tantalum chloride (V), tantalum oxide (V), tantalum bromide (V), tantalic acid, potassium tantalate, strontium metatantalate, sodium metatantalate, lithium metatantalate, tantalum iodide (V), tantalum oxyacetylaceto Tantalum salts such as nate, metatantalic acid, ammonium metatantalate, potassium heptafluorotantalate, or the like;

Telluric acid, ammonium metatellurate, potassium metatellurate, sodium metatellurate, tellurium iodide (IV), potassium tellurate, sodium tellurate, at telluric acid, potassium atluate, sodium atluate, barium tellurate Tellurium salts, such as lithium atherosulfate, tellurium chloride (IV), tellurium oxide (IV), tellurium bromide (IV), nitrate trinitrate, zinc atelurate, and tellurium salts;

Tris (acetylacetonato) indium (III), indium amide sulfate (III), indium dichloride, indium chloride (I), indium chloride (III), indium acetate (III), indium bromide (III), indium iodide (III) ), Indium salts such as indium nitrate, indium sulfate (III), indium fluoride (III), indium oxide (III), and indium hydroxide (III);

Bis (acetylacetonato) diaquabarium (II), barium selenite, barium atate, barium benzoate, barium aluminate, barium chloride, barium formate, barium citrate, barium oxide, barium bromide, barium oxalate, barium tartarate , Barium metazirconate, barium hydroxide, barium metastannate, barium tungsten, barium metatitanate, barium metaniobate, barium lactate, barium metaborate, barium molybdate, barium iodide, barium hydrogen phosphate, barium carbonate, barium fluoride, etc. Barium salts;

Tetrakis (acetylacetonato) hafnium (IV), hafnium chloride (IV), hafnium oxide (IV), hafnium iodide (IV), hafnium sulfate (IV), hafnium nitrate (IV), hafnium oxyoxalate (IV), fluorine Hafnium salts such as lohafnium acid, fluorohafnium acid salts, and hafnium fluoride;

Potassium selenite, potassium hydrogen selenite, cesium triselenide, sodium selenite, sodium selenite, copper selenite (II), sodium selenite, barium selenite, selenium chloride, selenium chloride (I), selenium chloride (IV), selenium oxide (IV), aluminum selenite, selenic acid, zinc selenite, potassium selenite, ammonium selenate, calcium selenate, cesium selenite, cobalt selenate, selenic acid Selenium salts such as copper (II), nickel selenite, sodium selenite, barium selenite, zinc selenate, or the like;

Scandium such as scandium chloride (III), scandium formate (III), scandium acetate (III), scandium nitrate (III), scandium oxide (III), scandium fluoride (III), scandium iodide (III), and scandium sulfate (III) Salts;

Niobium (II) oxide, niobium oxide (V), OH (hydrogen oxalate) niobium, niobium hydroxide (V), nioboxyacetylacetonate, metaniobate, calcium metaniobate, strontium metaniobate, barium niobate, Niobium salts such as magnesium metaniobate, lithium metaniobate, ammonium metaniobate, sodium metaniobate, niobium contaminated or the like;

Copper amide sulfate (II), copper benzoate (II), tetraammine copper (II) nitrate, copper citrate (II), copper oxide (I), copper bromide (I), copper oxalate (II), copper formate (II), Copper acetate (II), Copper propionate (II), Copper valeric acid (II), Copper gluconate (II), Copper tartarate (II), Copper chloride (II), Copper bromide (II), Copper hydroxide (II), Copper acetate (II), copper nitrate (II), copper sulfate (II), copper carbonate (II), copper oxide (II), hydroxy cupric nitrate, copper tungsten (II), copper carbonate (II), lactic acid Copper salts such as copper (II), copper fluoride (II) and copper iodide (I);

Tris (acetylacetonato) yttrium (III), yttrium chloride (III), yttrium formate (III), yttrium citrate (III), yttrium acetate (III), yttrium oxide (III), yttrium oxalate (III), yttrium nitrate ( Yttrium salts such as III, yttrium carbonate, yttrium fluoride, yttrium iodide, yttrium sulfate and yttrium phosphate;

Tris (acetylacetonato) lanthanum (III), lanthanum chloride (III), lanthanum formate (III), lanthanum acetate (III), lanthanum oxide (III), lanthanum oxalate (III), lanthanum nitrate (III), lanthanum carbonate ( Lanthanum salts such as III), lanthanum fluoride (III), lanthanum ititanate (III), lanthanum sulfate (III), lanthanum phosphate (III), and lanthanum iodide (III);

Tris (acetylacetonato) neodymium (III), neodymium chloride (III), neodymium formate (III), neodymium acetate (III), neodymium oxide (III), neodymium bromide (III), neodymium oxalate (III), neodymium nitrate (III) Neodymium salts, such as (III), neodymium carbonate (III), neodymium nitrate (III), neodymium fluoride (III), neodymium iodide (III), neodymium sulfate (III), and neodymium phosphate (III), etc. are mentioned. These compounds may be anhydrides or hydrates. Moreover, you may use independently and may use in combination of 2 or more type. Moreover, it may melt | dissolve in the aqueous metal surface treating agent solvent, and may be disperse | distributed.

The sum total (B = B1 + B2) of content of 1 type (s) or 2 or more types of crosslinkable compound (B) chosen from a crosslinkable organic compound (B1) and a crosslinkable inorganic compound (B2) is 5 mass%-with respect to total solid content. It is preferable that it is 90 mass%, It is more preferable that it is 10 mass%-80 mass%, It is especially preferable that it is 20 mass%-80 mass%. When content of a crosslinking | crosslinked compound (B) exists in the range of 5 mass%-90 mass%, the adhesiveness of surface treatment film and chemical-resistance adhesive-resistance retention improve further.

(solvent)

In order to improve the workability at the time of apply | coating to the surface of a metal material, the aqueous metal surface treating agent which concerns on this invention can contain various solvents as needed.

Examples of the solvent include water; alkanes such as hexane and pentane; aromatic solvents such as benzene and toluene; alcohol solvents such as ethanol, 1-butanol and ethyl cellosolve; tetrahydrofuran and dioxane Ether solvents; ester solvents such as ethyl acetate and butoxyethyl acetate; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfone solvents such as dimethyl sulfoxide; hexamethyl phosphate triamide, etc. Phosphate amide solvents; and the like. These solvents may use one type of said each solvent, and may mix and use 2 or more types. Among them, water is preferable for reasons of environmental and economic advantages.

(Other additives)

The aqueous metal surface treatment agent which concerns on this invention can contain surfactant, an antifoamer, a leveling agent, antibacterial antiseptic agent, a coloring agent, etc. in the range which does not impair the meaning and film performance of this invention.

(Preparation method of an aqueous metal surface treating agent)

The manufacturing method of the water-based metal surface treating agent which concerns on this invention is not specifically limited. For example, an organic compound (A) and a crosslinkable compound (B) can be mixed with the additive contained arbitrarily, the solvent optionally contained, etc., and can be prepared by fully mixing using a stirrer, such as a mixing mixer.

[Metallic materials]

As shown in FIG. 1, the metal material 10 which concerns on this invention has the base metal 1 and the surface treatment film 2 formed by apply | coating the water-based metal surface treatment agent which concerns on this surface to the surface. "Application | coating" means applying an aqueous metal surface treating agent to the surface of the base metal 1 by the application | coating process mentioned later. "Have" means that the structure may have other configurations than the base metal 1 and the surface-treated coating 2. For example, you may have the resin film 3 formed by the lamination process on the surface treatment film 2. Since the surface treatment film 2 is formed by applying the above-mentioned water-based metal surface treatment agent to the base metal 1 according to the present invention, the surface treatment film 2 is excellent in adhesion and chemical-resistance adhesion retention.

Since the metal material 10 has such a surface treatment film 2, after forming the resin film 3 or the resin coating film 3 on the surface treatment film 2, deep drawing process, ironing process, or Even when strict molding processing such as stretch draw processing is performed or when exposed to acid or the like, the resin film 3 or the resin coating film 3 can be prevented from being peeled from the metal material 10.

In addition, although the example in which the surface treatment film 2 and the resin film 3 or the resin coating film 3 were formed in one surface of the base metal 1 is shown in FIG. 1, the base metal 1 is shown. The surface treatment film 2 may be formed on both surfaces of the surface, that is, the other surface, and the resin film 3 or the resin coating film 3 may be formed.

The kind of base metal 1 is not specifically limited, Various things are applicable. For example, although the metal material applicable to the body or cover material of a food can, the food container, a battery container, the exterior material of a secondary battery, etc. is mentioned, It is not limited to these, A metal material applicable to a wide use can be used. have. Particularly, metal materials usable as exterior materials of lithium ion secondary batteries for mobiles used in cellular phones, electronic notebooks, notebook computers or video cameras, and exterior materials of lithium ion secondary batteries used as driving energy of electric vehicles or hybrid vehicles. have. Of these metal materials, a surface treatment film can be formed on the surface thereof, and a resin film can be laminated on the surface treatment film, and thereafter, strict molding processing such as deep drawing processing, ironing processing, or stretch draw processing. The metal material which can implement can be used preferably.

Examples of such metal materials include copper materials such as pure copper and copper alloys, aluminum materials such as pure aluminum and aluminum alloys, iron materials such as ordinary steel and alloy steel, nickel materials such as pure nickel and nickel alloys, and the like. Can be mentioned.

As a copper alloy, it is preferable to contain 50 mass% or more of copper, For example, brass etc. can be used. As alloy components other than copper in a copper alloy, Zn, P, Al, Fe, Ni etc. are mentioned, for example. As an aluminum alloy, it is preferable to contain 50 mass% or more of aluminum, For example, an Al-Mg type alloy etc. can be used. As alloy components other than aluminum in an aluminum alloy, Si, Fe, Cu, Mn, Cr, Zn, Ti etc. are mentioned, for example. As alloy steel, it is preferable to contain 50 mass% or more of iron, For example, stainless steel etc. can be used. As alloy components other than iron in alloy steel, C, Si, Mn, P, S, Ni, Cr, Mo etc. are mentioned, for example. As nickel alloy, it is preferable to contain 50 mass% or more of nickel, For example, Ni-P alloy etc. can be used. As alloy components other than nickel in a nickel alloy, Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, P etc. are mentioned, for example.

The base metal 1 may be formed by forming a film containing the above-described metal element on the surfaces of metal materials, ceramic materials or organic materials other than the above-described metal materials. Such a metal film can be formed by methods, such as plating, vapor deposition, and a clad, for example. Moreover, the shape, structure, etc. of the base metal 1 are not specifically limited, For example, a plate-shaped or thin metal material can be used.

As described above, according to the water-based metal surface treatment agent which concerns on this invention, 1 type chosen from said organic compound (A), said crosslinkable organic compound (B1), and said crosslinkable inorganic compound (B2), or Since it contains 2 or more types of crosslinking | crosslinked compound (B), while the surface treatment film obtained by processing with this aqueous metal surface treating agent has high adhesiveness, high adhesiveness can be maintained even if exposed to an acid etc. As a result, even when a resin film is laminated or the resin coating film is formed in the metal material in which the surface treatment film was formed, after that, even if strict molding processing such as deep drawing processing, ironing processing or stretch draw processing is performed, an acid or an organic solvent is used. Even when exposed to the back, the laminate film or the resin coating film can be prevented from being peeled from the metal material.

[Surface Treatment Method]

The method for treating a metal surface using the water-based metal surface treatment agent may be formed by a coating step of applying the water-based metal surface treatment agent to the surface of the base metal and a drying step of drying without washing with water after the coating step to form a surface treatment film. Can be.

(Coating step)

An application | coating process is a process of apply | coating an aqueous metal surface treating agent to the surface of a base metal. The method of apply | coating is not specifically limited, For example, the method of spray coat, dip coat, roll coat, curtain coat, spin coat, or these combination can be used. The use conditions of an aqueous metal surface treating agent are not specifically limited. For example, it is preferable that it is 10 degreeC-90 degreeC, and, as for the temperature of the water-based metal surface treatment agent and a metal material at the time of application | coating, it is more preferable that it is 20 degreeC-60 degreeC. If temperature is 60 degrees C or less, use of wasteful energy can be suppressed. Moreover, the time to apply and the quantity to apply can be suitably set according to the film thickness requested | required of the surface treatment film obtained.

(Drying step)

A drying process is a process of drying without washing with water after an application | coating process and forming a surface treatment film. Drying temperature can be made into the temperature according to the solvent to be used. For example, when water is used as a solvent, it is preferable that it is the range of 50 degreeC-250 degreeC. The drying apparatus is not particularly limited, but a batch type, continuous or hot air circulation type drying furnace, a conveyor hot air drying furnace, or an electromagnetic induction heating furnace using an IH heater can be used. Can be set arbitrarily.

The surface treatment film thus obtained is further formed with a resin film (laminate film) or a resin coating film, and then subjected to a strict molding process such as a deep drawing process, ironing process or stretch draw process. Even if it exposes, peeling of the resin film which consists of a laminated film or a resin coating film can be prevented.

Moreover, it is preferable to set it as 0.01 micrometer-1 micrometer, and, as for the film thickness of the surface treatment film obtained, it is more preferable to set it as 0.02 micrometer-0.05 micrometer. By setting the film thickness in the range of 0.01 µm to 1 µm, the adhesion of the surface-treated film and the chemical-resistance adhesion retention can be further improved.

Example

Hereinafter, an Example and a comparative example demonstrate this invention in detail. This invention is not limited by the following example. In addition, below, "part" means a "mass part", and "mass%" is synonymous with "weight%", and may be represented simply as "%" unless there is particular notice below. "Ppm" has the same meaning as "mg / L".

Organic Compound (A)

The used organic compound (A) is shown below. In addition, functional group content is the value which divided the molecular weight of the organic compound (A) by the total content of the carboxyl group and / or the hydroxyl group contained in 1 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)

[Crosslinkable Organic Compound (B1)]

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

700 parts (2.87 mol) of m-tetramethyl xylylene diisocyanate are reacted at 180 degreeC for 32 hours in presence of 14 parts of 3-methyl-1- phenyl- 2-phosphorene-1-oxides (carbodiimidation catalyst) The polycarbodiimide compound which is both isocyanate group and condensation degree 12 was obtained. 115 parts of polyoxyethylene monomethyl ether of the polymerization degree 12 were added to 224 parts of obtained polycarbodiimide compounds, and it reacted at 100 degreeC for 48 hours, and sealed the isocyanate group of both terminals. Subsequently, 509 mass parts of distilled water was gradually added at 50 degreeC, and the polycarbodiimide compound aqueous solution B1a was obtained.

(Organic compound II having carbodiimide bond; symbol B1b)

338 parts (1.35 mol) of diphenylmethane diisocyanate and 354 parts (1.35 mol) of 4,4'- dicyclohexyl methane diisocyanate are 3-methyl-1-phenyl-2-phosphorene-1-oxides (car Body imidation catalyst) It was made to react at 180 degreeC for 32 hours in presence of 2.9 parts, and the polycarbodiimide compound which is an isocyanate group and condensation degree 12 was obtained. 115 parts of polyoxyethylene monomethyl ether of the polymerization degree 12 were added to 224 parts of obtained polycarbodiimide compounds, and it reacted at 100 degreeC for 48 hours, and sealed the isocyanate group of both terminals. Subsequently, 509 parts of distilled water were gradually added at 50 degreeC, and the polycarbodiimide compound aqueous solution B1b was obtained.

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

700 parts of m-tetramethylxylylene diisocyanate was reacted at 180 ° C. for 32 hours in the presence of 14 parts of 3-methyl-1-phenyl-2-phosphorene-1-oxide (carbodiimidation catalyst), The polycarbodiimide compound which is an isocyanate group and condensation degree 12 was obtained. After 224.4 parts of obtained polycarbodiimide compounds and 10.2 parts of 3,3-bis (dimethylamino) propylamine were reacted at 80 ° C for 1 hour, 12.6 g of dimethyl sulfate was added and stirred for 1 hour. Subsequently, 509.1 g of distilled water was added gradually at 50 degreeC, and the polycarbodiimide compound aqueous solution B1c was obtained.

(Organic compound I having an oxazoline group; symbol B1d)

In a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, 220 parts of deionized water, 380 parts of 1-methoxy-2-propanol, 5 parts of sodium persulfate, 200 parts of 2-isopropenyl-2-oxazoline And 200 parts of ethyl acrylate were injected | poured, and it heated at 50 degreeC, flowing nitrogen gas slowly. The temperature in the flask was maintained at 50 ± 1 ° C., stirring was continued for 10 hours to complete the reaction, followed by cooling to obtain a water-soluble oxazoline group-containing resin B1d having a nonvolatile content of 40.0%. The number average molecular weight of this polymer was about 20,000, and the oxazoline group content per 1 g of polymers was 4.5 mmol / g.

(Organic compound II having oxazoline group; symbol B1e)

To a 1-liter separable flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, 228.1 parts of deionized water, 1.23 parts of a 25% aqueous solution of a surfactant nonylphenolethoxylate (6 moles of ethylene oxide) and 1.9 parts of 7% ammonia aqueous solution was injected | poured, and it heated up at 70 degreeC, flowing nitrogen gas slowly. Then, in this separable flask, 283.5 parts of butyl (meth) acrylate, 211.4 parts of styrene, 0.6 parts of divinylbenzene, 55.1 parts of 2-isopropenyl-2-oxazoline, 158.4 parts of deionized water, and surfactant nonylphenol Toxylate (Addition of 6 mol of ethylene oxide) 10 mass% of the preemulsion which consists of 31.0 parts of 25-% aqueous solution of ammonium sulfate salt, and 0.6 part of 7% ammonia water was added as initial injection. Then, the initiator aqueous solution which melt | dissolved 2.8 parts of potassium persulfate in 34.4 parts of pure waters was further added to this separable flask, and superposition | polymerization was started. Furthermore, the remaining preemulsion was dripped over 2.5 hours, it was made to react with stirring, and it was aged at 80 degreeC after dripping for 2.5 hours. After the reaction was completed, 1.4 parts of 7% ammonia water was added, and the pH was adjusted to 8.8 to obtain an oxazoline group-containing acrylic aqueous dispersion B1e having a nonvolatile content of 55.6% by mass. The theoretical oxazoline group equivalent was 0.90 mmol / g.

(Organic compound III having an oxazoline group: symbol B1f)

In a 1-liter separable flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 228.1 parts of deionized water, 1.23 parts of a 25% aqueous solution of a surfactant nonylphenolethoxylate (6 moles of ethylene oxide), And 1.9 parts of a 7% aqueous ammonia solution were injected, and the temperature was raised to 70 ° C while flowing nitrogen gas slowly. After heating up at 70 degreeC, 170.1 parts of butyl (meth) acrylates, 159.9 parts of styrene, 0.4 parts of divinylbenzenes, 95.0 parts of deionized water, surfactant nonylphenol ethoxyl which were prepared as a material of a 1st stage polymerization reaction in this separable flask 10 mass% of the pre-emulsion (henceforth "pre-emulsion of 1st stage") consisting of 18.6 parts of 25% aqueous solution of ammonium sulfate and 0.4 parts of 7% ammonia water of the ammonium sulfate salt was added as initial injection. Then, the initiator aqueous solution which melt | dissolved 2.8 parts of potassium persulfate in 34.4 parts of pure waters was added to this separable flask, and superposition | polymerization was started. Furthermore, the remaining 1st stage preemulsion was dripped over 1.3 hours, and it was made to react, stirring.

10 minutes after completion of the dropwise addition, 113.4 parts of butyl (meth) acrylate, 62.5 parts of styrene, 0.2 parts of divinylbenzene, 44.1 parts of 2-isopropenyl-2-oxazoline, 63.4 parts of deionized water, Surfactant nonylphenol ethoxylate (6 mole addition of ethylene oxide) A preemulsion (hereinafter, referred to as "second stage preemulsion") consisting of 12.4 parts of 25% aqueous solution of ammonium sulfate and 0.2 parts of 7% ammonia water is used as the separable flask. It dripped over 1.3 hours, and made it react with stirring. After completion of the second drop of the preemulsion, the mixture was aged at 80 ° C. for 2.5 hours. After the reaction was completed, 1.4 parts of 7% ammonia water was added, and the pH was adjusted to 8.9 to obtain an oxazoline group-containing acrylic aqueous dispersion B1f having a nonvolatile content of 55.6 mass% and a core / shell ratio of 6/4. The theoretical oxazoline group equivalent was 0.72 mmol / g.

(Organic compound having glycidyl ether group; symbol B1g)

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

(Organic compound having isocyanate group; symbol B1h)

Hexamethylene diisocyanate-acetoacetate acetate block body was used.

(Organic compound having a methylol group; symbol B1i)

Methylolmelamine was used.

[Crosslinkable Inorganic Compound (B2)]

The used crosslinkable inorganic compound (B2) is shown below.

B2a ： Titanium hydrofluoric acid (concentration 40.0 mass%)

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

B2c: silica (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 (10.0 mass% of non volatile matter concentration, particle diameter 10-30 nm, pH = 2.8)

B2f ： Hydrofluoric acid (concentration 40.0 mass%)

B2g: Chromium fluoride (III) (Cr concentration 1.0 mass%)

B2h: Iron fluoride (III) (Fe concentration 2.5 mass%)

B2i's selenium oxide (IV)

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

B2k; Chromium acetate (III)

[Aqueous Metal Surface Treatment Agent]

Organic compound Aa-Aj, 1 type (s) or 2 or more types chosen from crosslinkable organic compounds B1a-B1i and crosslinkable inorganic compounds B2a-B2k are combined with predetermined content, and a solvent is used as Table 1-Table 6, and The aqueous metal surface treating agents of Examples 1-91 and Comparative Examples 1-20 which were shown were prepared. In addition, "concentration" in Table 1-Table 6 shows the non volatile matter concentration (mass%) of each compound contained in an aqueous metal surface treating agent. Moreover, "A density | concentration" shows content (mass%) of the organic compound (A) with respect to the total solid in an aqueous metal surface treatment agent, and "B1 + B2 concentration" shows the crosslinkable compound (B) with respect to the total solid in an aqueous metal surface treatment agent. As content of the sum total content (mass%) of crosslinkable organic compound B1 and crosslinkable inorganic compound B2 is shown.

[Metallic materials]

The metal material used as a base metal is shown below.

Al: A1100P, thickness 0.3 mm

Cu: C1020P, thickness 0.3 mm

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

SUS ： SUS304 plate, thickness 0.3 mm

Ni-plated Cu: Electro-Ni-plated Cu plate (thickness 0.3 mm, Ni plating thickness 2 micrometers)

From these metal materials, the metal material shown by the "base material" column of Table 1-Table 6 was selected, and it prepared as the base metal of Examples 1-91 and Comparative Examples 1-24.

[Production of test materials]

(Surface treatment)

After spray-degreasing at 65 degreeC for 1 minute with 3% aqueous solution of the cleaner 359E (an alkali degreasing agent by Nippon Parkarizing Co., Ltd.) which used the base metal of Examples 1-91 and Comparative Examples 1-20 shown in Table 1-Table 6, The surface was washed by washing with water. Subsequently, in order to evaporate the water | moisture content of the surface of a metal material, it heat-dried at 80 degreeC for 1 minute. On the surface of the base metal degreased and cleaned, the aqueous metal surface treatment agents of Examples 1 to 90 and Comparative Examples 1 to 20 shown in Tables 1 to 6, respectively, were coated with a bar coat using a # 3 SUS Meier Bar (coating Process) and it dried in 200 degreeC for 1 minute in a hot-air circulation type drying furnace (drying process), and obtained the metal material which has a surface treatment film. In addition, two metal materials surface-treated using the same type of water-based metal surface treatment agent were prepared, respectively, and as shown below, lamination processing was performed on the surface treatment film by a different method.

Moreover, the metal material of Comparative Examples 21-24 was prepared, it was heat-dried after degreasing and water washing similarly to the above, without apply | coating an aqueous metal surface treating agent, and the metal material which does not have a surface treatment film was obtained. Moreover, two metal materials of the same kind were prepared, and the lamination process was given to the surface by the different method, respectively, as shown below.

(Lamination processing)

About one of the metal materials which have the surface treatment film prepared by two, the lamination process by heat lamination was performed on the surface treatment film. On the other surface treatment film, lamination processing by dry lamination was performed. Also about the metal material which does not have a surface treatment film, heat lamination was performed to one one side of two, and dry lamination was performed to the other one side surface.

Lamination processing by heat lamination was performed as follows. Dispersion of acid-modified polypropylene (manufactured by Mitsui Chemicals Co., Ltd., "R120K", non-volatile content 20 mass%) was applied by a bar coat using a # 8 SUS Meier bar, followed by 200 ° C in a hot air circulating drying furnace. The adhesive bond layer was formed by drying for 1 minute. Then, this adhesive bond layer and the 30-micrometer-thick polypropylene film (Toppero Co., Ltd. make, "CPPS") are thermally crimped at 190 degreeC and 2 Mpa for 10 minutes, and the lamination process by heat lamination is performed and polypropylene The metal material in which the film was laminated | stacked was obtained.

Lamination processing by dry lamination was performed as follows. After urethane-based dry laminate adhesive (Toyo Morton Co., Ltd. make, "AD-503 / CAT10", non-volatile content concentration 25 mass%) was apply | coated by the bar coat using ＃ 8 SUS Meier bar, 80 in hot-air circulation type drying furnace. After drying at 1 degreeC for 1 minute, after crimping | bonding this adhesive bond layer and the corona discharge treated surface of a 30 micrometer unstretched polypropylene film (The FTAmura Chemical Industry Co., Ltd. product, "FCZX") to 100 degreeC and 1 MPa, By curing for 4 days at ° C, lamination was performed by dry lamination to obtain a metal material on which a polypropylene film was laminated.

(Molding)

The polypropylene film laminated metal material obtained by heat lamination and the polypropylene film laminated metal material obtained by dry lamination were each deep-drawn by drawing ironing test. The coated metal plate punched out to 160 mm in diameter was draw-processed (first time), and the cup of diameter 100mm was produced. Subsequently, the cup was again drawn into the diameter of 75 mm (second time), and further drawn into the diameter of 65 mm (third time) to prepare a can as a test material. In addition, the ironing (thin powder) rates in the 1st drawing process, the 2nd drawing process, and the 3rd drawing process were 5%, 15%, and 15%, respectively.

[Performance evaluation]

(Adhesion)

About the can after a shaping | molding process, the presence or absence of peeling of a polypropylene film (henceforth "initial adhesiveness") was evaluated. A can was produced, the thing which peeled off the film and was excellent in initial stage adhesiveness was made into "three points", the thing which peeled a part of film into "two points", and the thing in which the film peeled from the whole surface was made into "one point". . The results of the evaluation test are shown in Tables 7 to 9.

(Drug-resistance adhesion retention)

Among chemical-resistance adhesive-resistance, it evaluated about adhesive-resistance (henceforth "electrolyte solution adhesion retention" hereafter) with respect to electrolyte solution. In detail, the presence or absence of the peeling of a polypropylene film was evaluated about the can after the molding process and after immersing in electrolyte solution as follows.

Of the can after the deep drawing, the charge in the closed container, the ion-exchanged water 1000 ppm addition of a lithium ion secondary battery electrolyte (electrolyte; 1 ㏖ / ℓ of LiPF _6, solvent; EC: DMC: DEC = 1 : 1: It was immersed in 1 (vol%)), and it put in the 60 degreeC thermostat for 7 days. In addition, "EC" is ethylene carbonate, "DMC" is dimethyl carbonate, and "DEC" is diethyl carbonate.

Thereafter, the test material was taken out and washed by immersion and shaking in ion-exchanged water for 1 minute, and then dried at 100 ° C. for 10 minutes in a hot air circulation drying furnace. After that, the surface of the film was scraped off with a tweezers tip, and the film had no peeling and was excellent in electrolyte-resistance adhesion retention, and the film was peeled off the entire surface. It evaluated as "one point." The results of the evaluation test are shown in Tables 7 to 9.

As shown to Table 7-Table 9, the metal material which has a surface treatment film formed by apply | coating the water-based metal surface treatment agent of Examples 1-91, also has initial stage adhesiveness and electrolyte solution adhesion | attachment in any of heat lamination and dry lamination. It was confirmed that the retention was very excellent.

1: base metal
2: surface treatment film
3: resin film (laminate film) or resin coating film
10: metal material having a surface treatment film

Claims (4)

A structural unit capable of reacting two or more carboxyl groups and / or hydroxyl groups in one molecule at a molecular weight of 30 to 300 in one molecule, having a molecular weight of 10000 or less, and the carboxyl group and / or the hydroxyl group It contains 1 type (s) or 2 or more types of crosslinkable compounds (B) chosen from the crosslinkable organic compound (B1) which has and the crosslinkable inorganic compound (B2) containing the element which can react with the said carboxyl group and / or the said hydroxyl group. An aqueous metal surface treatment agent. The method of claim 1,
The water-based metal surface treatment agent in which the said crosslinkable organic compound (B1) has 1 type (s) or 2 or more types of structural units chosen from a carbodiimide bond, an oxazoline group, a glycidyl ether group, an isocyanate group, and a methylol group. 3. The method according to claim 1 or 2,
The crosslinkable inorganic compound (B2) is Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, An aqueous metal surface treating agent containing one or two or more elements selected from Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd, and La. The metal material which has a surface treatment film formed by apply | coating the water-based metal surface treatment agent in any one of Claims 1-3 on the metal material surface.

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