KR20120079478A - Surface treatment agent for laminated metal material and method for producing laminated metal material - Google Patents

Abstract

assignment
Provided is a metal surface treatment agent for forming a surface treatment film on the surface of a metal material that can impart high adhesion to the laminate film or extruded laminate resin and high corrosion resistance to the metal material.
Solution
A silane coupling agent (A), cationic urethane resin (B), Zr compound (C1), Ti compound (C2) and a fluorine-containing inorganic compound (D) are contained, and a compounding ratio (A) / (B) is 1 by weight ratio / 50 or more and 20/1 or less, compounding ratio (C) / (B) is 1/100 or more and 1/2 or less by weight ratio (however, the weight of (C) is the sum of (C1) and (C2)), The above-mentioned problems are solved by a metal surface treatment agent in which a fluorine atom) / (B) is 1/1000 or more and 2/1 or less by weight ratio and the compounding ratio (C1) / (C2) is 1/10 or more and less than 2/1 by weight ratio. It was.

Description

SURFACE TREATMENT AGENT FOR LAMINATED METAL MATERIAL AND METHOD FOR PRODUCING LAMINATED METAL MATERIAL}

The present invention is directed to forming a surface treatment film which improves the adhesion (including processing adhesion) of the surface of the metal material and the laminated film, and also improves the corrosion resistance (particularly strong acid resistance and strong alkali resistance) of the metal material laminated the film. A surface treating agent for a laminated metal material and a method for producing the laminated metal material.

More specifically, after laminating a resin film on the surfaces of metal materials such as aluminum-based metal foil and stainless steel-based metal foil, even when severe molding processing such as deep drawing processing, ironing processing or stretch draw processing is performed, the laminated film The present invention relates to a surface treatment agent for a laminate metal material and a method for producing a laminate metal material for imparting high adhesion that does not peel off and for forming an article (molded article) having a superior corrosion resistance.

Lamination processing is a processing means for heat-pressing (or pressing through a glue) a resin film (hereinafter referred to as a resin film or a laminate film) on the surface of a metal material, and the surface of the metal material for the purpose of protecting the surface or providing designability. It is used in various fields as one of the coating methods. This lamination process is less in the amount of generation | occurrence | production of waste gas and warming gas, such as a solvent and carbon dioxide which generate | occur | produce in baking drying, compared with the method of apply | coating and baking-drying a resin composition, and forming a resin film, ie, coating. Therefore, it is preferable from the viewpoint of environmental conservation, and the use is expanded, for example, the body or lid | cover material of the can for foodstuffs made from aluminum thin plate material, steel thin plate material, aluminum foil for packaging, stainless steel foil, etc., a container for foodstuffs, etc. Or battery containers.

In particular, in recent years, as an exterior material of a lithium ion secondary battery for mobile devices used in cellular phones, electronic notebooks, notebook PCs, video cameras, and the like, metal foils such as aluminum foil and stainless steel foil having high barrier properties are preferably used. Lamination processing for metal foil is applied. Moreover, although the lithium ion secondary battery is examined as a driving energy of an electric vehicle or a hybrid vehicle, the metal foil processed by lamination is also examined as the exterior material.

Since the laminate film used for such a lamination process is heat-compression-bonded after directly bonding to a metal material, waste of raw materials can be suppressed compared with the general resin film formed by apply | coating a resin composition and then heat-drying. There are many advantages such as less pinholes (defects) and excellent workability. As a material of a laminate film, polyester-based resins, such as polyethylene terephthalate and polyethylene naphthalate, or polyolefin, such as polyethylene and a polypropylene, are used generally.

When the laminate film is laminated on the surface of the metal material (also referred to simply as metal surface), in order to improve the adhesion and corrosion resistance of the laminate film and the metal surface, after degreasing and cleaning the metal surface, usually chemical conversion treatment such as phosphate chromate 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, chemical conversion treatment such as phosphate chromate is used because a treatment liquid containing hexavalent chromium is used, and it tends to be light in recent environmental considerations.

On the other hand, when lamination processing is performed on the metal surface without carrying out 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 put into the container or packaging material after lamination processing, heat treatment for sterilization is performed, but the laminate film is peeled from the metal surface during the heat treatment. have. Moreover, in the exterior material etc. of a lithium ion secondary battery, the process with high workability is received in the manufacturing process. When such an exterior material is used for a long time, moisture in the atmosphere penetrates inside, and it reacts with the electrolyte to produce hydrofluoric acid, which penetrates the laminate film, causing peeling of the metal surface and the laminate film, There is a problem of corrosion.

In response to such a problem, various methods have been proposed for forming a film for improving adhesion with a laminate film on a metal surface prior to the lamination processing.

For example, Patent Document 1 proposes a method for producing an aluminum alloy for deep drawing ironing cans in which a chemical conversion film is formed on one surface of an aluminum alloy bath and a resin film is coated on the chemical conversion film. have. This chemical conversion film is a film formed of a chemical conversion treatment liquid containing one metal component selected from chromium, titanium and zirconium, and the adhesion and corrosion resistance with the resin film change according to the metal adhesion amount. ? It is said that the case of 50 mg / m <2> is preferable.

Moreover, the patent document 2 has proposed the surface treatment agent for adhesive bases for forming the surface treatment film which improves the interlayer adhesion of a metal surface and a laminated film, and also improves the corrosion resistance of the metal material which laminated the film. This surface treatment agent contains an aminated phenolic polymer and at least one metal compound selected from Ti, Zr, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V and trivalent Cr, 1.5? It is said that it is preferable that it is the range of 6.0.

In addition, Patent Document 3 proposes a surface treatment agent for forming a coated base film that enhances the adhesion of the coating film formed on the metal surface, not a surface treatment agent for forming a surface treatment film that enhances the adhesion between the metal surface and the laminate film. have. This surface treatment agent is a surface treatment agent for precoat metal materials containing a silane coupling agent (A), a cationic urethane resin (B), a Zr compound and / or a Ti compound (C), and a fluorine-containing inorganic compound (D), ( The mass ratio of A) / (B) is 1/50? 20/1, and the mass ratio of (Zr and / or Ti atom) / (B) is 1 / 1,000? 1/2, and the mass ratio of fluorine atom / (B) is 1 / 1,000? 2/1.

Japanese Laid-Open Patent Publication 2005-120422 Japanese Laid-Open Patent Publication 2003-138382 Japanese Laid-Open Patent Publication 2006-328445

In particular, in recent years, high workability and corrosion resistance are applied to mobile lithium ion secondary batteries used in cellular phones, electronic notebooks, notebook PCs or video cameras, or exterior materials of lithium ion secondary batteries as driving energy of electric vehicles or hybrid vehicles. This has been required. For this reason, high adhesion and corrosion resistance to metal materials have been required for surface treatment films formed prior to the lamination processing for such metal materials.

The present invention is able to meet the recent high level demands, and its object is to perform a severe molding process such as deep drawing, ironing or stretch draw processing after laminating a resin film on the surface of a metal material. Also in the case, it is providing the surface treating agent for laminated metal materials for forming the surface treatment film which can provide the high adhesiveness and high corrosion resistance which a laminated film does not peel. Moreover, another object of this invention is to provide the manufacturing method of the laminated metal material which has a surface treatment film formed from such a surface treating agent.

The present inventors examined whether or not the surface treatment agent for the coated base film described in Patent Document 3 can be used also as a surface treatment agent for a laminate metal material, but cannot form a surface treatment film excellent in adhesion and corrosion resistance as it is, It has been found that the present invention can be achieved by defining a specific range, and the present invention has been completed.

Surface treatment agent for a laminate metal material which concerns on this invention for solving the said subject is a silane coupling agent (A), cationic urethane resin (B), Zr compound (C1), Ti compound (C2), and a fluorine-containing inorganic compound (D ), And the blending ratio (A) / (B) is 1/50 or more and 20/1 or less by weight ratio, and the blending ratio (C) / (B) is 1/100 or more and 1/2 or less or less by weight ratio ((C) Is the sum of (C1) and (C2)), and the compounding ratio (fluorine atom) / (B) is 1/1000 or more and 2/1 or less by weight ratio, and the compounding ratio (C1) / (C2) is 1 / by weight ratio. It is characterized by being 10 or more and less than 2/1.

In the surface treating agent for the laminated metal material according to the present invention, the cationic urethane resin (B) contains an amino functional group selected from a secondary amino group and a tertiary amino group.

In the surface treating agent for the laminate metal material according to the present invention, at least 5% by mass of the entire silane coupling agent (A) is amino selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. It is a silane coupling agent which has a functional group.

In the surface treating agent for the laminate metal material according to the present invention, the Zr compound (C1) and the Ti compound (C2) are fluorides or fluoroacids or fluoroacid salts.

MEANS TO SOLVE THE PROBLEM In the manufacturing method of the laminated metal material which concerns on this invention, the surface treating agent for the laminated metal material of this invention was apply | coated and dried on the surface of metal material, and it was 0.01-degree. A 1 g / m <2> film is formed, and then a polyester resin, a polyethylene resin, a polypropylene resin, or a modified resin thereof is laminated.

In the manufacturing method of the laminated metal material which concerns on this invention, the said metal material is metal foil of aluminum type or stainless steel type.

According to the surface treating agent for a laminate metal material according to the present invention, a laminate metal material, a laminate metal container, or a laminate metal packaging material having excellent adhesion to the laminate film (including processing adhesion) and corrosion resistance (especially strong acid resistance and alkali resistance) is produced. It exhibits an excellent effect as a surface treating agent for making. Moreover, according to the surface treating agent for laminated metal materials which concerns on this invention, it does not have hexavalent chromium, and is chromium-free which considered the recent environmental problem, and exhibits the effect that there is little environmental load. Moreover, according to the manufacturing method of the laminated metal material which concerns on this invention, the outstanding effect that the metal container or packaging material excellent in adhesiveness and corrosion resistance can be provided is provided.

The surface treating agent for the laminated metal material and the manufacturing method of the laminated metal material according to the present invention will be described in detail below. In addition, in this application, a weight ratio and a mass ratio, weight and mass are all the same meaning.

[Surface Treatment Agent for Laminated Metal Materials]

The surface treatment agent for laminate metal materials (hereinafter, also simply referred to as "surface treatment agent") according to the present invention includes a silane coupling agent (A), a cationic urethane resin (B), a Zr compound (C1), a Ti compound (C2), and fluorine-containing An inorganic compound (D) is contained as an essential component. In addition, a fluorine-containing inorganic compound (D) may be mix | blended as a single compound, and may be a Zr compound (C1) or Ti compound (C2) containing fluorine. When Zr compound (C1) or Ti compound (C2) contains fluorine, Zr compound (C1) or Ti compound (C2) containing fluorine can also be called a fluorine-containing inorganic compound (D). By apply | coating such a surface treating agent to a metal surface and drying, the surface treatment film suitable as a base film for laminated metal materials can be formed.

(Silane coupling agent)

The silane coupling agent (A) has a high -OH activity of the silanol group generated by hydrolysis, and forms a strong chemical bond of -Si-O-M via the metal material M as the base material and an oxygen atom. This chemical bonding contributes in particular to good adhesion with the metal material M. Moreover, a silane coupling agent (A) contributes also to the adhesive improvement with a laminated film by reaction with the organic functional group contained in the laminated film formed as an upper layer. When the functional group which made O, N, etc. which have strong polarity into the silane coupling agent (A) is introduce | transduced, adhesiveness with a laminate film improves further.

As the silane coupling agent (A), for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-propyltrimethoxysilane, N-phenyl-3-propyltrie Methoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, N- (2-aminoethyl) aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane, N-β- (N -Vinylbenzylaminoethyl) -3-aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercapto Propylmethyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxy Silane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilino Propyltriethoxysilane, γ-anilino Lofilmethyldiethoxysilane, isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, ureidepropyltriethoxysilane, bis (trimethoxysilyl) aminovinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltri Ethoxysilane, vinylmethyldiethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (Triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldiethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichloro Silane, dimethyldichlorosilane, trimethylchlorosilane, and the like.

The silane coupling agent (A) has a compatibility with a laminate film (resin film or extruded laminate resin to be described later) laminated as an upper layer, and there are cases in which performance does not appear as expected depending on the combination. In the use of the present invention in which the surface treating agent is used for a laminate metal material, when the silane coupling agent (A) having an amino group is applied, the compatibility with the laminate film is good. Therefore, in the surface treating agent which concerns on this invention, it is preferable that a silane coupling agent (A) contains at least 1 type (1 type or 2 or more types) which has an amino functional group.

Here, an amino functional group is a functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. Examples of counter ions in the case of having a quaternary ammonium group include halogen ions including chlorine ions, phosphate ions, nitrate ions, sulfate ions and organic acid ions. More preferable amino functional group is a tertiary amino group. The reason for this is that adhesiveness with a laminate film is also good, but when used industrially, stability (storage stability) as a surface treating agent is important. From this point of view, the inventors found out that a tertiary amino group that gives high adhesion and has excellent storage stability and accompanying operational stability is most preferred.

It is preferable that content with respect to the whole silane coupling agent (A) is 5 mass% or more, It is more preferable that it is 10 mass% or more, It is especially preferable that it is 20 mass% or more of the silane coupling agent which has such at least 1 type of amino functional group. Do. The silane coupling agent (A) having such a content can eliminate or minimize the adverse effects such as adhesion and corrosion resistance to the laminate film, which may occur depending on the type of the laminate film.

When using 2 or more types in mixture as a silane coupling agent (A), it is preferable to use the silane coupling agent (A) which has a functional group which reacts with each other and produces a new bond. By doing in this way, film adhesiveness (process adhesiveness) can be improved further, and corrosion resistance can also be improved. For example, as a silane coupling agent which reacts with a silane coupling agent having a primary amino group and / or a secondary amino group to generate a new bond, (i) a silane coupling agent having a glycidyl group as the functional group is preferable. And (ii) use of a silane coupling agent (eg, a silane coupling agent having a glycidyl group as a functional group) and a silane coupling agent having an isocyanate group as the functional group. Preferred is mentioned. The mixing ratio of the silane coupling agents having functional groups which react with each other to form a bond as in the latter (ii) does not have to be an amount in which the functional groups react with each other without excessive or insufficient, and it is not one functional group (for example, a primary amino group or As an equivalent ratio of the secondary amino group) and the other functional group (for example, glycidyl group), 50: 1? It is preferable that it is the range of 1:50, and it is 30: 1? It is more preferable that it is the range of 1:30.

(Cation urethane resin)

The cationic urethane resin (B) is in the form of a water-soluble or aqueous emulsion. Dissolution or dispersion of the cationic urethane resin (B) in water may be achieved on the basis of self solubility or self dispersibility, and also cationic surfactants (for example, alkyl quaternary ammonium salts, etc.) and / or nonionic surfactants. You may disperse | distribute by presence of (for example, alkylphenyl ether etc.). Such cationic urethane resin (B) provides flexibility to the surface treatment film obtained, and contributes to the improvement of the adhesiveness of a laminated film, and acts effectively to improve process adhesiveness.

The cationic urethane resin (B) is a polyol which is a monomer component constituted so long as it has at least one kind (at least one kind or two or more kinds) of cationic functional groups selected from secondary amino groups, tertiary amino groups and quaternary ammonium salts. And the polyisocyanate component and the polymerization method are not particularly limited. Especially, it is preferable to have at least a tertiary amino group. On the other hand, since the primary amino group reacts vigorously and reacts directly with a glycidyl group or the like, it is not preferable because the stability or adhesiveness of the drug is significantly lowered and it is not contained. The proportion of tertiary amino groups in the cationic functional group is 30? It is preferable that it is 100%, and is 60%? It is more preferable that it is 100%, and especially the surface treatment film for lamination metal material uses can improve the adhesiveness by making tertiary amine into this range.

The cationic urethane resin (B) is, for example, aliphatic, alicyclic or aromatic diisocyanates such as hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI) and isophorone diisocyanate (IPDI); The polyol which introduce | transduced the amino group in chains, such as a polyester polyol, a polyether polyol, and a polycarbonate polyol, can be obtained by superposing | polymerizing by a conventionally well-known method and quaternizing an amine with alkyl sulfate etc. partially. Substituents on nitrogen as cationic functional groups include substituents such as hydrogen, alkyl, aryl, alkenyl, alkynyl, hydroxyalkyl groups, but are not limited to these. You may mix 2 or more types of cationic urethane resins (B) with a surface treating agent.

In the above, as the aliphatic, alicyclic or aromatic polyisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4 '-Dicyclohexyl methane diisocyanate, 2,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalenedi Isocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, Phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc. are mentioned. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1, 4- cyclohexylene diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, 2,4 When an aliphatic or alicyclic polyisocyanate compound such as' -dicyclohexyl methane diisocyanate or isophorone diisocyanate is used, a surface treated film excellent in chemical resistance and anticorrosiveness is obtained.

In the above, as the polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1 , 3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 2-methyl-1 , 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentane Diol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptane Aliphatic diol compounds such as diol, 3,5-heptane diol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, trimethylolethane, Trimethylolpropane, hexitols, pentitols, glycerin, diglycerine, polyglycerol, pentaerythritol, dipentaerythritol, tet Methylolacrylamide and the like having three or more aliphatic or alicyclic alcohol compounds such as propane.

In the above, as the polyether polyol, for example, ethylene oxide adducts such as ethylene glycol, diethylene glycol, triethylene glycol, propylene oxide adducts such as propylene glycol, dipropylene glycol and tripropylene glycol, and the polyol Ethylene oxide and / or propylene oxide adducts, polytetramethylene glycol, and the like.

In the above, as the polyester polyol, for example, the polyol and the like, ester-forming derivatives such as polyhydric carboxylic acids or esters thereof, anhydrides and halides in amounts less than the stoichiometric amounts thereof, and / or lactones Or what is obtained by the direct esterification and / or transesterification reaction of the hydroxycarboxylic acid compound obtained by the hydrolysis ring opening is mentioned. As a polyhydric carboxylic acid, For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeline acid, suveric acid, azelaic acid, sebacic acid, dodecaneic acid, 2-methyl succinic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-methylpentane diacid, 2-methyloctanoic acid, 3,8-dimethyldecane diacid, 3,7-dimethyldecane diacid, dimer acid, hydrogenated dimer acid, etc. Aliphatic dicarboxylic acids; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid; Tricarboxylic acids such as trimellitic acid, trimesic acid, and trimers of castor oil fatty acid; Polycarboxylic acids, such as tetracarboxylic acids, such as a pyromellitic acid, are mentioned. As the ester-forming derivative, acid anhydrides of these polyhydric carboxylic acids; Halides such as chlorides and bromides of the polyvalent carboxylic acids; Lower aliphatic esters, such as methyl ester of this polyhydric carboxylic acid, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, amyl ester, etc. are mentioned. Examples of the lactones include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, and δ-valerolactone.

In the above, as a polycarbonate polyol, what is obtained by esterifying a carbonic acid and a fatty acid polyol, etc. can be used, for example. Specifically, diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, dimethylene carbonate and diphenyl And reaction products such as carbonate and phosgene.

In cationic urethane resin (B), since the use of surfactant as a solubilizer or an emulsifier may adversely affect the adhesiveness or water resistance to a metal material, the soap free or the usage-amount which does not use such surfactant is suppressed. One is more preferable.

The weight average molecular weight of cationic urethane resin (B) is 1,000? It is preferable that it is 1,000,000, and 2,000? It is more preferable that it is 500,000. When the weight average molecular weight is less than 1,000, the formability of the surface treatment film tends to be insufficient, while when the weight average molecular weight exceeds 1,000,000, the stability of the surface treatment agent tends to be lowered.

Moreover, as long as it is compatible with cationic urethane resin (B), you may mix and use acrylic resin, ester resin, amino resin, epoxy resin, or phenol resin. These resins preferably have water solubility or water dispersibility. It will be compatible with the surface treating agent of this invention, and will not specifically limit, unless it reduces the performance of the film formed. Moreover, the ionicity of resin, such as cationic, anionic, and nonionic, is not limited, either. Moreover, in order to improve the film forming property and to form a more uniform and smooth film, you may use the organic solvent.

As for cationic urethane resin (B), it is preferable that compounding ratio (A) / (B) with a silane coupling agent (A) is 1/50 or more and 20/1 or less by weight ratio. By setting it as such a compounding ratio, the adhesiveness excellent in the laminated film which is an upper layer can be obtained. Moreover, the more preferable ranges of compounding ratio (A) / (B) are 1/20 or more and 10/1 or less, and still more preferable ranges are 1/10 or more and 5/1 or less. When the compounding ratio (A) / (B) is less than 1/50, the hardness of the obtained surface treated film is lowered and sufficient processing adhesiveness is not obtained well, and when the compounding ratio (A) / (B) exceeds 20/1, Rather, adhesiveness with the metal surface which is a base metal is hard to be obtained, and the adhesiveness of the laminated film through a surface treatment film may deteriorate.

(Zr compound and Ti compound)

Zr compound (C1) and Ti compound (C2) act so that the obtained surface treatment film may improve corrosion resistance of a metal material. In the surface treating agent which concerns on this invention, this Zr compound (C1) and Ti compound (C2) are made into essential components, and the compounding ratio (C1) / (C2) is 1/10 or more and less than 2/1 by weight ratio. It is essential configuration to do. In this invention, by making Zr compound (C1) and Ti compound (C2) into an essential component, adhesiveness with the resin film or extrusion laminated resin laminated on the obtained surface treatment film can be improved compared with the case where only one of them is contained. Moreover, the corrosion resistance of a metal surface can be improved.

As the Zr compound (C1) and the Ti compound (C2), carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluorides, fluoroacids (salts), organic acid salts, organic complexes and the like of Zr or Ti can be used. Among these, fluorides and fluoroacids (salts) which serve as fluorine-containing inorganic compounds (D) to be described later are preferable. Specifically, basic zirconium carbonate, zirconium oxycarbonate, ammonium zirconium carbonate, zirconyl ammonium carbonate (NH ₄ ) ₂ [Zr (CO ₃ ) ₂ (OH) ₂ ], zirconium oxide (IV) (zirconia), titanium oxide ( IV) (titania), zirconium nitrate, zirconyl nitrate ZrO (NO ₃ ) ₂ , titanium nitrate, zirconium sulfate (IV), zirconyl sulfate, titanium (III), titanium sulfate (IV), titanium sulfate TiOSO ₄ , Zirconium oxyphosphate, zirconium pyrophosphate, zirconium dihydrogen phosphate, zirconium fluoride, titanium fluoride (III), titanium fluoride (IV), hexafluorozirconate H ₂ ZrF ₆ , ammonium hexafluoro zirconate [(NH ₄ ) ₂ ZrF ₆ ], hexafluorotitanic acid H ₂ TiF ₆ , ammonium hexafluorotitanate [(NH ₄ ) ₂ TiF ₆ ], zirconyl acetate, titanium laurate, zirconiumacetylacetonate Zr (OC (= CH ₂ ) CH ₂ COCH _{3) 4,} di-isopropoxy titanium-bis acetone _{(C 5 H 7 O 2)} 2 Ti [OCH (CH 3) 2] 2, titanium acetyl O Sat carbonate and the like can be mentioned _{Ti (OC (= CH 2)} CH 2 COCH 3) 3. These may be anhydrides or hydrates. Each compound of a Zr compound and a Ti compound may be used individually, or may be used in combination of 2 or more type.

The total compounding amount (C = C1 + C2) of the Zr compound (C1) and the Ti compound (C2) is that the compounding ratio (C) / (B) to the cationic urethane resin (B) is 1/100 or more and 1/2 or less by weight ratio. It is preferable that it is 1/50 or more and 1/4 or less, and it is more preferable that they are 1/20 or more and 1/10 or less. If the compounding ratio (C) / (B) is less than 1/100, the corrosion resistance is insufficient. If the compounding ratio (C) / (B) is more than 1/2, the adhesion of the laminate film or the storage stability of the surface treatment agent tends to be lowered. .

Moreover, it is necessary for the Zr compound (C1) and the Ti compound (C2) to have a compounding ratio (C1) / (C2) in the range of 1/10 to 2/1 by weight ratio. By coexisting a Zr compound (C1) and Ti compound (C2) within this range, the adhesiveness of the obtained surface treatment film and the laminated resin film or extrusion laminated resin can be improved, and also the corrosion resistance of a metal surface can be improved. In addition, when Zr compound (C1) and Ti compound (C2) do not coexist within this range, sufficient characteristic (adhesiveness and corrosion resistance) as a base film for laminated metal materials cannot be acquired. Specifically, when the compounding ratio (C1) / (C2) is less than 1/10, the adhesiveness decreases or appearance defects occur, and when the compounding ratio (C1) / (C2) is 2/1 or more, the corrosion resistance tends to be lowered.

Therefore, the present invention, as can be seen from the results of Examples and Comparative Examples described later, by coexisting the Zr compound (C1) and Ti compound (C2), and paying attention to the content ratio of both to be within the above specific range It has been found that all of the problems of obtaining high adhesion (including processing adhesion) and high corrosion resistance (particularly strong acid resistance and strong alkali resistance) can be solved.

(Fluorine-containing inorganic compound)

The fluorine-containing inorganic compound (D) releases free fluoride ions or complex fluoride ions in the liquid, and serves as an etching agent for the metal surface to be formed as a surface treatment film. It does not specifically limit as a fluorine-containing inorganic compound (D), For example, hydrofluoric acid, ammonium fluoride, sodium fluoride etc. are mentioned as a thing which releases free fluoride ion. Examples of the complex fluoride include hexafluorosilicate, hexafluorosilicate zinc, hexafluorosilicate manganese, hexafluorosilicate silicate, hexafluorosilicate, hexafluorotitanic acid, hexafluorozirconic acid and the like. have. The said compound may be used individually by 1 type, and may mix and use 2 or more types.

A fluorine-containing inorganic compound (D) may be mix | blended as a single compound and said Zr compound (C1) or Ti compound (C2) may be sufficient as it. When a Zr compound (C1) or Ti compound (C2) contains fluorine, the Zr compound (C1) or Ti compound (C2) containing fluorine turns into a fluorine-containing inorganic compound (D) here. In this case, the Zr compound (C1) or the Ti compound (C2) may be contained together with another fluorine-containing inorganic compound.

The fluorine-containing inorganic compound (D) requires that the compounding amount (fluorine atom) / (B) of the fluorine atom to the cationic urethane resin (B) be 1/1000 or more and 2/1 or less by weight ratio, and 1/500 or more 1 / It is preferable that it is 1 or less, and it is more preferable that it is 1/250 or more and 1/2 or less. When fluorine atom / (B) is less than 1/1000, adhesiveness will become inadequate, and when fluorine atom / (B) exceeds 2/1, stability of an aqueous surface treating agent will fall. In addition, a fluorine atom is atomic conversion mass.

(Other optional ingredients)

As the surface treatment agent according to the present invention, as an optional component, V compound, Mo compound, W compound, Co compound, Al compound, Zn compound, Ni compound, Mn compound, Ce compound, Nb compound, Sn compound, Mg compound and Cr At least 1 sort (s) of metal compound (E) chosen from a compound can be mix | blended. These metal compounds (E) have the effect of especially improving corrosion resistance. Examples of the metal compound (E) include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluoride complexes, organic acid salts and organic complexes of the above metals.

Specific examples of the V compound, Mo compound, W compound, Co compound, Al compound, and Zn compound include vanadium pentoxide, metavanadate HVO ₃ , ammonium metavanadate, vanadium oxytrichloride VOCl ₃ , and vanadium trioxide V ₂ O ₃ , vanadium dioxide, vanadium oxysulphate VOSO ₄ , vanadiumoxyacetylacetonate VO (OC (= CH ₂ ) CH ₂ COCH ₃ ) ₃ , vanadium trichloride VCl ₃ ; Invanad molybdate H _15-X [PV _12-X MoO ₄₀ ]? NH ₂ O (6 <X <12, n <30), molybdenum oxide, molybdate H ₂ MoO ₄ , ammonium molybdate, ammonium paramolybdate , Sodium molybdate, molybdate phosphate compound (eg ammonium molybdate phosphate (NH ₄ ) ₃ [PO ₄ Mo ₁₂ O ₃₆ ]-3H ₂ O, sodium molybdate phosphate Na ₃ [PO ₄ Mo ₁₂ O ₃₆ ]? NH ₂ O and the like); Metatungstate H ₆ [H ₂ W ₁₂ O ₄₀ ], ammonium metatungstate (NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ], sodium metatungstate, paratungstate H ₁₀ [W ₁₂ O ₄₆ H ₁₀ ] Ammonium paratungstate and sodium paratungstate; Cobalt chloride, chloropentaminminecobalt chloride [CoCl (NH ₃ ) ₅ ] Cl, hexaammine cobalt chloride [Co (NH ₃ ) ₆ ] Cl ₂ , cobalt chromate, cobalt sulfate, ammonium cobalt sulfate, cobalt nitrate, cobalt oxide 2aluminum CoO? Al ₂ O ₃ , cobalt hydroxide, cobalt phosphate; Nickel nitrate, nickel sulfate, nickel carbonate, nickel acetylacetonate Ni (OC (= CH ₂ ) CH ₂ COCH ₃ ) ₃ , nickel chloride, hexaammine nickel chloride [Ni (NH ₃ ) ₆ ] Cl ₂ , nickel oxide, hydroxide Nickel; Aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide; Zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, zinc acetylacetonate Zn (OC (= CH ₂ ) CH ₂ COCH ₃ ) ₂ , zinc dihydrogen phosphate and the like.

Specific examples of the Mn compound, Ce compound, Nb compound, Sn compound, Mg compound, and Cr compound include permanganate HMnO ₄ , potassium permanganate, sodium permanganate, manganese dihydrogen phosphate Mn (H ₂ PO ₄ ) ₂ , and manganese nitrate Mn (NO ₃ ) ₂ , manganese sulfate (II), (III) or (IV), manganese fluoride (II) or (III), manganese carbonate, manganese acetate (II) or (III), ammonium manganese sulfate, manganese acetylaceto Nate Mn (OC (= CH ₂ ) CH ₂ COCH ₃ ) ₃ , manganese iodide, manganese oxide, manganese hydroxide; Cerium oxide, cerium acetate Ce (CH ₃ CO ₂ ) ₃ , cerium nitrate (III) or (IV), cerium ammonium nitrate, cerium sulfate, cerium chloride; Niobium pentoxide (Nb ₂ O ₅ ), sodium niobate (NaNbO ₃ ), niobium fluoride (NbF ₅ ), ammonium hexafluoroniobate (NH ₄ ) NbF ₆ ; Tin oxide (IV), sodium stannate Na ₂ SnO ₃ , tin chloride (II), tin chloride (IV), tin nitrate (II), tin nitrate (IV), hexafluorotartrate (NH ₄ ) SnF ₆ ; Magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, ammonium phosphate magnesium, magnesium hydrogen phosphate, magnesium oxide; Chromium acetate, chromium sulfate, chromium nitrate, chromium fluoride, chromium phosphate, chromium acetylacetonate (Cr (C ₅ H ₇ O ₂ ) ₃ ), and the like.

As for the metal compound (E), 1/1000 or more and 1/2 or less are suitable with weight ratio of a compounding ratio (E) / (B) with respect to cationic urethane resin (B), and it is more than 1/100 or more and 1/4 or less It is more preferable that it is 1/50 or more and 1/8 or less. When the compounding ratio (E) / (B) of the metal compound (E) and the cationic urethane resin (B) is less than 1/1000 in weight ratio, it is ineffective in improving the adhesiveness, and when it exceeds 1/2, the storage stability of the drug. This is considerably lowered. In addition, "(E)" in a compounding ratio (E) / (B) is an atomic conversion mass of a metal compound (E).

Moreover, you may contain a silica component in the surface treating agent which concerns on this invention as needed. For example, vapor phase silica, colloidal silica, hydrophobic silica, etc. can be used as a silica component. By containing a silica component, while acting as a defoaming agent of a surface treating agent, the preferable effect which can improve adhesiveness with a laminate can be brought.

As for such a silica, 1/100 or more and 1/5 or less are suitable for a cationic urethane resin (B) by weight ratio of a compounding ratio (silica) / (B), and it is more preferable that they are 1/50 or more and 1/10 or less. If the blending ratio (silica) / (B) of the silica and the cationic urethane resin (B) is less than 1/100 by weight ratio, it is ineffective in adhesiveness and the like. On the other hand, when it exceeds 1/5, the coating recedes and the adhesiveness is significantly reduced. . In addition, "(silica)" in a compounding ratio (silica) / (B) is an atomic conversion mass of silicon oxide.

The surface treatment agent according to the present invention may further contain, as an optional component, a surfactant or a thickener such as a wettability enhancer for obtaining a uniform coating on the surface to be coated in a range that does not impair the liquid stability and the coating performance of the aqueous surface treatment agent. have.

(Other configurations)

Although the medium used by the surface treating agent which concerns on this invention is water normally, a small amount (for example, 10 volume% or less of the whole aqueous medium) of alcohol, a ketone, and a cellosol is used for the purpose of improving the dryness of the surface treatment film obtained. You may use together a brominated water-soluble organic solvent.

Although there is no restriction | limiting in particular about the pH of the surface treating agent which concerns on this invention, 3? It is preferable that it is the range of 12, and 4? It is more preferable that it is the range of 8. In the case of using aluminum or its alloy as the target material, when the pH is less than 3, the etching is excessive, the function as the surface treatment agent cannot be sufficiently exhibited, and the liquid stability also tends to be lowered. When pH exceeds 12, there exists a tendency for the dissolution rate of aluminum or its alloy to increase, and to adversely affect the storage stability of a silane coupling agent (A). When pH adjustment is necessary, alkaline components, such as ammonia, dimethylamine, and triethylamine, or acidic components, such as acetic acid and phosphoric acid, can also be added.

The lower limit of the total solid concentration in the surface treatment agent according to the present invention is not particularly limited as long as the effect of the present invention can be achieved, but the upper limit is limited in view of liquid stability. The total solid concentration of the surface treating agent of the present invention is 0.1? It is preferable to adjust to the range of 40 mass%, and it is 1? It is more preferable to adjust to the range of 30 mass%, and 5? It is even more preferable to adjust to the range of 25 mass%.

The surface treatment agent which concerns on this invention, a silane coupling agent (A), cationic urethane resin (B), Zr compound (C1), Ti compound (C2), a fluorine-containing inorganic compound (D), and a case Is manufactured by adding and stirring a metal compound (E) in the water which is a dispersion medium. There is no restriction | limiting in particular in the addition order.

[Surface Treatment Method]

Next, the surface treatment method to which the surface treating agent concerning this invention is applied is demonstrated. As a metal material which can apply the surface treating agent which concerns on this invention, aluminum foil, aluminum alloy foil, stainless steel foil, etc. are mentioned as a preferable raw material. Although the thickness of such a metal material is not specifically limited, It can apply about what is called foil, a sheet, and a plate, In this invention, after forming a surface treatment film with a surface treating agent, it laminates, and after that, a deep drawing process, Since it is processed into the exterior material of a lithium ion secondary battery etc. by performing ironing process, a stretch draw process, etc., it is preferable to have thickness used for such use. For example, thickness 0.01? A foil of about 2 mm can be preferably applied as the metal material.

In the surface treatment method using the surface treating agent, the preceding pretreatment step is not particularly limited, but is usually washed with an alkali degreasing agent or an acidic degreasing agent in order to remove oil or contaminants adhering to the metal material before the present treatment, Hot water washing, solvent washing, etc. are performed. Then, surface adjustment by an acid, an alkali, etc. is performed as needed. After performing these processes, it is preferable to wash with water so that a washing | cleaning agent may not remain on the surface of a metal material.

Conventional coating methods such as roll coats, curtain flow coats, air sprays, airless sprays, dipping, bar coats, brush coatings and the like can be adopted for the application of the surface treating agent to the metal material. . Although there is no restriction | limiting in particular also about the temperature of a surface treating agent, Since the solvent of this treating agent is an aqueous treatment agent mainly having water, the temperature is 0? It is preferable that it is 60 degreeC, and 5? It is more preferable that it is 40 degreeC.

In the drying step after the treatment with the surface treating agent to form the surface treatment film, the curing of the cationic urethane resin (B) does not need to be accelerated and only the removal of the adhered water does not necessarily require heat. The water may be removed only by air drying or air blow. However, in order to accelerate hardening of cationic urethane resin (B), or to heat-soften the formed surface treatment film and to raise the uniform coating effect on a base metal material, it is preferable to heat-process. The heat treatment temperature is 50? 250 degreeC is preferable and 60? 220 degreeC is more preferable.

[Surface Treatment Coating]

As for the surface treatment film formed by the said surface treatment method, the adhesion amount is 0.01? It is preferable that it is the range of 1 g / m <2>. The more preferable range of adhesion amount is 0.01? It is the range of 0.5 g / m <2>, More preferably, it is 0.03? 0.25 g / m 2. If the deposition amount is less than 0.005 g / m 2, the coating amount is small, resulting in insufficient corrosion resistance. Moreover, when adhesion amount exceeds 1 g / m <2>, adhesiveness worsens but it also becomes disadvantageous also in cost. You may process a surface treatment film on the single side | surface of the metal material surface according to the objective.

[Method for Producing Laminated Metal Material]

Next, the manufacturing method of the laminated metal material which concerns on this invention is demonstrated. The laminated metal material forms a surface treatment film on the surface of the metal material by the surface treatment method using the surface treatment agent according to the present invention, and further, a resin film (also called a laminate film) or an extrusion laminate on the surface treatment film. It is produced by laminating resin. The resin film may be formed only on one side of the surface-treated metal material or may be formed on both sides depending on the purpose.

The laminate of the resin film is (i) a method of directly laminating the resin film after formation of the surface treatment film, which is a base film, and (ii) an adhesion improving agent called a primer after formation of the surface treatment film, which is a base film (polyester-based adhesive, polyether System adhesive) and the like, and are largely classified into two methods of laminating a resin film thereafter. Whichever you choose depends on your quality and cost requirements. In addition, any of the methods of laminating a resin film and the method of laminating resin of a molten state (it is generally called "extrusion lamination", and the resin is called "extrusion lamination resin") can be used for lamination. Although it does not restrict | limit especially as a resin material of the resin film laminated or extrusion laminated resin, A polyester type resin, a polyethylene type resin, a polypropylene resin, or these modified resins are mentioned preferably.

In the manufacturing method of the laminated metal material which concerns on this invention, the above-mentioned surface treating agent is applied. The surface treatment agent is excellent in adhesiveness (including processing adhesion) and corrosion resistance (particularly strong acid resistance and strong alkali resistance) with a laminate film, and is particularly preferable for preparing a laminated metal material, a laminated metal container or a laminated metal packaging material. to be. In addition, the surface treatment agent does not have hexavalent chromium, is completely chromium-free in consideration of recent environmental problems, and has the advantage of low environmental load. As mentioned above, the manufacturing method of the laminated metal material which concerns on this invention exhibits the outstanding effect that a metal container or packaging material excellent in adhesiveness and corrosion resistance can be provided as a laminated metal material.

Example

Hereinafter, an Example and a comparative example are given and this invention is demonstrated further more concretely. This invention is not limited only to a following example. In addition, "part" is a weight part (same meaning as a mass part) below.

[Example 1? 30, comparative example 1? 21]

(Test Materials and Pretreatment)

As the test material, a commercially available aluminum alloy plate (aluminum-manganese alloy plate: JIS A 3004, plate thickness: 0.3 mm, plate size: 200 mm × 300 mm) was used. About this aluminum alloy, it wash | cleaned by spraying 8% aqueous solution of a commercially available acidic cleaner (Falcline 500: Nippon Parker Co., Ltd.) at 75 degreeC for 20 second, and then it washes with water and made the surface clean. On the other hand, commercially available stainless steel sheets (JIS SUS304, plate thickness: 0.3 mm, plate size: 200 mm × 300 mm) were used. About this stainless steel plate, it wash | cleaned by spraying a 2% aqueous solution of a commercially available washing | cleaning agent (Fine Cleaner 4328: Nippon Parkarizing Co., Ltd.) at 60 degreeC for 20 second, and then, it washed with water and made the surface clean.

(Surface Treatment & Surface Treatment Agent)

Using the surface treatment agent formed by the formulation shown in Table 1 on the surface (one side) of the test material after pretreatment, it apply | coated so that a dry film weight (adhesion amount) may be set to 0.1 g / m <2> by a roll coater, and the test material reached | attained in a hot air drying furnace. It dried so that temperature might be 80 degreeC.

In Table 1, No. 1? 30 is a surface treatment agent (Example 1-30) which concerns on this invention, and No.31? 47 is a surface treating agent (Comparative Examples 1-17) outside the scope of the present invention. The equivalent ratio of the amino group of A1 and the glycidyl group of A3 constituting the silane coupling agent (A) of No. 15 is 5: 1. In addition, in Table 1, (A) / (B) is a compounding mass ratio of a silane coupling agent (A) and a cationic urethane resin (B), and (C1) / (C2) is a Zr compound (C1) and a Ti compound The compounding mass ratio of (C2), (C) / (B) is the compounding mass ratio of the sum total of a Zr compound and Ti compound, and a cationic urethane resin (B), (E) / (B) is the metal which comprises a metal compound It is a compounding mass ratio of the species (E) (atomic weight) and cationic urethane resin (B), and fluorine / (B) is fluorine (atomic weight) and cationic urethane resin which comprises a fluorine-containing inorganic compound (D) It is a compounding mass ratio of B). The content of each component in Table 1 is shown below.

<Silane coupling agent (A)>

A1: gamma-aminopropyltriethoxysilane

A2: 2-aminoethyl-3-aminopropyltrimethoxysilane

A3: gamma-glycidoxypropyltrimethoxysilane

A4: gamma -mercaptopropyltrimethoxysilane

<Cationically Water-based Polyurethane Resin (B)>

B1: Cationic Polyether Polyurethane Water Dispersion

B2: Cationic Polyester Polyurethane Water Dispersion

B3: Cationic Polycarbonate Polyurethane Water Dispersion

B4: Super Flex 410 (Anionic polycarbonate-based polyurethane water dispersion, manufactured by Daiichi Pharmaceutical Co., Ltd.)

B5: private K-3 (polyacrylic resin, manufactured by ROHM AND HAAS)

Among these, B1, B2, and B3 were prepared with the following method.

『B1: Cationic Polyether Polyurethane Resin (Water Dispersion)』

150 parts by mass of polyether polyol (synthetic component: polytetramethylene glycol and ethylene glycol, molecular weight 1500), 6 parts by mass of trimethylolpropane, 24 parts by mass of N-methyl-N, N-diethanolamine, and 94 parts by mass of Isophorone diisocyanate and 135 mass parts of methyl ethyl ketone are fractionated to a reaction container, and it is 70 to 15 parts by mass of dimethyl sulfate is added to the urethane prepolymer which is reacted while maintaining at 75 ° C., and 50? 30 at 60 ℃? It was made to react for 60 minutes, and the cationic urethane prepolymer was obtained. Furthermore, after adding 576 mass parts of water to the said cationic urethane prepolymer and emulsifying it uniformly, methyl ethyl ketone was collect | recovered and the cationic water-soluble polyurethane resin (B1) was obtained.

『B2: Cationic Polyester Polyurethane Resin (Water Dispersion)』

135 parts by mass of polyester polyol (synthetic component: isophthalic acid, adipic acid and 1,6-hexanediol, ethylene glycol, molecular weight 1700), 5 parts by mass of trimethylolpropane, and 22 parts by mass of N-methyl-N, N Diethanolamine, 86 parts by mass of isophorone diisocyanate, and 120 parts by mass of methyl ethyl ketone were aliquoted to a reaction vessel, followed by 70? 17 mass parts of dimethyl sulfate is added to the urethane prepolymer which is made to react at 75 degreeC, and is 50-50 degreeC. 30 at 60 ℃? It was made to react for 60 minutes, and the cationic urethane prepolymer was obtained. Furthermore, 615 mass parts of water was added to the said cationic urethane prepolymer, and it emulsified uniformly, methyl ethyl ketone was collect | recovered and the cationic water-soluble polyurethane resin (B2) was obtained.

『B3: Cationic Polycarbonate Polyurethane Resin (Water Dispersion)』

130 parts by mass of polycarbonate polyol (synthetic component: 1,6-hexanecarbonate diol, ethylene glycol, molecular weight 2000), 4 parts by mass of trimethylolpropane, 21 parts by mass of N-methyl-N, N-diethanolamine, 75 mass parts of isophorone diisocyanate and 115 mass parts of methyl ethyl ketone were fractionated to a reaction container, and it was 70? 22 mass parts of dimethyl sulfate is added to the urethane prepolymer which is made to react at 75 degreeC, and is 50-50 degreeC. 30 at 60 ℃? It was made to react for 60 minutes, and the cationic urethane prepolymer was obtained. Furthermore, after adding 633 mass parts of water to the said cationic urethane prepolymer and emulsifying it uniformly, methyl ethyl ketone was collect | recovered and the cationic water-soluble polyurethane resin (B3) was obtained.

<Zr compound (C1)>

C11: hexafluorozirconium acid

C12: Ammonium hexafluorozirconate

C13: zirconium acetylacetonate

C14: Zirconium Ammonium Carbonate

C15: Zirconia Sol

<Ti compound (C2)>

C21: Titaniumacetylacetonate

C22: titanyl sulfate

C23 hexafluorotitanic acid

C24: hexafluoroammonium carbonate

C25: titanium laurate

<Fluorine-containing inorganic compound (D)>

D1: ammonium fluoride

D2: hydrofluoric acid

D3: hexafluorosilicic acid

<Metal Compound (E)>

E1: vanadilacetylacetonate

E2: ammonium molybdate

E3: ammonium metatungstate

E4: Cobalt Nitrate

E5: Aluminum Hydroxide

E6: Cerium Ammonium Nitrate

E7: Nickel Carbonate

<Silica>

Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex O) was used as the silica. The surface treating agent which added silica is the surface treating agent of No. 6 and No. 7 in Table 1. Although the compounding ratio of silica was not described in Table 1, the surface treating agent of No. 6 was mix | blended with the compounding ratio (silica) / (B) as 1/50 to the surface treating agent of No. 5, and the surface treating agent of No. 7 was It mix | blends the compounding ratio (silica) / (B) to 1/10 to the surface treating agent of No.5.

(Film laminate)

The thermoplastic polyester film (film thickness of 30 micrometers) was heat-laminated on 250 degreeC for 5 second on the test material with which the surface treatment film was formed, and the laminated metal material was obtained. The surface pressure at the time of heat lamination was performed at 50 kg / cm <2>.

[Comparative Example 18? 21]

As Comparative Example 18, a commercially available phosphate chromate treatment agent (AM-K702: manufactured by Nippon Parker Co., Ltd.) was sprayed at 50 ° C. for 5 seconds, washed with water to remove unreacted drug, and heated at 80 ° C. for 1 minute to dry the test piece ( Cr adhesion amount was 20 mg / m <2>). In addition, as Comparative Example 19, a commercially available zirconium phosphate treatment agent (AL-404: manufactured by Nippon Parker Co., Ltd.) was sprayed at 40 ° C. for 20 seconds, washed with water to remove unreacted chemicals, heated at 80 ° C. for 1 minute, and dried. (Zr adhesion amount was 15 mg / m <2>). Moreover, as Comparative Examples 20 and 21, only test pieces of degreasing were also produced.

[Evaluation test]

(Primary adhesion)

The laminated metal material laminated with film was punched out at φ 140 mm, and the punched plate was drawn to prepare a drawing cup. Subsequently, this cup was again drawn and the ironing process was performed with three dies, and the drawing ironing can (can body) was shape | molded.

The appearance of the can body after the drawing ironing process was observed, and the case where breakage occurred was "x", and the case where breakage was not broken but "accumulation" occurred as "Δ" and no breakage or scratch was evaluated as "o". And the leakage current was measured by the commercially available enamelizer (made by Peco) using the can body evaluated by "(circle)." The current value after 4 second was measured at 6.3V using 0.5% saline solution as a measurement liquid. The lower the current value is, the lower the value, the lower the value, the lower the value of the current. Evaluated.

(Secondary adhesion)

The can body into which 5% aqueous sodium hydroxide solution was injected and the can body into which 5% sulfuric acid aqueous solution was injected were stored at 25 ° C for two weeks. Subsequently, these cans were washed with water and rinsed, and then leakage current was measured by a commercially available enamelizer (manufactured by Peco) in the same manner as before. The measurement liquid also measured the electric current value after 4 second in 6.3V using the same 0.5% saline solution. As for the current value, it is preferable that the lower side is the same as before, and the case of less than 0.1 mA is "◎", the case of 0.1 mA or more and less than 0.3 mA is "△", and the case of 0.3 mA or more and less than 1.0 mA is "△" and 1.0 mA or more. It evaluated as "x". Inferior acid resistance and alkali resistance increase the current value at this time.

(Storage stability)

The surface treating agent was stored for 3 months in a constant temperature device at 40 ° C, and the state of gelation or precipitation thereafter was visually observed, and storage stability was evaluated according to the following criteria. At this time, the case where there was no change was evaluated as "(circle)", the case where it thickened as "(triangle | delta)" and the case where it gelatinized or precipitated as "x".

[Evaluation results]

Example 1? 32 and Comparative Example 1? The said test was implemented about each test piece of 21, and it judged according to the evaluation criteria. The results are shown in Table 2. As is clear from the results in Table 2, it was found that the surface treatment agent according to the present invention exhibits excellent performance when applied as a surface treatment agent for laminate films. In particular, it was found that, by coexisting the Zr compound (C1) and the Ti compound (C2) and the content ratio of both of them, from 1/10 to less than 2/1, the secondary adhesion to both strong acids and strong alkalis was particularly excellent. Moreover, it turned out that Example 6 and Example 7 which used the surface treating agent containing silica were excellent in all the evaluation items. Moreover, Example 9 which made a component composition into a more preferable form and range? 12 and Example 15 were found to be excellent in all items.

Claims (6)

Containing a silane coupling agent (A), cationic urethane resin (B), Zr compound (C1), Ti compound (C2) and fluorine-containing inorganic compound (D),
The compounding ratio (A) / (B) is 1/50 or more and 20/1 or less by weight ratio, and the compounding ratio (C) / (B) is 1/100 or more and 1/2 or less by weight ratio (However, the weight of (C) is (C1 ) And (C2)), and the compounding ratio (fluorine atom) / (B) is 1/1000 or more and 2/1 or less by weight ratio, and the compounding ratio (C1) / (C2) is 1/10 or more and 2/1 by weight ratio It is less than, The surface treating agent for laminated metal materials. The method of claim 1,
The surface treating agent for laminated metal materials in which the said cationic urethane resin (B) contains the amino functional group chosen from a secondary amino group and a tertiary amino group. The method according to claim 1 or 2,
5 mass% or more of the said silane coupling agent (A) whole is the surface for laminated metal materials which is a silane coupling agent which has an amino functional group chosen from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. Treatment agent. The method according to any one of claims 1 to 3,
The surface treating agent for laminate metal materials, wherein the Zr compound (C1) and the Ti compound (C2) are fluoride, fluoro acid, or fluoro acid salt. The surface treating agent for the laminated metal material according to any one of claims 1 to 4 is applied and dried on the surface of the metal material to obtain 0.01? A 1 g / m <2> film is formed, and then a polyester resin, a polyethylene resin, a polypropylene resin, or these modified resins are laminated. The manufacturing method of the laminated metal material characterized by the above-mentioned. The method of claim 5, wherein
A method for producing a laminated metal material, wherein the metal material is an aluminum or stainless steel metal foil.