JP6709872B2 - Aqueous metal surface treatment agent, metal surface treatment film and metal material with metal surface treatment film - Google Patents

Description

The present invention is provided between a metal material and a laminate film, for improving the adhesion of the laminate film, and for forming a surface-treated film capable of improving the corrosion resistance of the metal material, The present invention relates to an aqueous metal surface treatment agent, a metal surface treatment film formed by the aqueous metal surface treatment agent, and a metal material with the metal surface treatment film.

Metal materials such as aluminum, magnesium, iron, copper, zinc, nickel or alloys thereof, for the purpose of improving their protective performance and design, various resin coating layers are provided on the surface, automobile parts, It is widely used in the fields of home electric appliances, building materials and beverage containers. Various characteristics are required for metal materials used in such fields. Examples of means for forming the resin coating layer include methods such as painting, film laminating and printing.

Among them, the film laminating is a processing means for heating and pressing a resin film (hereinafter referred to as a laminated film) on the surface of a metal material, and a metal for the purpose of protecting the surface or imparting a design property. It is used in various fields as one of the methods for coating the material surface. This film laminating process is a method in which a resin composition is dissolved or dispersed in a solvent and applied to the surface of a metal material and dried to form a resin coating film. The amount of greenhouse gases generated is small. Therefore, the film laminating process is preferably applied from the viewpoint of environmental protection, and its application is expanded, for example, aluminum thin plate material, steel thin plate material, copper thin plate material, nickel-plated copper thin plate material, aluminum foil or stainless foil for packaging, etc. It is used as a method for coating a laminated film on a building material, a food can body or lid material, a food container, a dry battery container, or the like.

In the surface treatment of metal materials, chromate surface treatment using a surface treatment agent containing hexavalent chromium is often used because it is inexpensive. In recent years, regulations on the use of harmful metals (compounds and ions) such as hexavalent chromium, lead and cadmium in Europe, PRTR (Environmental Pollutant Emission Transfer Registration System) in Japan, or publication of a list of environmental hormone substances have been applied to the human body. Not only the influence but also the trend for the purpose of global environment conservation is becoming larger on a global scale. Under such circumstances, there has been a great deal of crisis awareness of adverse effects on the human body and the environment, and there is an alternative technology for the surface treatment agent containing hexavalent chromium, which is generally used as a surface treatment agent for metallic materials, Surface treatment agents that do not use chromium at all have been proposed.

Furthermore, recently, it has been desired to develop a chromium-free treatment agent that does not contain trivalent chromium. For example, as a chromium-free undercoating agent for lamination, in Patent Document 1, a specific amount of a water-soluble zirconium compound, a specific structure of a water-soluble or water-dispersible acrylic resin, and a water-soluble or water-dispersible thermosetting cross-linking agent. A base treatment agent containing is proposed. Further, Patent Document 2 proposes a metal surface treatment agent comprising a water-soluble zirconium compound and/or a water-soluble titanium compound, an organic phosphonic acid compound, and tannin. Further, Patent Document 3 proposes a base treatment agent containing a basic zirconium compound and/or a cerium compound, a carboxyl group-containing resin, and an oxazoline group-containing acrylic resin and containing no fluorine.

JP, 2002-265821, A JP, 2003-313680, A JP, 2009-84516, A

As described above, a metal material with a laminate film, which is obtained by providing a laminate film on the surface of a metal material, is widely used in various fields and is used as a container material or a packaging material for accommodating various contents. Especially in the field of food packaging such as food containers, from the viewpoint of improvement and convenience of eating habits, a variety of foods are filled, sauces, vinegar, animal fats and oils, various spices, citrus beverages, alcohol-containing substances. I do not know that the diversification of contents will stop. Therefore, there is a demand for a container material or a packaging material that does not reduce the adhesion of the laminate film or the corrosion resistance of the metal material depending on the contained contents. Also, the sterilization temperature of foods rises to 100°C (boiled foods), 120°C (retort foods), 135°C (high retort foods), and the durability of container materials or packaging materials at high temperatures is required. ing. Similar performance is required in other industrial fields.

However, for the surface treatment described in Patent Documents 1 to 3 described above, further improvement in durability and adhesion between the metal material and the laminate film is desired, and the metal material in a severe environment is desired. Further improvement in corrosion resistance is desired.

The present invention has been made in order to meet such a demand, and an object thereof is to be provided between a metal material and a laminate film so that the adhesion of the laminate film can be improved and the metal material can be improved. Provided are a water-based metal surface-treating agent, a metal surface-treated coating formed by the water-based metal surface-treating agent, and a metal material with the metal surface-treated coating for forming a surface-treated coating capable of improving the corrosion resistance of Especially.

(1) The aqueous metal surface treatment agent according to the present invention for solving the above-mentioned problems is one or two kinds selected from oxides of zirconium, titanium or hafnium having an average particle size within a range of 1 nm to 500 nm. The above metal compound (A), one or more phosphorus or fluorine-containing compounds (B) selected from the phosphorus compound group and the fluorine compound group, and a polyester resin, a urethane resin, a polyolefin resin, an acrylic resin, a polyvinyl resin It is characterized by containing at least one or two or more water-based resins (C) selected from resins, polyamide resins, polyimide resins, natural polysaccharides, epoxy resins and elastomers.

In the aqueous metal surface treatment agent according to the present invention, the content of the metal compound (A) is preferably in the range of 5% by mass or more and 90% by mass or less based on the total solid content.

In the water-based metal surface treatment agent according to the present invention, the content of the water-based resin (C) is preferably in the range of 5% by mass or more and 90% by mass or less based on the total solid content.

In the aqueous metal surface treatment agent according to the present invention, the pH is preferably in the range of 3 or more and 11 or less.

The water-based metal surface treatment agent according to the present invention is preferably used for a laminate base.

(2) The metal surface treatment film according to the present invention for solving the above-mentioned problems has one or more kinds selected from oxides of zirconium, titanium or hafnium having an average particle size in the range of 1 nm to 500 nm. Metal compound (A), one or more phosphorus- or fluorine-containing compounds (B) selected from a phosphorus compound group and a fluorine compound group, and a polyester resin, urethane resin, polyolefin resin, acrylic resin, polyvinyl resin And a water-based metal surface treatment agent containing at least one or more water-based resins (C) selected from polyamide resin, polyimide resin, natural polysaccharides, epoxy resin and elastomer. And

(3) A metal material with a metal surface treatment film according to the present invention for solving the above-mentioned problems has a metal material and the metal surface treatment film according to the present invention provided on the surface of the metal material. Characterize.

The metal material with a metal surface treatment film according to the present invention is configured to further include a laminate film provided on the metal surface treatment film.

According to the water-based metal surface treatment agent of the present invention, it is provided between the metal material and the laminate film, the adhesion of the laminate film can be improved, and the corrosion resistance of the metal material can be improved. A metal surface treatment film can be formed.

The metal surface treatment film according to the present invention is provided between the metal material and the laminate film, and can improve the adhesion of the laminate film and the corrosion resistance of the metal material.

The metal material with a metal surface treatment film according to the present invention has excellent adhesion between the metal material and the laminate film via the metal surface treatment film, and also has excellent corrosion resistance of the metal material.

It is a typical sectional view showing an example of a metal material with a metal surface treatment film concerning the present invention.

Hereinafter, the water-based metal surface treatment agent, the metal surface treatment film, and the metal material with the metal surface treatment film according to the present invention will be described in detail. The present invention can be arbitrarily modified within the scope including the gist thereof and is not limited to the following embodiments.

[Aqueous metal surface treatment agent]
The water-based metal surface treatment agent according to the present invention includes one or more metal compounds (A) selected from oxides of zirconium, titanium, or hafnium having an average particle diameter in the range of 1 nm to 500 nm, and phosphorus. One or more phosphorus- or fluorine-containing compounds (B) selected from the compound group and the fluorine compound group, and a polyester resin, urethane resin, polyolefin resin, acrylic resin, polyvinyl resin, polyamide resin, polyimide resin, natural poly It contains at least one or two or more water-based resins (C) selected from sugars, epoxy resins and elastomers.

Hereinafter, the components of the water-based metal surface treatment agent and the treatment target will be described in detail.

(Metal compound)
Examples of the metal compound (A) include oxides of zirconium, titanium or hafnium having an average particle size of 1 nm or more and 500 nm or less. Specific examples thereof include zirconium oxide, titanium oxide, hafnium oxide, and the like. Specific examples thereof include zirconium oxide (IV) (ZrO ₂ ), titanium oxide (IV) (TiO ₂ ), hafnium oxide (HfO ₂ ), and the like. These metal compounds (A) may be used alone or in combination of two or more. Of these, zirconium oxide is particularly preferable.

The metal compound (A) is preferably used as a dispersion solution (for example, sol) in which solid particles are previously dispersed in an aqueous solvent. This dispersion solution has the advantage that it is easier to handle than the solid particles of the metal compound (A) itself and the production of the water-based metal surface treatment agent becomes easier.

The aqueous solvent is a solvent containing 50% by mass or more of water. Solvents other than water contained in the aqueous solvent include alkane solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; alcohol solvents such as ethanol, 1-butanol and ethyl cellosolve; tetrahydrofuran, dioxane and the like. Ether-based solvent; ester-based solvent such as ethyl acetate and butoxyethyl acetate; amide-based solvent such as dimethylformamide and N-methylpyrrolidone; sulfone-based solvent such as dimethylsulfoxide; phosphoric amide-based solvent such as hexamethylphosphoric triamide; Etc. can be mentioned. These solvents other than water may be used alone or in combination of two or more.

The method for preparing the above-mentioned dispersion solution is, for example, the first method of obtaining or synthesizing solid particles of the metal compound (A), and then dispersing using a dispersant in an aqueous solvent, and the precursor of the metal compound (A). There is a second method of producing a dispersion of the metal compound (A) in an aqueous solvent using a water-soluble salt which is the body. Of these, the second method is preferably used.

In the second method, specifically, an alkaline agent is added to an acidic aqueous solution of a water-soluble salt of zirconium, titanium or hafnium and, if necessary, a dispersant is added to remove an oxide of zirconium, titanium or hafnium. It is a method of generating in water, and then removing excess impurity ions by separation. By this second method, a dispersion solution containing solid particles of oxide of zirconium, titanium or hafnium can be prepared.

As the water-soluble salt of zirconium, titanium or hafnium, a conventionally known salt can be used. Specifically, zirconium chloride, zirconium oxychloride, titanium chloride, hafnium chloride, zirconium nitrate, titanium nitrate, hafnium nitrate, zirconium sulfate, titanium sulfate, hafnium sulfate, fluorozirconic acid, fluorotitanic acid, fluorohafnium acid, zirconium acetate. , Titanium acetate, hafnium acetate, zirconium lactate, titanium lactate, hafnium lactate and the like. Also, these salts may be hydrates.

As the above-mentioned alkaline agent, a conventionally known alkaline agent can be used. Specifically, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used. Further, depending on the purpose of use of the sol, it may not be preferable to include sodium or potassium. In that case, ammonia, ammonium hydrogen carbonate or urea can be used.

As the dispersant described above, a conventionally known dispersant can be used. Of these, a hydroxycarboxylic acid is preferable, and specific examples thereof include citric acid, malic acid, tartaric acid, lactic acid, hydroxyvaleric acid, glyceric acid, tropic acid, and benzylic acid. In particular, a hydroxycarboxylic acid having a divalent or higher carboxylic group such as citric acid, malic acid or tartaric acid can be preferably used because it can be dispersed with a small content.

As the above-mentioned separation, there are a separation method using an ion exchange resin, a separation method using a membrane filtration, and the like, but a separation method using an ultrafiltration membrane is simpler and more preferable.

The content of the metal compound (A) in the water-based metal surface treatment agent is 1% by mass or more, preferably 5% by mass or more, based on the total solid content. The upper limit of the content of the metal compound (A) is not particularly limited, but is about 90 mass% with respect to the total solid content. When the content of the metal compound (A) is in this range, the initial adhesion between the metal material and the laminate film via the metal surface treatment film is good, and particularly the high adhesion even under the environment of contact with an acidic liquid. (Durable adhesion) can be obtained, and the corrosion resistance of the metal material can be improved.

Although the mechanism of action of the metal compound (A) has not been elucidated at this point, it is prepared by using an aqueous metal surface treatment agent which does not contain the metal compound (A) but instead contains a water-soluble salt of zirconium, titanium or hafnium. The inventors of the present invention have found that the metal surface-treated coating does not exhibit performance. The metal compound (A), which is an oxide of zirconium, titanium, or hafnium, has high acid resistance as compared with a water-soluble salt and is difficult to dissolve even when contacted with an acidic liquid or the like. It is considered that the metal surface-treated film prepared with the aqueous metal surface-treating agent containing A) has high durability and adhesion.

The metal compound (A) is dispersed in the water-based metal surface treatment agent, and the average particle size of the metal compound (A) dispersed in the water-based metal surface treatment agent is preferably in the range of 1 nm or more and 500 nm or less. .. When the average particle size is less than 1 nm, the acid resistance is low, and the durability and adhesion between the metal surface treatment film and the laminate film under the environment of contact with an acidic liquid are deteriorated. On the other hand, if the average particle size exceeds 500 nm, the volume ratio of the portion where the metal compound (A) having acid resistance does not exist in the metal surface treatment film after film formation increases, so especially in an environment in which an acid liquid is contacted. The durability and adhesion may deteriorate. The average particle diameter is more preferably in the range of 5 nm or more and 100 nm or less.

The average particle size of the metal compound (A) dispersed in the aqueous metal surface treatment agent can be measured by a conventionally known measuring method such as a dynamic light scattering method, a laser diffraction method, a centrifugal sedimentation method. Specifically, it can be measured using a dynamic light scattering photometer (DLS-8000 series) manufactured by Otsuka Electronics Co., Ltd., a laser diffraction/scattering particle size distribution meter (LA-920) manufactured by Horiba, Ltd., and the like. it can. The average particle diameter of the metal compound (A) in the metal surface-treated coating provided on the metal material with a metal surface-treated coating described below is measured by a transmission electron microscope (TEM) on the surface or cross section of the metal surface-treated coating. It can be measured by direct observation.

(Phosphorus or fluorine containing compound)
As the phosphorus- or fluorine-containing compound (B), one or both of a phosphorus compound and a fluorine compound, that is, one or more selected from the phosphorus compound group and the fluorine compound group is used.

Examples of the phosphorus compound group may include a group composed of a plurality of phosphorus-containing compounds such as phosphoric acid, phosphoric acid ester, and organic phosphonic acid. Specific examples of the phosphoric acids include condensed phosphoric acid including phosphoric acid (orthophosphoric acid), metaphosphoric acid, and polyphosphoric acid, and salts thereof (ammonium salt, sodium salt, calcium salt, magnesium salt, lithium salt, etc.). Can be mentioned. The metaphosphoric acid includes trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid and the like. Polyphosphoric acid is a chain phosphoric acid condensate, and includes pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid and the like. Specific examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, phytic acid and salts thereof (ammonium salt, sodium salt). , Calcium salt, magnesium salt, lithium salt, etc.) and riboflavin phosphate ester. Specific examples of the organic phosphonic acid include aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid. The phosphorus-containing compounds may be used alone or in combination of two or more.

Among them, sodium salt, potassium salt, ammonium salt, magnesium salt and lithium salt of phosphoric acid; sodium salt and potassium salt of condensed phosphoric acid including polyphosphoric acid (including pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, etc.) Salts, ammonium salts, magnesium salts and lithium salts; sodium salts, potassium salts, ammonium salts, magnesium salts and lithium salts of phytic acid; and organic phosphonic acids (aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-). Diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid) are preferably used, and one or more selected from sodium salt, potassium salt, ammonium salt, magnesium salt and lithium salt. These phosphorus-containing compounds may be used alone or in combination of two or more. The condensed phosphate includes polyphosphate, metaphosphate, ultraphosphoric acid, etc., and the atomic ratio of metal to phosphorus is Me ₂ O/P ₂ O ₅ (this is represented as R, and Me is monovalent). It is classified as a metal). It is said that polyphosphate is in the case of 2≧R>1, metaphosphate is in the case of R=1, and ultraphosphate is in the case of R<1.

Phytic acid and organic phosphonic acid have two or more phosphon groups in one molecule as compared with phosphate, and therefore, it is considered that the crosslinking density is further increased and the durability and adhesion are further increased. On the other hand, the condensed phosphate has a large amount of phosphon groups per molecule as compared with the phosphate, but is easily hydrolyzed and eventually becomes a phosphate. Therefore, in the range where the condensed phosphate is compared with phytic acid or organic phosphonic acid, it is considered that the condensed phosphate is not as durable as phytic acid or organic phosphonic acid.

The fluorine compound group includes hydrofluoric acid, silicofluoric acid, sodium fluoride, potassium fluoride, ammonium fluoride, lithium fluoride, sodium acid fluoride, potassium acid fluoride, ammonium acid fluoride, fluorozirconic acid, fluorozirconic acid. There may be mentioned a group consisting of a plurality of fluorine-containing compounds such as ammonium, fluorotitanic acid and ammonium fluorotitanate. These fluorine-containing compounds may be used alone or in combination of two or more.

Among them, it is preferable to use one or more selected from sodium, potassium, ammonium and lithium salts of hydrofluoric acid.

The content of these phosphorus- or fluorine-containing compound (B) is the phosphorus- or fluorine-containing compound (B) with respect to the sum of the molar amounts of the metal atoms (zirconium atom, titanium atom, hafnium atom) constituting the metal compound (A). It is preferable to adjust the ratio (B/A) of the total sum of the molar amounts of phosphorus atoms and fluorine atoms constituting the above to be in the range of 0.005 or more and 5.0 or less. The content of the phosphorus- or fluorine-containing compound (B) may be adjusted so that the above-mentioned ratio falls within the range of 0.01 or more and 2.0 or less in terms of initial adhesion and durable adhesion. It is more preferable to adjust it so that it is in the range of 0.02 or more and 0.5 or less.

The mechanism of action of the phosphorus- or fluorine-containing compound (B) has not yet been elucidated at this point, but the dissolution of the phosphorus-containing compound and/or fluorine-containing compound in the water-based metal surface treatment agent results in When the surface treatment agent comes into contact with the metal material, the surface of the metal material is slightly etched by the phosphorus-containing compound or fluorine-containing compound to form fine unevenness, and the anchor effect due to the fine unevenness causes initial adhesion and durable adhesion. It is thought that the property has improved. Further, it is considered that the presence of the phosphorus-containing compound or the fluorine-containing compound in the metal surface treatment film reduces the permeability of the anion, which is a corrosion factor, and as a result, improves the corrosion resistance of the metal material. The phosphorus-containing compound and the fluorine-containing compound are chemically adsorbed on the surface of the particles of the metal compound (A) in the film and also act as a crosslinking agent. Particularly, it is considered that the phosphorus-containing compound is less likely to break the crosslink when exposed to a chemical such as an acid, and has higher durable adhesiveness than the fluorine-containing compound.

The anchor effect due to the fine unevenness is particularly effective when the average particle diameter of the metal compound (A) described above is within the range of 5 nm or more and 100 nm or less. If the average particle size of the metal compound (A) becomes too fine, the particles easily enter fine irregularities, and there is little room for the resin to contact the base material, and the effect of improving initial adhesion and durability adhesion is suppressed. There is.

(Water-based resin)
A conventionally known water-based resin can be applied as the water-based resin (C). Specifically, mention may be made of one or more water-based resins selected from polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, natural polysaccharides, epoxy resins and elastomers. You can

The water-based resin (C) may be either water-soluble or water-dispersible (emulsion, dispersion). Further, the polarity of the water-based resin (C) in the water-based metal surface treatment agent may be any of cationic, nonionic and anionic as long as the stability of the treatment agent is not impaired.

As the polyester resin, for example, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, isophthalic acid, terephthalic acid, trimellitic acid, Polybasic acids such as trimesic acid, pyromellitic acid and naphthalenedicarboxylic acid were condensed with polyols such as ethylene glycol, diethylene glycol, trimethylolpropane, neopentyl glycol, 1,4-CHDM and 1,6-hexanediol. Polyester polyols; condensation resins obtained by condensing the above-mentioned polybasic acids with polyols such as polymer polyols, polycaprolactone polyols, polycarbonate diols, polybutadiene polyols, neopentyl glycol and methylpentadiol; and the like.

Further, an aqueous resin obtained by using a monomer having three or more carboxyl groups such as trimellitic acid and pyromellitic acid as a part of the monomer and neutralizing unreacted carboxylic acid with an alkali to solubilize or disperse it in water Alternatively, an aqueous resin in which a sulfonated monomer such as sulfophthalic acid is used as a part of the monomer to be solubilized or dispersed in water can be used.

The urethane resin is a urethane resin which is a polycondensation product of a polyol such as polyester polyol, polyether polyol, or polycarbonate polyol, and an aliphatic polyisocyanate, an alicyclic isocyanate and/or an aromatic polyisocyanate compound, As a part of the polyol, there may be mentioned polyurethane obtained by using a polyol having a polyoxyethylene chain such as polyethylene glycol or polypropylene glycol.

Such a polyurethane can be made water-soluble or water-dispersed in a nonionic state by increasing the introduction ratio of the polyoxyethylene chain. Further, from a polyisocyanate and a polyol, a urethane prepolymer having isocyanato groups at both ends is produced, and a carboxylic acid having two or more hydroxyl groups or a reactive derivative thereof is reacted therewith to obtain a derivative having an isocyanate group at both ends. Then, add triethanolamine or the like to form an ionomer (triethanolamine salt), add the ionomer to water to form an emulsion or dispersion, and further add a diamine as necessary to extend the chain to give an anionic property. The urethane resin can be obtained.

The above-mentioned carboxylic acid and reactive derivative used for producing the water-dispersible urethane resin having anionic property are used for introducing an acidic group into the urethane resin and for making the urethane resin water-dispersible. Examples of the carboxylic acid may include dimethylolalkanoic acid such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolhexanoic acid. Further, examples of the reactive derivative include a hydrolyzable ester such as an acid anhydride.

Examples of the polyolefin resin include polypropylene; polyethylene; a copolymer of propylene, ethylene, and α-olefin; a modified polyolefin obtained by modifying a polyolefin with an unsaturated carboxylic acid (for example, acrylic acid or methacrylic acid); ethylene and acrylic acid ( Copolymers with methacrylic acid); and the like. These polyolefin resins may be copolymerized with a small amount of another ethylenically unsaturated monomer. Examples of means for making the aqueous solution include means for neutralizing the carboxylic acid introduced into the polyolefin resin with ammonia or amines.

Examples of the acrylic resin include homopolymers or copolymers of acrylic monomers, and further copolymers of addition polymerizable monomers copolymerizable with these acrylic monomers. Such acrylic resin is not particularly limited in polymerization form as long as it can stably exist in the water-based metal surface treatment agent.

Examples of the acrylic monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, 2- Examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, sulfoethyl acrylate and polyethylene glycol methacrylate. Examples of the addition-polymerizable monomer that can be copolymerized with the acrylic monomer include maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, diacetone acrylamide, styrene, acrylonitrile, and vinyl sulfonic acid.

The polymerization of the above-mentioned monomers is carried out in a solvent in the presence of an initiator under an inert gas flow in the range of 30°C to 80°C, preferably in the range of 40°C to 75°C, more preferably 50°C. It can be performed within the range of 75° C. or higher and 75° C. or lower. When the polymerization temperature is low, the polymerization may not proceed, and when the polymerization temperature is high, a gelled product may be formed.

The polymerization time is appropriately in the range of 1 hour to 24 hours. The solvent is preferably water-soluble, for example, methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, ethylene glycol, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, diethylene glycol, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, tri Examples thereof include ethylene glycol, triethylene glycol monoalkyl ether, triethylene glycol dialkyl ether, propylene glycol and glycerin.

Among these, isopropyl alcohol having an action as a chain transfer agent can be preferably used. Isopropyl alcohol is in the range of 20 parts by mass to 90 parts by mass with respect to 100 parts by mass of water, preferably in the range of 25 parts by mass to 65 parts by mass, more preferably in the range of 30 parts by mass to 60 parts by mass. Within. If the amount of isopropyl alcohol added is small, the polymerization may not proceed, and if the amount of isopropyl alcohol added is large, gelation may not be suppressed during the polymerization, and a gel may be formed.

As the initiator, a water-soluble radical initiator is preferable. Examples of the polymerization initiator in the copolymerization step include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, hydrogen peroxide, and azoamidines such as 2,2′-azobis-2-methylpropionamidine hydrochloride. Examples include compounds, cyclic azoamidine compounds such as 2,2′-azobis-2-(2-imidazolin-2-yl)propane hydrochloride, and azo initiators such as azonitrile compounds such as 2-carbamoylazoisobutyronitrile. be able to. At this time, alkali metal sulfites such as sodium hydrogen sulfite, metadisulfite, sodium hypophosphite, Fe(II) salts such as Mohr salt, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride, thiourea , L-ascorbic acid (salt), erythorbic acid (salt) and the like may be used in combination. From the viewpoint of hygiene, the water-soluble radical initiator is more preferably ammonium persulfate, sodium persulfate, or potassium persulfate. The radical initiator may be mixed and dissolved in the reaction system from room temperature at room temperature, or may be added dropwise to the reaction system over several hours.

Examples of polyvinyl resins include polyvinyl alcohol, partially saponified or completely saponified polyvinyl acetate, and polyvinylpyrrolidone.

The above-mentioned polyvinyl alcohol includes partially saponified products and fully saponified products of polyvinyl acetate, and partially saponified products and fully saponified products of copolymers of vinyl acetate and other monomers. Further, a modified polymer obtained by introducing an anionic group such as carboxylic acid, sulfonic acid, phosphoric acid or the like into the polymer after polymerization; or having crosslinking reactivity such as diacetone acrylamide group, acetoacetyl group, mercapto group, silanol group, etc. A modified polymer in which a functional group is introduced; and the like can also be applied.

Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth)acrylic acid and esters thereof, ethylene, propylene and the like. α-Olefin; olefin sulfonic acids such as (meth)acrylic sulfonic acid, ethylene sulfonic acid, and sulfonic acid malate; sodium (meth)allyl sulfonic acid, sodium ethylene sulfonic acid, sodium sulfonic acid (meth)acrylate, sodium sulfonic acid (mono) Alkyl malate), olefin sulfonic acid alkali salt such as sodium disulfonic acid alkyl malate; amide group-containing monomer such as N-methylol acrylamide, acrylamide alkyl sulfonic acid alkali salt; N-vinylpyrrolidone, N-vinylpyrrolidone derivative; Etc. can be mentioned.

Examples of the polyamide resin and the polyimide resin include a polyamide resin, a polyimide resin, and a polyamideimide resin. The means for water solubilization is carried out by introducing a carboxyl group into the structure.

Examples of natural polysaccharides include natural polysaccharides such as chitosan and its derivatives, and their derivatives. Chitosan is obtained by deacetylating 60 to 100 mol% of chitin, which is a natural polymer extracted from crustaceans such as crab and shrimp. For example, 100 mol% deacetylated chitosan is a polymer substance in which N-acetyl-β-D-glucosamine is bonded at the 1-position and 4-position.

The above-mentioned chitosan derivative is a reaction product obtained by carboxylating, glycolating, tosylating, sulfating, phosphorylating, etherifying or alkylating a hydroxyl group and/or an amino group of chitosan. Specific examples thereof include chitosan, carboxymethyl chitosan, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, glycerylated chitosan and salts thereof with an acid. Further, a reaction product obtained by introducing a tertiary or quaternized amino group into chitosan using a compound having a tertiary or quaternary amino group or both; alkylating the amino group of chitosan directly with an alkylating agent. , A so-called cationized chitosan having a tertiary or quaternized tertiary or quaternary amino group, or both in a molecule; and a salt thereof with an acid.

As the epoxy resin, an epoxy compound having two or more glycidyl groups; an epoxy resin obtained by cationizing an epoxy compound having two or more glycidyl groups with a diamine such as ethylenediamine; two or more glycidyl groups Nonionic epoxy resin in which polyethylene glycol is added to the side chain of the epoxy compound has; and the like.

Specific examples of the above-mentioned epoxy compound, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol diglycidyl ethers, triglycidyl isocyanurate, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl Examples thereof include ether, pentaerythritol tetraglycidyl ether, and triglycidyl ether of glycerol alkylene oxide adduct. These may be used alone or in combination of two or more.

A conventionally known elastomer can be used as the elastomer. Specifically, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, acrylonitrile butadiene styrene rubber, methyl methacrylate butadiene rubber and other diene rubbers; butyl rubber, ethylene propylene rubber, urethane rubber, silicone Examples thereof include rubber, chlorosulfonated rubber, chlorinated polyethylene, acrylic rubber, epichlorohydrin rubber, fluororubber, and the like, which can be dispersed in water. These elastomers may be used alone or in combination of two or more. Further, these elastomers are those modified with a functional group such as a hydroxyalkyl group such as an amino group, a hydroxyl group and a methylol group, a carboxyl group, a sulfone group, a phosphone group, an epoxy group, an isocyanate group, a carbodiimide group, and the like. Good. Of these elastomers, it is preferable to use butadiene rubber, acrylonitrile butadiene styrene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, methyl methacrylate butadiene rubber, acrylic rubber and the like.

The various water-based resins (C) described above may be used alone or in combination of two or more.

The content of the aqueous resin (C) is preferably in the range of 5% by mass or more and 95% by mass or less based on the total solid content of the aqueous metal surface treatment agent. When the content of the water-based resin (C) is in this range, the initial adhesion and durable adhesion between the metal surface treatment film and the laminate film are improved, and the corrosion resistance of the metal material is further improved. The preferred content of the water-based resin (C) is in the range of 10% by mass or more and 90% by mass or less, and the more preferred content thereof is the range of 30% by mass or more and 90% by mass or less.

Although the mechanism of action of the water-based resin (C) is still unclear at present, the presence of the water-based resin (C) in the metal surface-treated coating increases the denseness of the metal surface-treated coating, and the water-based resin It is considered that (C) itself contributes to the performance because it has high chemical resistance to acids and the like. It is also considered to play a role of firmly fixing the metal compound (A) in the film.

(Other)
The aqueous metal surface treatment agent according to the present invention may contain various solvents, if necessary, from the viewpoint of workability when applied to the surface of a metal material. Specific examples of the solvent include water; alkanes such as hexane and pentane; aromatics such as benzene and toluene; alcohols such as ethanol, 1-butanol and ethyl cellosolve; ethers such as tetrahydrofuran and dioxane. Ester type such as ethyl acetate and butoxyethyl acetate; amide type such as dimethylformamide and N-methylpyrrolidone; sulfone type solvent such as dimethyl sulfoxide; phosphoric acid amide such as hexamethylphosphoric triamide; Of these, one kind of solvent may be used, or two or more kinds of solvents may be mixed and used.

In addition to these, a surfactant, a defoaming agent, a leveling agent, a cross-linking agent, a plasticizer, an antibacterial and antifungal agent, a coloring agent and the like may be added within a range that does not impair the purpose and film performance of the present invention.

The cross-linking agent is not particularly limited as long as it can bond with the resin (C) to form a strong film, and examples thereof include melamine-based, isocyanate-based, epoxy-based, polyvalent metal ion-based and the like. be able to. When a cross-linking agent is added, a curing catalyst may be further added to accelerate the cross-linking.

The pH of the aqueous metal surface treatment agent is preferably in the range of 3 or more and 11 or less. When the pH is out of the range of 3 or more and 11 or less, the metal compound (A) is partially dissolved in the water-based metal surface treatment agent, and a metal surface treatment film is formed especially in an environment where the metal compound is in contact with an acidic liquid. The durability and adhesion with the laminate film may decrease. A more preferable pH is in the range of 6 or higher and 10 or lower.

(Production of treatment agent)
The method for producing the water-based metal surface treatment agent is not particularly limited. For example, the metal compound (A), the phosphorus- or fluorine-containing compound (B), the water-based resin (C) and other additives, and the solvent are sufficiently mixed by using a stirrer such as a mixing mixer, and the water-based metal surface A treating agent can be produced.

(Component analysis)
For the metal compound (A), for example, a sample coating obtained by applying an aqueous metal surface treatment agent to an aluminum plate (A1050P) and then drying at 80° C. is subjected to thin film X-ray diffraction analysis, and its diffraction pattern is analyzed. It can be measured by The thin film X-ray diffraction analysis is performed using a thin film X-ray diffraction device (model number: Xpert-MPD) manufactured by PANalytical under the conditions of wide angle method, tube voltage-current: 45 kV-40 mA, scan speed: 0.025 degree/second. ..

The phosphorus- or fluorine-containing compound (B) can be measured by applying a water-based metal surface treatment agent to an aluminum plate (A1050P) and then drying at 80° C. to perform a XPS analysis on a sample film obtained. For XPS analysis, an XPS analyzer (model number: ESCA-850) manufactured by Shimadzu Corporation is used, and excitation X-ray: Mg-Kα, output: 8 kV-30 mA, measurement area: F1s, P2p, sputtering time: 2 minutes ( The depth direction analysis is performed under the condition of (5 seconds interval).

The water-based resin (C) is an undiluted solution of the water-based metal surface treatment agent, or a solution diluted with water as needed, and FT-IR analysis (Thermo Fisher Scientific, model number: NicoletiS10, specular reflection method) and other analysis. It can be measured and identified by the method.

(Processing object)
The water-based metal surface treatment agent is treated by using a metal material as an object. Examples of the metal material include pure copper, copper alloy (these are also referred to as “copper material”), pure aluminum, aluminum alloy (these are also referred to as “aluminum material”), ordinary steel, and alloy steel (these are referred to as “iron”). Materials), pure nickel, nickel alloys (these are also referred to as “nickel materials”), pure zinc, zinc alloys (these are also referred to as “zinc materials”), and the like.

The shape and structure of the metal material are not particularly limited, and examples thereof include a plate shape and a foil shape. Further, the metal material is a copper material, an aluminum material, an iron material, a nickel material, a zinc material, or the like described above on a base material such as another metal material, a ceramic material, or an organic material by a method such as plating, vapor deposition, or clad. May be coated.

The copper alloy preferably contains 50 mass% or more of copper, and examples thereof include brass. Examples of alloy components other than copper in the copper alloy include Zn, P, Al, Fe, and Ni. The aluminum alloy preferably contains aluminum in an amount of 50% by mass or more, and examples thereof include Al—Mg based alloys. Examples of alloy components other than aluminum in the aluminum alloy include Si, Fe, Cu, Mn, Cr, Zn, and Ti. The alloy steel preferably contains iron in an amount of 50% by mass or more, and examples thereof include stainless steel. Examples of alloy components other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr and Mo. The nickel alloy preferably contains nickel in an amount of 50 mass% or more, and examples thereof include a Ni-P alloy. Examples of alloy components other than nickel in the nickel alloy include Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, and P. The zinc alloy preferably contains zinc in an amount of 50% by mass or more, and examples thereof include Zn-Al based alloys. Examples of alloy components other than aluminum in the aluminum alloy include Al, Si, Fe, Cu, Mn, Cr, Zn, and Ti.

[Metal surface treatment film and method for forming the same]
The metal surface treatment film according to the present invention is a film formed from the above-mentioned water-based metal surface treatment agent. The forming method is a step of applying an aqueous metal surface treatment agent to the surface of a metal material (application step) and a step of forming a metal surface treatment film by drying without washing with water after the application step (film formation step). Have and. Note that a pretreatment step of degreasing or pickling the metal material may be included in advance.

(Coating process)
The coating step is a step of coating the surface of the metal material with the water-based metal surface treatment agent. The coating method in this coating step is not particularly limited, and for example, spray coating, dip coating, roll coating, curtain coating, spin coating, or a combination thereof can be used for coating.

In this coating step, the conditions for using the water-based metal surface treatment agent are not particularly limited. For example, the temperature of the treatment agent and the metal material when applying the aqueous metal surface treatment agent is preferably in the range of 10°C or higher and 90°C or lower, and is in the range of 20°C or higher and 60°C or lower. Is more preferable. When the temperature is 60° C. or less, use of wasteful energy can be suppressed, which is more preferable from the economical viewpoint. Further, the coating time can be set appropriately.

(Drying process)
The drying step is a step of drying without washing with water after the coating step. By this step, the metal surface treatment film can be formed. As the drying conditions, it is preferable that the maximum temperature to be reached is in the range of 50° C. or higher and 250° C. or lower. When the highest temperature is less than 50°C, it may take a very long time to evaporate the solvent in the aqueous metal surface treatment agent, which is not preferable in practice. On the other hand, if the maximum temperature reached exceeds 250° C., energy will be wasted, which is not preferable from an economical point of view. The drying method is not specified, and a drying method using a batch drying oven, a continuous hot air circulating drying oven, a conveyor hot air drying oven, an electromagnetic induction heating oven using an IH heater, or the like can be applied. The air volume, the air speed, etc. set by the drying method are arbitrarily set.

(Metal surface treatment film)
The metal surface treatment film can be obtained by the above-mentioned forming method. The coating amount of the metal surface treatment coating is preferably in the range of 5 mg/m ² or more and 5000 mg/m ² or less. If the coating amount is less than 5 mg/m ² , the barrier property of the metal surface-treated film may be low, and the durable adhesion between the metal surface-treated film and the laminate film and the corrosion resistance of the metal material may be insufficient. On the other hand, when the coating amount exceeds 5000 mg/m ² , many cracks may occur in the metal surface treatment coating, and the initial adhesion and durability adhesion between the metal surface treatment coating and the laminate film, and the metal material. The corrosion resistance of may become insufficient. The more preferable coating amount for these characteristics is in the range of 10 mg/m ² or more and 3000 mg/m ² or less, and the particularly preferable coating amount is in the range of 100 mg/m ² or more and 2500 mg/m ² or less. ..

The obtained metal surface treatment film contains the metal compound (A). Among them, it is preferable that the oxide is contained. The presence or absence of this metal compound (A) can be confirmed by a thin film X-ray diffraction method for the obtained metal material with a metal surface treatment film. Specifically, a metal surface treatment film is taken as a measurement sample, and the measurement sample is subjected to thin film X-ray diffraction analysis (Xpert-MPD manufactured by PANalytical, wide-angle method, tube voltage/current: 45 kV-40 mA, scan speed: 0. The presence or absence of the metal compound (A) can be confirmed from the obtained diffraction pattern.

The average particle size of the metal compound (A) contained in the metal surface treatment film is preferably in the range of 1 nm or more and 500 nm or less. If the average particle size is less than 1 nm, the crystal size is small, so the crystallinity is low, and in some cases it may exist in an amorphous state. Then, as a result, the acid resistance becomes low, and the durable adhesion between the metal surface treatment film and the laminate film in the environment where the acid liquid comes into contact may be deteriorated. On the other hand, if the average particle size exceeds 500 nm, the volume ratio of the portion where the metal compound (A) having acid resistance does not exist in the metal surface treatment film after film formation increases, so especially in an environment in which an acid liquid is contacted. In some cases, the durable adhesion between the metal surface treatment film and the laminate film may decrease. A preferable average particle diameter is in the range of 1 nm or more and 100 nm or less. The average particle size can be measured by a transmission electron microscope (TEM) on the surface or cross section of the metal surface treatment film.

The metal surface treatment film thus obtained can be provided between the metal material and the laminate film to improve the adhesion of the laminate film and the corrosion resistance of the metal material.

[Metal material with metal surface treatment film]
As shown in FIG. 1 , a metal material 10 with a metal surface treatment film according to the present invention has a metal material 1 and the metal surface treatment film 2 provided on the surface thereof. The metal material 10 usually further has a laminate film 3 provided on the metal surface treatment film 2. The laminated film 3 is optional, and the laminated film 3 may be omitted until the laminated film 3 is laminated. Such a metal material 10 has excellent adhesion to the laminate film 3 and excellent corrosion resistance.

The laminate film 3 is arbitrarily selected according to the application in consideration of adhesiveness, gas barrier property, conductivity or designability, corrosion resistance of the metal material 10, etc., and is not particularly limited. Examples of the material of the laminate film 3 include polyester resin, polyethylene resin, polypropylene resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyamide resin, polyvinyl acetate resin, epoxy resin, and polyimide resin. As the laminate film, films made of these resin materials are used and laminated on the metal surface treatment film 2.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the examples below.

[Metal substrate]
-"Al"... A1100P (pure aluminum, JIS H4000:1999), thickness 0.3 mm
"ADC"... ADC12 (Al-Si-Cu based aluminum alloy, JIS H5302:2006), thickness 2.0 mm
・"Cu"...C1020P (oxygen-free copper plate, JISH-3100), thickness 0.3 mm
・"Ni"... Pure nickel plate (purity 99 mass% or more), thickness 0.3 mm
・"SUS"...SUS304 plate (austenitic stainless steel), thickness 0.3mm
・"EG"... Electrogalvanized steel sheet (thickness 0.8 mm, zinc plating thickness 20 μm)

[1. Preparation of water-based metal surface treatment agent]
The solvent is water, the metal compound sol (A) shown below is combined with the phosphorus- or fluorine-containing compound (B), the water-based resin (C), and optionally the additive (D), and further ammonia or acetic acid is used. The aqueous metal surface treatment agents of Examples 1 to 41 shown in Tables 1 and 2 and the aqueous metal surface treatment agents of Comparative Examples 1 to 15 shown in Table 3 were prepared by adjusting pH. The "solid content ratio" in the table indicates the ratio (% by mass) of each compound described above to the total solid content of the water-based metal surface treatment agent.

<Metal compound sol (A)>
The metal compound sol (A) used is shown below. The average particle size of the following metal compound sol (A) is a value measured using a dynamic light scattering photometer (DLC-6500) manufactured by Otsuka Electronics Co., Ltd.

A1; zirconium (IV) oxide sol (solid content 20% by mass, average particle size 30 nm)
A2: Hafnium (IV) oxide sol (solid content 15% by mass, average particle size 50 nm)
A3: Titanium (IV) oxide sol (solid content 6% by mass, average particle size 20 nm)
A4: Fluorotitanic acid (solid content 40% by mass)
A5: Ammonium zirconium carbonate (solid content 31% by mass)
A6: Copper (II) oxide sol (solid content 20% by mass, average particle size 20 nm)
A7: Zirconium (IV) oxide sol (solid content 15% by mass, average particle size 200 nm)

<Phosphorus- or fluorine-containing compound (B)>
B1; ammonium phosphate _{[(NH 4) 3 PO 4} ]
B2; sodium tripolyphosphate [Na ₅ P ₃ O ₁₀ ].
B3; sodium hexametaphosphate _{[(NaPO 3) 6] (} 65~70% as P 2 _{O 7)}
B4: Ammonium fluoride [NH ₄ F]
B5: Sodium acid fluoride [NaFHF]
B6; phytic acid _{[C 6 H 18 O 24 P} 6]
B7: Hydroxyethylidene diphosphonic acid [C ₂ H ₈ O ₇ P ₂ ]

<Water-based resin (C)>
(C1; polyester resin)
An alcohol component consisting of ethylene glycol (90 mol%) and trimethylolpropane (10 mol%), isophthalic acid (40 mol%), terephthalic acid (41 mol%), dimethyl isophthalate-5-sulfonate (2 mol%), and trihydrate anhydrous. An anionic polyester resin (solid content (NVC.) 30%) by a condensation reaction with an acid component consisting of meritic acid (17 mol%) was synthesized by the following method. In a 1000 mL round-bottomed flask equipped with a Claisen tube and an air cooler, 1 mol of all acid components, 2 mol of all alcohol components, and a catalyst (calcium acetate 0.25 g, N-butyl titanate 0.1 g) were put, and the system was cooled down. Was purged with nitrogen and heated to 180° C. to melt the contents. Then, the bath temperature was raised to 200° C., and the mixture was heated and stirred for about 2 hours to cause esterification or transesterification reaction. Next, the bath temperature was raised to 260° C., and after about 15 minutes, the pressure inside the system was reduced to 0.5 mmHg, and the reaction (polycondensation reaction) was performed for about 3 hours. After completion of the reaction, the contents were taken out by cooling with introduction of nitrogen. To the contents taken out, an appropriate amount of aqueous ammonia having a final pH of 6 to 7 (water has a solid content of 25%) was added, and the mixture was heated and stirred in an autoclave at 100° C. for 2 hours to give a polyester resin of an aqueous emulsion. Obtained.

(C2; urethane resin)
100 parts by mass of polyester polyol (adipic acid/3-methyl-1,5-pentanediol, number average molecular weight 1000, number of functional groups 2.0, hydroxyl value 112.2), 3 parts by mass of trimethylolpropane, dimethylolpropionic acid 25 By mass, and 85 parts by mass of isophorone diisocyanate were reacted in MEK to obtain a urethane prepolymer. 9.4 parts by mass of triethylamine was mixed with this, poured into water, the urethane prepolymer was dispersed in water, and extended with ethylenediamine to obtain a dispersion. Methyl ethyl ketone was distilled off to obtain an aqueous urethane resin dispersion containing a nonvolatile content of 30% by mass. The acid value of the carboxyl group-containing polyurethane dispersed in the obtained aqueous dispersion was 49 (KOHmg/g).

(C3; polyolefin resin)
In a four-necked flask, 100 parts by mass of a propylene-ethylene-α-olefin copolymer (68 mol% of propylene component, 8 mol% of ethylene component, 24 mol% of butene component, mass average molecular weight 60,000), 10 parts of maleic anhydride. Parts by mass, 10 parts by mass of methyl methacrylate, and 1 part by mass of dicumyl peroxide were added, and the mixture was stirred and reacted at 180° C. for 2 hours. A modified polyolefin resin composition having a mass average molecular weight of 45,000 and a graft mass of maleic anhydride of 8.4 mass% was obtained. Then, 100 parts by mass of the modified polyolefin, 10 parts by mass of dimethylethanolamine, and 10 parts by mass of polyoxyethylene alkyl ether sulfate were charged into a four-necked flask, and stirred uniformly with a stirring blade at 100° C. for 2 hours. After melting, 300 parts by mass of ion-exchanged water at 90° C. was added and stirred for 1 hour to obtain an aqueous polyolefin resin having a pH of 8.0.

(C4; acrylic resin 1)
Acrylic resin aqueous solution (nonvolatile content concentration: 15.0 mass %, viscosity: 3 Pa·s, pH=3.5, Tg: 130) obtained by copolymerization using butyl acrylate, acrylamide, and hydroxyethyl acrylate as monomers. (°C, anion) was used.

(C5; acrylic resin 2)
A temperature control regulator, a cooling pipe and a stirrer were attached to a reaction vessel consisting of a separable 4-neck flask, and at room temperature, 390 parts by mass of ion-exchanged water, 210 parts by mass of isopropyl alcohol, and 120 parts by mass of N-methylolacrylamide as an acrylic monomer. Parts and 30 parts by mass of acrylamide were charged and dissolved. Further, 1.5 parts by mass of potassium persulfate, 0.06 parts by mass of sodium hydrogen sulfite, and 1.5 parts by mass of anhydrous sodium acetate were charged and dissolved. Then, after the reaction vessel was replaced with nitrogen, the temperature was raised to 65° C. in 30 minutes and the reaction was performed at 65° C. for 3 hours. The reaction product was cooled to room temperature, filtered and taken out. The obtained acrylic resin aqueous solution had a nonvolatile concentration of 20% by mass, a viscosity of 2.86 dPa·s, and a pH of 5.6.

(C6; polyvinyl alcohol)
An acetoacetylated polyvinyl alcohol having a saponification degree of 99%, a viscosity of 12 mPa·S, an acetoacetylation degree of 9.8% and an average molecular weight of 50,000 was used.

(C7; polyamideimide resin)
1106.2 g of trimellitic anhydride, 1455.8 g of 4,4-diphenylmethane diisocyanate and 2562.0 g of N-methyl-2-pyrrolidone were placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and a nitrogen stream was dried. The temperature was gradually raised to 130°C over about 2 hours with stirring. The temperature was kept at 130° C. while paying attention to the rapid foaming of carbon dioxide gas generated by the reaction, and the heating was continued for about 6 hours and then the reaction was stopped to obtain a polyamideimide resin solution. The nonvolatile content (200° C.-2 h) of this polyamideimide resin solution was about 50 mass %, and the viscosity (30° C.) was about 85.0 Pa·s. The number average molecular weight of the polyamide-imide resin was about 17,000, and the acid value of the combined carboxyl group and carboxyl group obtained by ring-opening the acid anhydride group was about 40. 2,700 g of this polyamideimide resin solution was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 50° C. with stirring in a dry nitrogen stream. When the temperature reached 50° C., 447.1 g (4 equivalents) of triethylamine was added, and after sufficiently stirring while maintaining the temperature at 50° C., ion-exchanged water was gradually added while stirring. Finally, ion-exchanged water was added until the amount reached 1348.8 g (30% by mass) to obtain a transparent and uniform heat-resistant polyamide-imide resin.

(C8; natural polysaccharide)
Glycerylated chitosan having the following structural formula (number average molecular weight: 10,000 to 100,000, glycerylated: 1.1) was used.

(C9; epoxy resin)
Polyethylene glycol diglycidyl ether (n=9, bifunctional, epoxy equivalent 268 WPE, viscosity 70 mPa·s) was used.

(C10; Elastomer 1)
An aqueous dispersion of acrylonitrile butadiene styrene rubber having a carboxyl group and a methylol group (solid content concentration: 47%, pH=8, viscosity: 45 mPa·s, Tg: 18° C., specific gravity: 1.01) was used.

(C11; Elastomer 2)
An aqueous dispersion of styrene-butadiene rubber having a carboxyl group (solid content concentration: 48.5%, pH=7.8, viscosity: 104 mPa·s, particle size 170 nm, Tg: −5° C.) was used.

(C12; acrylic resin 3)
Acrylic resin aqueous solution (nonvolatile component concentration: 20.0 mass %, viscosity: 300 mPa·s, pH=4.0, anion) obtained by copolymerization using methyl methacrylate and N-methylol acrylamide as monomers was used. ..

(C13; Elastomer 3)
A nitrogen-substituted polymerization vessel was charged with 200 parts of water, 4.5 parts of rosin acid soap, 66 parts of butadiene, 26 parts of styrene, 8 parts of acrylonitrile, and 0.3 part of t-dodecyl mercaptan. Then, the temperature of the polymerization vessel was set to 5° C., 0.1 part of p-menthane hydroperoxide as a polymerization initiator, 0.07 part of ethylenediaminetetraacetic acid sodium salt, and 0.05 part of ferrous sulfate heptahydrate. , And 0.15 parts of sodium formaldehyde sulfoxylate were added to initiate polymerization. When the conversion of polymerization reached 60%, diethylhydroxyamine was added to terminate the polymerization. Then, unreacted monomers were recovered by steam stripping to obtain a dispersion liquid containing a diene rubber having a solid content concentration of 21%.

<Other additives (D)>
(D1; isocyanate-based curing agent 1)
Hexamethylene diisocyanate-ethyl acetoacetate block was used.

(D2: Epoxy curing agent 1)
Ethylene glycol diglycidyl ether (n=1, bifunctional, epoxy equivalent 113 WPE, viscosity 20 mPa·s) was used.

(D3; isocyanate curing agent 2)
A toluene diisocyanate-diethylene glycol monoethyl ether block product was used.

(D4; epoxy curing agent 2)
Glycerol polyglycidyl ether (n=2, trifunctional, epoxy equivalent 141 WPE, viscosity 150 mPa·s) was used.

D5: Aluminum monoacetylacetonate bis(ethylacetonate)
D6; titanium lactate D7; N-methylol acrylamide D8; dimethylol urea D9; polyglycerin (average molecular weight 750, hydroxyl value 890)
D10: Triethylene glycol

[2. Preparation of test material]
The metal substrates described in Examples 1 to 41 shown in Tables 1 and 2 and Comparative Examples 1 to 15 shown in Table 3 were treated with a 2% aqueous solution of Fine Cleaner 359E (an alkaline degreasing agent manufactured by Nihon Parkerizing Co., Ltd.). After degreasing by spraying at 10°C for 10 seconds, the surface was cleaned by washing with water. Then, in order to evaporate the water on the surface of the metal base material, it was heated and dried at 80° C. for 1 minute. On the surface of the degreased and washed metal base material, the water-based metal surface treating agents of Examples 1 to 41 shown in Tables 1 and 2 and Comparative Examples 1 to 15 shown in Table 3 were applied by bar coating using a #8SUS Meyer bar. Then, it was dried at 180° C. for 1 minute in a hot air circulation type drying furnace to form a metal surface treatment film on the surface of the metal substrate. Further, the metal base materials described in Comparative Examples 16 to 21 in Table 3 were degreased, washed with water as described above, and then dried by heating, which were also used in the test. Tables 1 to 3 summarize the water-based metal surface treatment agents used in each example or each comparative example and the film formation amount of the obtained metal surface treatment film.

[3. Measurement of average particle size of metal compound sol (A)]
Cross-sections of the metal materials with metal surface-treated coatings obtained in Examples 3, 6 and 13 were observed with a transmission electron microscope (TEM) to estimate the average particle size of the metal compound (A). .. The average particle size of the metal compound (A) was about 100 nm, 30 nm, and 20 nm, respectively.

[4. Lamination performance evaluation]
Then, a laminating film was laminated on the metal surface treatment film of the metal substrate by the laminating method shown below.

(Laminate 1)
On the surface of the metal base material on which the metal surface treatment film is formed, a polyester film (thickness 16 μm) having one surface subjected to corona treatment is thermocompression-bonded at 250° C. and a surface pressure of 5 MPa for 10 seconds. A metal material with a surface treatment film was manufactured.

(Laminate 2)
An adhesive layer having a thickness of 5 μm was obtained by roll-coating a dispersion of acid-modified polypropylene on the surface of the metal base material on which the metal surface-treated film was formed, and then drying at 200° C. for 1 minute in a hot-air circulation drying oven. Formed. Then, the adhesive layer and a polypropylene film having a thickness of 30 μm were thermocompression-bonded at 250° C. and 0.1 MPa for 10 seconds to produce a metal material with a metal surface-treated coating in which polypropylene films were laminated.

<4.1. Initial adhesion>
The metal material with the metal surface treatment film provided with the laminate film by the laminate 1 and the laminate 2 was subjected to a cross-cut tape peeling test (1 mm pitch) after being extruded by an Erichsen tester by 5 mm, and the initial adhesion of the laminate film was measured as follows. It was evaluated in ranks 1 to 3.

3: There is no peeling of the laminated film.
2: A part of the laminated film was peeled off.
1: The laminate film was peeled off the entire surface.

<4.2. Durable adhesion>
A pressure cooker test was carried out on the metal material with the metal surface treatment film provided with the laminate film by the laminate 1. The conditions were 125° C. and 2 atm for 1 hour, and a commercially available sterilizer was used. After that, it was dried, cut into a width of 15 mm, and 180° peel strength was measured. The adhesion between the laminate film and the metal material was evaluated according to the following ranks 1 to 9.

9: Peel strength is 10 N or more.
8: The peel strength is in the range of 9 N or more and less than 10 N.
7: The peel strength is in the range of 8N or more and less than 9N.
6: The peel strength is in the range of 7N or more and less than 8N.
5: The peel strength is in the range of 6N or more and less than 7N.
4: The peel strength is in the range of 5N or more and less than 6N.
3: The peel strength is in the range of 3N or more and less than 5N.
2: The peel strength is in the range of 1N or more and less than 3N.
1: The laminate film has already been peeled off, or less than 1N.

<4.3. Corrosion resistance>
With respect to the metal material with the metal surface-treated coating provided with the laminate film by the laminate 2, the appearance after the CASS test was carried out for 24 hours was visually observed according to JIS H8502, and evaluated with the following ranks 1 to 9.

9: No change in appearance.
8: The area ratio of peeling (floating) of the laminate film and corrosion under the laminate film was more than 0% and 5% or less.
7: The area ratio of peeling (floating) of the laminate film and corrosion under the laminate film was more than 5% and 10% or less.
6: The area ratio of peeling (floating) of the laminate film and corrosion under the laminate film was more than 10% and 15% or less.
5: The area ratio of peeling (floating) of the laminated film and corrosion under the laminated film exceeds 15% and 20% or less.
4: The area ratio of peeling (floating) of the laminate film and corrosion under the laminate film was more than 20% and 25 or less.
3: The area ratio of peeling (floating) of the laminated film and corrosion under the laminated film was more than 25% and 40% or less.
2: The area ratio of peeling (floating) of the laminate film and corrosion under the laminate film was more than 40% and 60% or less.
1: The area ratio of peeling (floating) of the laminate film and corrosion under the laminate film exceeds 60%.

<4.4. Content resistance 1>
The metal material with a metal surface-treated film obtained by laminating a polyester film with Laminate 1 was immersed in model juice (citric acid monohydrate: sodium chloride: deionized water = 5:5:990 (mass ratio)), and 60 After allowing to stand at 1° C. for 1 week, it was taken out, cut into a width of 15 mm and subjected to 180° peel strength measurement. The adhesion between the laminate film and the metal material was evaluated according to the following ranks 1 to 9.

9: Peel strength is 10 N or more.
8: The peel strength is in the range of 9 N or more and less than 10 N.
7: The peel strength is in the range of 8N or more and less than 9N.
6: The peel strength is in the range of 7N or more and less than 8N.
5: The peel strength is in the range of 6N or more and less than 7N.
4: The peel strength is in the range of 5N or more and less than 6N.
3: The peel strength is in the range of 3N or more and less than 5N.
2: The peel strength is in the range of 1N or more and less than 3N.
1: The laminate film has already been peeled off, or less than 1N.

<4.5. Content resistance 2>
Regarding a metal material with a metal surface-treated coating obtained by laminating a polypropylene film with Laminate 2, an electrolytic solution manufactured by Kishida Chemical Co., Ltd. (trade name: LBG-00015, electrolyte: 1M-LiPF ₆ , solvent: EC/DMC/DEC=1/ After dipping in 1/1 (volume %)), it was placed in a constant temperature bath at 60° C. for 7 days. Then, the sample material was taken out, rocked while being immersed in ion-exchanged water for 1 minute to be washed, and then dried in a hot air circulation type drying furnace at 100° C. for 10 minutes. Then, it was cut into a width of 15 mm and subjected to 180° peel strength measurement. The adhesion between the laminate film and the metal material was evaluated according to the following ranks 1 to 9.

9: Peel strength is 10 N or more.
8: The peel strength is in the range of 9 N or more and less than 10 N.
7: The peel strength is in the range of 8N or more and less than 9N.
6: The peel strength is in the range of 7N or more and less than 8N.
5: The peel strength is in the range of 6N or more and less than 7N.
4: The peel strength is in the range of 5N or more and less than 6N.
3: The peel strength is in the range of 3N or more and less than 5N.
2: The peel strength is in the range of 1N or more and less than 3N.
1: The laminate film has already been peeled off, or less than 1N.

[result]
The results are shown in Tables 4-6.

As shown in Tables 4 and 5, it was confirmed that the metal materials with metal surface-treated coatings obtained in Examples 1 to 41 were excellent in initial adhesion, durability adhesion, corrosion resistance, etc. after forming a laminate film. It was As shown in Table 6, the metal materials with metal surface treatment coatings obtained in Comparative Examples 1 to 15 were inferior to the Examples in initial adhesion, durable adhesion, corrosion resistance and the like.

Aqueous metal surface treatment agent according to the present invention, a metal surface treatment film formed by the water-based metal surface treatment agent, and a metal material with the metal surface treatment film is used in a wide range of fields such as home appliances, food, and construction, It can be applied to metal materials such as aluminum, magnesium, copper, iron, zinc, nickel or alloys thereof. And a container for filling contents, which contains an organic acid such as acetic acid and citric acid, and an inorganic acid such as sulfuric acid and hydrofluoric acid, specifically, a food container, a detergent container, a lithium ion secondary battery container, and the like. Can be preferably applied as.

1 Metal Material 2 Metal Surface Treatment Coating 3 Laminate Film 10 Metal Material with Metal Surface Treatment Coating

Claims (8)

A metal compound (A) which is an oxide of titanium having an average particle diameter in the range of 20 nm or more and 500 nm or less, and one or more phosphorus or fluorine-containing compounds (B) selected from a phosphorus compound group and a fluorine compound group. ) And one or more water-based resins (C) selected from polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, natural polysaccharides, epoxy resins and elastomers. An aqueous metal surface-treating agent containing at least one. The aqueous metal surface treatment agent according to claim 1, wherein the content of the metal compound (A) is in the range of 5% by mass or more and 90% by mass or less based on the total solid content. The water-based metal surface treatment agent according to claim 1 or 2, wherein the content of the water-based resin (C) is in the range of 5% by mass or more and 90% by mass or less based on the total solid content. The aqueous metal surface treatment agent according to any one of claims 1 to 3, which has a pH in the range of 3 or more and 11 or less. The aqueous metal surface treatment agent according to any one of claims 1 to 4, which is used for a laminate base. A metal compound (A) which is an oxide of titanium having an average particle diameter within the range of 20 nm or more and 500 nm or less, and one or more phosphorus or fluorine-containing compounds (B) selected from the phosphorus compound group and the fluorine compound group. ) And one or more water-based resins (C) selected from polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, natural polysaccharides, epoxy resins and elastomers. A metal surface treatment film, which is a film formed of at least an aqueous metal surface treatment agent contained therein. A metal material with a metal surface treatment film, comprising a metal material and the metal surface treatment film according to claim 6 provided on the surface of the metal material. The metal material with a metal surface treatment film according to claim 7, further comprising a laminate film provided on the metal surface treatment film.

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