TWI611044B - Aqueous metal surface treatment agent, metal surface treatment coating film and metal material having a metal surface treatment coating film - Google Patents

Abstract

An object of the present invention is to provide an aqueous metal surface treatment agent for forming a metal surface treatment film and a metal surface treatment film which are provided between a metal material and a laminate film, thereby improving adhesion and improving both. Corrosion resistance of metal materials. The present invention solves the problem by providing an aqueous metal surface treatment agent characterized by containing at least a metal compound (A), a phosphorus-containing or fluorine-containing compound (B), and a water-based resin (C), the aforementioned metal compound (A) Is one or more selected from the group consisting of oxides of zirconium, titanium, and hafnium, and the average particle diameter thereof is in the range of 1 nm or more and 500 nm or less, and the phosphorus-containing or fluorine-containing compound (B) is selected from the group consisting of phosphorus compounds. One or more of the group and the fluorine compound group, and the water-based resin (C) is selected from the group consisting of a polyester resin, a urethane resin, a polyolefin resin, an acrylic resin, a polyvinyl resin, and a polyamine. One or two or more of a resin, a polyimide resin, a natural polysaccharide, an epoxy resin, and an elastomer are used to solve the above problems.

Description

Water metal surface treatment agent, metal surface treatment film and metal material with metal surface treatment film

The present invention relates to an aqueous metal surface treatment agent for forming a surface treatment film, a metal surface treatment film formed of the water metal surface treatment agent, and a metal material to which the metal surface treatment film is attached, wherein the surface treatment film is provided on the metal material The adhesion between the laminated film and the laminated film can be improved, and the corrosion resistance of the metal material can be improved.

In order to improve the protection properties and design properties of metal materials such as aluminum, magnesium, iron, copper, zinc, nickel or alloys of these metals, various resin coating layers are provided on the surface of these metal materials, and thus are widely used. Automotive parts, home appliance parts, building components and beverage containers. Metal materials used in these fields are required to have various characteristics. Further, examples of the method of forming the resin coating layer include coating, film lamination, and printing.

Among them, the film lamination process is a film made of resin ( Hereinafter, a method of heat-pressing the surface of a metal material, which is a method of coating a metal surface for the purpose of protecting a metal surface or imparting design, is applied to various fields. Compared with a method of forming a resin coating film in which a coating liquid obtained by dissolving or dispersing a resin composition in a solvent is applied to a metal surface and dried, the film is laminated to treat a solvent such as a solvent or carbon dioxide generated during drying. Or the amount of greenhouse gas produced is small. Therefore, from the viewpoint of environmental protection, it is preferred to use a film lamination process, and its use is expanded, and a coating method as a laminated film has been used, for example, as an aluminum thin plate material, a steel thin plate material, a copper thin plate material, and a nickel plating. A construction material for a copper sheet material, an aluminum foil for packaging, or a stainless steel foil, a main body or a lid material for a food can, a food container, or a dry battery container.

In the substrate treatment of a metal material, a chromate substrate treatment using a surface treatment agent containing hexavalent chromium is often used because it is inexpensive. In recent years, the use of harmful metals (compounds, ions) such as hexavalent chromium, lead, and cadmium in Europe, the PRTR (Environmental Pollutant Emissions Transfer Registration System) in Japan, or the list of environmental hormone substances are disclosed to prevent The impact on the human body and the goal of protecting the global environment are further expanding worldwide. Under such circumstances, the crisis awareness of the adverse effects on the human body and the environment has been greatly improved, and an alternative technique containing a hexavalent chromium surface treatment agent which is generally used as a base treatment agent for metal materials has been proposed, that is, it is not used at all. Surface treatment agent for hexavalent chromium.

Further, it has recently been desired to develop a chromium-free treating agent that does not even contain trivalent chromium. For example, as a chromium-free substrate treatment agent for lamination, Patent Document 1 proposes a specific amount of a water-soluble zirconium compound and a specific structure. A substrate treatment agent for a water-soluble or water-dispersible acrylic resin, a water-soluble or water-dispersible thermosetting crosslinking agent. Further, Patent Document 2 proposes a metal surface treatment agent containing 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 ruthenium compound, a carboxyl group-containing resin, an oxazoline group-containing acrylic resin, and no fluorine.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-265821

Patent Document 2: Japanese Laid-Open Patent Publication No. 2003-313680

Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-84516

As described above, the metal material with a laminated film provided with a laminated film on a metal surface is widely used in various fields, and can be used as a material for containers or a material for packaging for accommodating various contents. In particular, in the field of food packaging such as food containers, from the viewpoint of improving food life and simplicity, there are various types of foods to be filled, such as sauces, vinegar, animal fats, various spicy seasonings, citrus drinks, and alcohol. Things, etc., the variety of content is not endless. Therefore, depending on the contents to be stored, a material for a container or a material for packaging which does not lower the adhesion of the laminated film and which does not deteriorate the corrosion resistance of the metal material is required. In addition, the sterilization temperature of the food It is also raised to 100 ° C (boiling food), 120 ° C (cooked food), and 135 ° C (high pressure cooking food), and the durability of the material for containers or the material for packaging at high temperatures is required. In addition, the same performance is required in other industrial fields.

However, in the substrate treatment described in the above Patent Documents 1 to 3, it is desirable that the durability adhesion property between the metal material and the laminate film is further improved, and it is also desired to further improve the corrosion resistance of the metal material in a severe environment.

The present invention has been made in view of such a demand, and an object thereof is to provide an aqueous metal surface treatment agent for forming a surface treatment film, a metal surface treatment film formed of the water metal surface treatment agent, and a metal having the metal surface treatment film In the material, the surface treatment film is provided between the metal material and the laminate film, and the adhesion of the laminate film can be improved, and the corrosion resistance of the metal material can be improved.

(1) The aqueous metal surface treatment agent of the present invention for solving the above problems contains at least a metal compound (A), a phosphorus-containing or fluorine-containing compound (B), and a water-based resin (C). The metal compound (A) is one or more selected from the group consisting of oxides of zirconium, titanium, and hafnium, and has an average particle diameter of 1 nm or more and 500 nm or less. The phosphorus-containing or fluorine-containing compound (B) is one or more selected from the group consisting of a phosphorus compound group and a fluorine compound group. The aqueous resin (C) is selected from the group consisting of polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, natural polysaccharides, and epoxy resins. One or two or more kinds of the resin and the elastomer.

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

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

The aqueous metal surface treatment agent of the present invention preferably has a pH of 3 or more and 11 or less.

The aqueous metal surface treatment agent of the present invention is preferably used for a laminate substrate.

(2) The metal surface treatment film of the present invention for solving the above problems is a film formed of an aqueous metal surface treatment agent, and the aqueous metal surface treatment agent contains at least a metal compound (A), a phosphorus-containing or fluorine-containing compound (B). And the water-based resin (C), wherein the metal compound (A) is one or more selected from the group consisting of oxides of zirconium, titanium, and hafnium, and has an average particle diameter of 1 nm or more and 500 nm or less. The phosphorus or fluorine-containing compound (B) is one or more selected from the group consisting of a phosphorus compound group and a fluorine compound group, and the water-based resin (C) is selected from the group consisting of polyester resins and ethyl urethanes. One or more of a resin, a polyolefin resin, an acrylic resin, a polyvinyl resin, a polyamide resin, a polyimide resin, a natural polysaccharide, an epoxy resin, and an elastomer.

(3) A metal material for a metal surface treatment film of the present invention for solving the above problems is characterized in that it has a metal material and the above-described metal surface treatment film of the present invention provided on the surface of the metal material.

It is preferable that the metal material with a metal surface treatment film of the present invention further has a laminated film which is provided on the above metal surface treatment film.

According to the aqueous metal surface treatment agent of the present invention, it is possible to form a metal surface treatment film which is provided between the metal material and the laminate film, which can improve the adhesion of the laminate film and at the same time improve the metal The corrosion resistance of the material.

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

In the metal material with a metal surface treatment film of the present invention, the adhesion between the metal material and the laminated film which are treated with the metal surface is excellent, and the metal material is also excellent in corrosion resistance.

1‧‧‧Metal materials

2‧‧‧Metal surface treatment film

3‧‧‧Laminated film

10‧‧‧Metal materials with metal surface treatment film

Fig. 1 is a schematic cross-sectional view showing an example of a metal material to which a metal surface treatment film of the present invention is applied.

Hereinafter, the aqueous metal surface treatment agent, the metal surface treatment film, and the metal material with the metal surface treatment film of the present invention will be described in detail. It is to be noted that the present invention can be arbitrarily changed within the scope of the gist of the invention, and is not limited to the following embodiments.

[Aqueous metal surface treatment agent]

The aqueous metal surface treatment agent according to the present invention contains at least a metal compound (A), a phosphorus-containing or fluorine-containing compound (B), and an aqueous resin (C) which is an oxidation selected from zirconium, titanium or hafnium. One or two or more of the above, and the average particle diameter thereof is in the range of 1 nm or more and 500 nm or less, and the phosphorus-containing or fluorine-containing compound (B) is one or two selected from the group consisting of a phosphorus compound group and a fluorine compound group. In the above, the aqueous resin (C) is selected from the group consisting of polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, and natural polysaccharides. One or two or more of an epoxy resin and an elastomer.

Hereinafter, the constituent elements and processing targets of the aqueous metal surface treatment agent will be described in detail.

(metal compound)

Examples of the metal compound (A) include oxides of zirconium, titanium, or hafnium having an average particle diameter of 1 nm or more and 500 nm or less. Specific examples thereof include an oxide of zirconium, an oxide of titanium, an oxide of cerium, and the like. Specific examples of each of them include zirconium (IV) oxide (ZrO ₂ ), titanium oxide (IV) (TiO ₂ ), and cerium (IV) oxide (HfO ₂ ). These metal compounds (A) may be used alone or in combination of two or more. Among them, a zirconium oxide is particularly preferred.

The metal compound (A) is preferably used in the form of a dispersion solution (for example, a sol) formed by dispersing solid particles in an aqueous solvent in advance. This dispersion solution has an advantage that it is easier to handle the solid particles itself of the metal compound (A) and facilitates the production of the aqueous metal surface treatment agent.

The aqueous solvent is a solvent containing 50% by mass or more of water. Examples of the solvent other than water contained in the aqueous solvent include an alkane solvent such as hexane or pentane; an aromatic solvent such as benzene or toluene; and an alcohol solvent such as ethanol, 1-butanol or ethyl cellosolve. An ether solvent such as tetrahydrofuran or dioxane; an ester solvent such as ethyl acetate or butoxyethyl acetate; a guanamine solvent such as dimethylformamide or N-methylpyrrolidone; a solvent such as a solvent; a guanamine phosphate such as hexamethylphosphoric acid phosphate; and the like. The solvent other than the water may be used singly or in combination of two or more.

The preparation method of the foregoing dispersion solution includes, for example, the first method in which a solid particle of the metal compound (A) is obtained or synthesized, and then dispersed in an aqueous solvent with a dispersant; and a precursor which is used as the metal compound (A) Water-soluble salt for the production of metal compounds in aqueous solvents The second method of the dispersion of (A). Among them, it is preferred to use the second method.

The second method is specifically a method of adding an alkali agent to an acidic aqueous solution of a water-soluble salt of zirconium, titanium or hafnium, adding a dispersant as needed, and forming an oxide of zirconium, titanium or hafnium in water, and then separating it. Remove excess impurity ions. According to this second method, a dispersion solution of solid particles containing an oxide of zirconium, titanium or hafnium can be prepared.

As a water-soluble salt of zirconium, titanium or hafnium, a conventionally known salt can be used. Specific examples include zirconium chloride, zirconium chloride, titanium chloride, barium chloride, zirconium nitrate, titanium nitrate, barium nitrate, zirconium sulfate, titanium sulfate, barium sulfate, fluorozirconic acid, fluorotitanate, and fluoroantimonic acid. Zirconium acetate, titanium acetate, barium acetate, zirconium lactate, titanium lactate, barium lactate, and the like. In addition, these salts may also be hydrates.

As the alkali agent, a conventionally known alkaline agent can be used. Specifically, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be used. Further, depending on the purpose of use of the sol, sodium or potassium may not be preferably used. In this case, ammonia, ammonium hydrogencarbonate or urea may be used.

As the dispersing agent, a conventionally known dispersing agent can be used. Among them, 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 diphenyl glycolic acid. In particular, since dispersion can be carried out with a small content, it is preferred to use a hydroxycarboxylic acid having two or more carboxyl groups such as citric acid, malic acid or tartaric acid.

As the foregoing separation, including the use of ion exchange resin The separation method using an ultrafiltration membrane, such as a separation method, a separation method using membrane filtration, etc., is preferable because it is simple.

The content of the metal compound (A) in the aqueous 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% by mass based on the total solid content. When the content of the metal compound (A) is within this range, the initial adhesion of the metal material and the laminated film which are treated with the metal surface through the metal surface is good, and in particular, high adhesion can be obtained even in an environment in contact with the acidic liquid. (Endurance adhesion), and also can improve the corrosion resistance of metal materials.

The mechanism of action of the metal compound (A) is now unexplained, but it has been found by the inventors' research that the metal compound (A) is not contained, and instead, a water system containing a water-soluble salt of zirconium, titanium or hafnium is used. The metal surface treatment film made of the metal surface treatment agent does not exhibit these properties. This is considered to be because the metal compound (A) which is an oxide of zirconium, titanium or hafnium has high acid resistance as compared with the water-soluble salt, and is hardly dissolved even when it is in contact with an acidic liquid or the like. The metal surface treatment film produced by the aqueous metal surface treatment agent containing the metal compound (A) can obtain high durability adhesion.

The metal compound (A) is dispersed in the aqueous metal surface treatment agent, and the average particle diameter of the metal compound (A) dispersed in the aqueous metal surface treatment agent is preferably in the range of 1 nm or more and 500 nm or less. When the average particle diameter is less than 1 nm, the acid resistance is lowered, and the durability adhesion between the metal surface treatment film and the laminated film is lowered in an environment in which the acidic liquid is contacted. On the other hand, when the average particle diameter exceeds 500 nm, the volume fraction of the portion of the metal surface treatment (A) which does not have acid resistance increases in the metal surface treatment film after film formation, and therefore, particularly in an environment in which an acidic liquid is contacted The durability of the durability is lowered. In addition, the average particle diameter of the metal compound (A) is more preferably in the range of 5 nm or more and 100 nm or less.

The average particle diameter of the metal compound (A) dispersed in the aqueous metal surface treatment agent can be measured by a conventionally known measurement method such as a dynamic light scattering method, a laser diffraction method, or a centrifugal sedimentation method. Specifically, it can be measured using a dynamic light scattering photometer (DLS-8000 series) manufactured by Otsuka Electronics Co., Ltd., or a laser diffraction/scattering particle size distribution analyzer (LA-920) manufactured by Horiba, Ltd. . In addition, the average particle diameter of the metal compound (A) in the metal surface treatment film provided on the metal material of the metal surface treatment film described later can be treated by a transmission electron microscope (TEM) on the metal surface treatment film. The surface or section is directly observed for measurement.

(containing phosphorus or fluorine-containing compounds)

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

Examples of the phosphorus compound group include a group consisting of a plurality of phosphorus-containing compounds such as phosphoric acid, phosphate, and organic phosphonic acid. Specific examples of the phosphoric acid include phosphoric acid (orthophosphoric acid), metaphosphoric acid, condensed phosphoric acid including polyphosphoric acid, and salts thereof (ammonium salt, sodium salt, calcium salt, magnesium salt, lithium salt) Wait). It should be noted that the metaphosphoric acid includes trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, and the like. Further, the polyphosphoric acid is a chain-shaped phosphoric acid condensate, and includes pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, and the like. Specific examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, and monobutyl phosphate. , dibutyl phosphate, phytic acid and salts thereof (ammonium, sodium, calcium, magnesium, lithium, etc.), riboflavin phosphate, and the like. Specific examples of the organic phosphonic acid include aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and divinyltriamine pentaethylene. Phosphonic acid and the like. The phosphorus-containing compounds may be used singly or in combination of two or more.

Among them, it is preferred to use one or more selected from the group consisting of sodium, potassium, ammonium, magnesium and lithium salts of phosphoric acid; including polyphosphoric acid (including pyrophosphoric acid, tripolyphosphoric acid, tetra Sodium, potassium, ammonium, magnesium and lithium salts of condensed phosphoric acid, such as polyphosphoric acid; sodium, potassium, ammonium, magnesium and lithium salts of phytic acid; and organic phosphonic acid (including amines) Sodium and potassium salts of benzyltriphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, divinyltriaminepentamethylenephosphonic acid , ammonium salts, magnesium salts and lithium salts. These phosphorus-containing compounds may be used singly or in combination of two or more. It should be noted that the condensed phosphate includes polyphosphate, metaphosphate, superphosphoric acid, etc., according to the atomic ratio of metal to phosphorus Me ₂ O/P ₂ O ₅ (the ratio is denoted as R, Me is calculated as a monovalent metal) sort. 2≧R>1 is a polyphosphate, when R=1, it is a metaphosphate, and when R<1, it is a superphosphate.

Compared with phosphate, phytic acid and organic phosphonic acid have two or more phosphonic acid groups in one molecule, and thus the crosslinking density is further increased, and the durability of the adhesive is further increased. On the other hand, although the condensed phosphate has more phosphonic acid groups per molecule than phosphate, it is more susceptible to hydrolysis and is eventually converted to phosphate. Therefore, in the range in which the condensed phosphate is compared with the phytic acid or the organic phosphonic acid, the condensed phosphate is considered to have no high durability of phytic acid or organic phosphonic acid.

Examples of the fluorine compound group include hydrofluoric acid, fluoroantimonic acid, sodium fluoride, potassium fluoride, ammonium fluoride, lithium fluoride, sodium hydrogen fluoride, potassium fluorohydride, ammonium hydrogen fluoride, fluorozirconic acid, and fluorozirconium. A group consisting of a plurality of fluorine-containing compounds such as ammonium acid, fluorotitanic acid, and ammonium fluorotitanate. These fluorine-containing compounds may be used singly or in combination of two or more.

Among them, one or two or more selected from the group consisting of a sodium salt, a potassium salt, an ammonium salt and a lithium salt of hydrofluoric acid are preferably used.

The content of these phosphorus-containing or fluorine-containing compound (B) constitutes a phosphorus-containing or fluorine-containing compound with respect to the sum of the molar amounts of metal atoms (zirconium atom, titanium atom, germanium atom) constituting the metal compound (A). The ratio (B/A) of the sum of the molar amounts of the phosphorus atom and the fluorine atom in (B) is preferably adjusted to be in the range of 0.005 or more and 5.0 or less. In addition, from the viewpoint of initial adhesion and durability, the ratio of the content of the phosphorus-containing or fluorine-containing compound (B) is preferably adjusted to be in the range of 0.01 or more and 2.0 or less, and particularly preferably It is adjusted to the range of 0.02 or more and 0.5 or less.

The mechanism of action of phosphorus or fluorine-containing compound (B) is not explained yet. a part of the bright material, but it is considered that the surface of the metal material is made of the phosphorus-containing compound or the fluorine-containing compound when the aqueous metal surface treatment agent is in contact with the metal material by dissolving the phosphorus-containing compound and/or the fluorine-containing compound in the aqueous metal surface treatment agent. The fine concavities and convexities are formed by etching, and the initial adhesion and the durability adhesion are improved by the anchoring effect by these fine concavities and convexities. In addition, it is considered that the phosphorus-containing compound or the fluorine-containing compound is present in the metal surface treatment film, and the anion permeability as a corrosion factor is lowered, and as a result, the corrosion resistance of the metal material is improved. 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 function as a crosslinking agent. In particular, when a phosphorus-containing compound is exposed to a chemical such as an acid, cross-linking is not easily broken, and it is considered to have higher durability than the fluorine-containing compound.

The anchoring effect by the fine unevenness is particularly effective when the average particle diameter of the metal compound (A) is in the range of 5 nm or more and 100 nm or less. When the average particle diameter of the metal compound (A) is too small, the particles easily enter the minute irregularities, and the portion where the resin contacts the substrate is reduced, and the improvement of the initial adhesion and the durability adhesion may be suppressed.

(water resin)

As the water-based resin (C), a conventionally known water-based resin can be used. Specifically, it may be selected from the group consisting of a polyester resin, a urethane resin, a polyolefin resin, an acrylic resin, a polyvinyl resin, a polyamide resin, a polyimide resin, a natural polysaccharide, and an epoxy resin. And one or more aqueous resins in the elastomer.

The aqueous resin (C) may be water soluble or water dispersible (milk Any one of liquid and dispersion (Dispersion). In addition, the polarity of the aqueous resin (C) in the aqueous metal surface treatment agent may be any one of cationic, nonionic, and anionic, as long as the stability of the treatment agent is not impaired.

Examples of the polyester resin include maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, sebacic acid, sebacic acid, dimer acid, and trimeric. Polyacids such as acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalene dicarboxylic acid, and ethylene glycol, diethylene glycol, trimethylolpropane, a polyester polyol obtained by condensing a polyol such as neopentyl glycol, 1,4-CHDM (1,4-cyclohexanedimethanol) or 1,6-hexanediol; the above polybasic acid and polymer polyol, a condensation resin obtained by condensing a polyhydric alcohol such as polycaprolactone polyol, polycarbonate diol, polybutadiene polyol, neopentyl glycol or methyl pentane glycol;

Further, a water-based resin may be used: a monomer having three or more carboxyl groups such as trimellitic acid or pyromellitic acid may be used as a part of the monomer, and the unreacted carboxylic acid may be neutralized with a base to be water-soluble or water-dispersed. An aqueous resin obtained by using the obtained water-based resin; or a part of the monomer obtained by using a deuterated monomer such as sulfophthalic acid to be water-soluble or water-dispersed.

The urethane resin is a polycondensate of a polyhydric alcohol such as a polyester polyol, a polyether polyol or a polycarbonate polyol, and an aliphatic polyisocyanate, an alicyclic isocyanate, and/or an aromatic polyisocyanate compound. An amine group obtained by using a polyoxyethylene chain-containing polyol such as polyethylene glycol or polypropylene glycol as a part of the above polyol Ethyl acetate and the like.

Such a urethane can be water-solubilized or water-dispersed in a nonionic state by increasing the introduction ratio of the polyoxyethylene chain. Further, a urethane prepolymer having an isocyanate group at both ends is produced from a polyisocyanate and a polyhydric alcohol, and reacted with a carboxylic acid having two or more hydroxyl groups or a reactive derivative thereof to have an isocyanate group at both ends. a derivative, then adding triethanolamine or the like to form an ionomer (triethanolamine salt), adding water to the ionomer to prepare an emulsion or dispersion, and optionally adding a diamine to carry out chain extension, thereby enabling An anionic urethane resin was obtained.

The carboxylic acid and the reactive derivative used in the production of the above anionic water-dispersible urethane resin are for introducing an acidic group into the urethane resin and for the urethane The ester resin is used in water dispersibility. Examples of the carboxylic acid include dimethylol alkanoic acid such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolvaleric acid or dihydroxymethylhexanoic acid. Further, examples of the reactive derivative include hydrolyzable esters such as acid anhydrides.

The polyolefin resin may be a modified polycondensate obtained by modifying a polyolefin such as polypropylene, polyethylene, propylene, or a copolymer of ethylene and an α-olefin with an unsaturated carboxylic acid (for example, acrylic acid or methacrylic acid). An olefin; a copolymer of ethylene and acrylic acid (methacrylic acid); and the like. A polyolefin resin obtained by further copolymerizing these polyolefin resins with a small amount of other ethylenically unsaturated monomers may also be used. As a method of water system, the carboxylic acid introduced into the polyolefin resin is neutralized with ammonia or an amine. method.

Examples of the acrylic resin include a homopolymer or a copolymer of an acrylic monomer, and a copolymer of these acrylic monomers and an addition polymerizable monomer copolymerizable with the acrylic monomer. Such an acrylic resin is not particularly limited as long as it can be stably present in the aqueous surface treatment agent.

Examples of the acrylic monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. , n-hexyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid Glycidyl ester, glycidyl methacrylate, sulfoethyl acrylate, polyethylene glycol methacrylate, and the like. Examples of the addition polymerizable monomer copolymerizable with the acrylic monomer include maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, acetamidine acetonamide, styrene, and acrylonitrile. , vinyl sulfonic acid, etc.

The polymerization of the above monomer can be carried out in the range of 30 ° C or more and 80 ° C or less, preferably 40 ° C or more and 75 ° C or less in the presence of a solvent, an initiator, and an inert gas stream. Further, it is preferably carried out in the range of 50 ° C or more and 75 ° C or less. When the polymerization temperature is low, the polymerization may not proceed, and when the polymerization temperature is high, a gel-like substance or the like may be formed.

The polymerization time is preferably 1 hour or more and 24 hours or less. Within the scope. The solvent is preferably a water-soluble solvent, and examples thereof include methanol, ethanol, isopropanol, propanol, butanol, ethylene glycol, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, and diethylene glycol. , diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, triethylene glycol, triethylene glycol monoalkyl ether, triethylene glycol dialkyl ether, propylene glycol, glycerin, and the like.

Among them, isopropanol having a chain transfer agent action can be preferably used. The amount of isopropyl alcohol is 20 parts by mass or more and 90 parts by mass or less, preferably 25 parts by mass or more and 65 parts by mass or less, more preferably 30 parts by mass or more and 60 parts by mass to 100 parts by mass of water. Within the range of parts by mass. When the amount of isopropyl alcohol added is small, polymerization may not proceed. If the amount of isopropyl alcohol added is large, gelation cannot be suppressed during polymerization, and there is a fear that a gel-like substance is formed.

As the initiator, a water-soluble radical initiator is preferred. The polymerization initiator in the above copolymerization step may, for example, be a persulfate such as ammonium persulfate, sodium persulfate or potassium persulfate, hydrogen peroxide or 2,2'-azo-2-methylpropyl hydrazine. An arsenazo compound such as hydrochloride, a cyclic azo compound such as 2,2'-azo-2-(2-imidazolin-2-yl)propane hydrochloride, 2-aminomethylmercaptoazo An azo initiator such as an azonitrile compound such as isobutyronitrile. In this case, an iron (II) salt such as an alkali metal sulfite such as sodium hydrogen sulfite, a metabisulfite, sodium hypophosphite or ammonium ferrous sulfate or a sodium hydroxymethanesulfinate dihydrate may be used in combination. Promoters such as hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), and isoascorbic acid (salt). The water-soluble radical initiator is more preferably ammonium persulfate, sodium persulfate or potassium persulfate from the viewpoint of hygiene. Free radical initiators start to mix at room temperature It may be dissolved or dissolved in the reaction system, or may be added dropwise to the reaction system through several hours.

Examples of the polyvinyl-based resin include polyvinyl alcohol, a partially saponified or fully saponified polyvinyl acetate, and polyvinylpyrrolidone.

The above polyvinyl alcohol comprises: a partially saponified and fully saponified product of polyvinyl acetate, and a partially saponified and fully saponified product of a copolymer of vinyl acetate and other monomers. Further, a modified polymer obtained by introducing an anionic group such as a carboxylic acid, a sulfonic acid or a phosphoric acid into the polymer after polymerization may be used; or, a diacetone acrylamide may be introduced into the polymer after polymerization. a modified polymer obtained by crosslinking a reactive functional group such as a acetyl group, an ethyl hydrazide group, a decyl group or a stanol group; and the like.

In addition, examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid, and (meth)acrylic acid, and esters thereof; Alpha-olefin such as ethylene or propylene; olefin sulfonic acid such as (meth) propylene sulfonic acid, ethylene sulfonic acid or sulfonic acid maleate; sodium (meth)allyl sulfonate, sodium vinyl sulfonate or sodium sulfonate Alkyne sulfonate alkali salt such as (meth) acrylate, sodium sulfonate (monoalkyl maleate), sodium disulfonate maleate; N-methylol acrylamide, propylene sulfonamide a mercapto group-containing monomer such as an alkali sulfonic acid base salt; N-vinylpyrrolidone, an N-vinylpyrrolidone derivative; and the like.

Examples of the polyamide resin and the polyimide resin include a polyamide resin, a polyimide resin, and a polyamide amine imide resin. The method of water system is carried out by introducing a carboxyl group into the structure.

Examples of the natural polysaccharides include natural polysaccharides such as chitosan and derivatives thereof, and derivatives thereof. Chitosan is obtained by deacetylating a natural polymer chitin extracted from crustaceans such as crabs and shrimps by 60 to 100 mol%. For example, a chitosan obtained by de-acetylation of 100 mol% is a polymer substance obtained by bonding the 1-position and the 4-position of N-acetyl-β-D-glucosamine.

The chitosan derivative is a reaction product obtained by carboxylating, diolating, toluenesulfonating, sulfating, phosphorylating, esterifying or alkylating a hydroxyl group and/or an amine group of chitosan. . Specific examples thereof include chitosan, carboxymethyl chitosan, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, glycerol chitosan, and salts thereof with an acid. . Further, a reaction product obtained by introducing the tertiary amino group or the tertiary ammonium group into chitosan using a compound having a 3-stage amine group, a 4-stage ammonium group or both; The chemical agent directly alkylates the amine group of the chitosan to directly carry out the tertiary amination or the tertiary amination, thereby having a tertiary amine group, a tertiary ammonium group, or both in the molecule. So-called cationized chitosan; and their salts with acids.

The epoxy resin may, for example, be an epoxy compound having two or more glycidyl groups, or an epoxy resin obtained by reacting an epoxy compound having two or more glycidyl groups with a diamine such as ethylenediamine to cause cationization. a nonionic epoxy resin obtained by adding a polyethylene glycol to a side chain of an epoxy compound having two or more glycidyl groups; and the like.

Specific examples of the epoxy compound include diglycidyl succinate, diglycidyl adipate, and 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 ether, triglycidyl isocyanurate, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol Ethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerin oxidized olefin adduct, and the like. These epoxy compounds may be used alone or in combination of two or more.

As the elastomer, a conventionally known elastomer can be used. Specific examples include: natural gum, isoprene gum, butadiene gum, styrene-butadiene gum, neoprene gum, nitrile gum, acrylonitrile-butadiene-styrene gum, methyl methacrylate-butadiene gum, etc. Diene gum; butyl gum, ethylene propylene gum, urethane gum, eucalyptus gum, chlorosulfonated gum, chlorinated polyethylene, acrylic gum, epichlorohydrin gum, fluoro gum, etc. can be dispersed in water Elastomer. These elastomers may be used alone or in combination of two or more. Further, these elastomers may be modified by a functional group such as an amino group such as an amino group, a hydroxyl group or a methylol group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, an epoxy group, an isocyanate group or a carbodiimide group. body. Among these elastomers, butadiene gum, acrylonitrile-butadiene-styrene gum, nitrile gum, styrene-butadiene gum, methyl methacrylate-butadiene gum, acrylic gum, and the like are preferably used.

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

Relative to all solids of the aqueous metal surface treatment agent The content of the aqueous resin (C) is preferably in the range of 5% by mass or more and 95% by mass or less. When the content of the aqueous resin (C) is within this range, the initial adhesion and the durability adhesion between the metal surface treatment film and the laminated film are improved, and the corrosion resistance of the metal material is further improved. The content of the aqueous resin (C) is more preferably in the range of 10% by mass or more and 90% by mass or less, and still more preferably in the range of 30% by mass or more and 90% by mass or less.

The mechanism of action of the aqueous resin (C) is still unexplained, but it is considered that the density of the metal surface treatment film is increased by the presence of the aqueous resin (C) in the metal surface treatment film, and the water-based resin (C) itself It has high chemical resistance to acids and the like and therefore contributes to its performance. Further, it is considered that the aqueous resin (C) also functions to firmly fix the film to the metal compound (A).

(other)

The aqueous metal surface treatment agent of the present invention may contain various solvents as needed from the viewpoint of workability at the time of coating the surface of the 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; tetrahydrofuran, dioxane, etc. Ethers; esters such as ethyl acetate and butoxyethyl acetate; decylamines such as dimethylformamide and N-methylpyrrolidone; anthracene such as dimethylhydrazine; and tridecylamine hexamethylphosphate Ethamamine phosphates; and so on. Among them, one type of solvent may be used, or two or more types of solvents may be used in combination.

Further, without impairing the gist of the present invention and the properties of the film In the range, a surfactant, an antifoaming agent, a leveling agent, a crosslinking agent, a plasticizer, an antibacterial fungicide, a coloring agent, or the like may be added.

In addition, the crosslinking agent is not particularly limited as long as it is a crosslinking agent capable of forming a strong film by bonding with the resin (C), and examples thereof include melamines, isocyanates, and epoxy resins. Multivalent metal ions and the like. In the case of adding a crosslinking agent, a suitable curing catalyst may be further added in order to promote crosslinking.

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 value deviates from the range of 3 or more and 11 or less, the metal compound (A) is partially dissolved in the aqueous metal surface treatment agent, particularly the durability between the metal surface treatment film and the laminated film in an environment in contact with the acidic liquid. Reduced sexuality. More preferably, the pH is in the range of 6 or more and 10 or less.

(Manufacture of treatment agent)

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

(component analysis)

For the metal compound (A), for example, after applying an aqueous metal surface treatment agent to an aluminum plate (A1050P), it is dried at 80 ° C, and the obtained sample film is subjected to thin film X-ray diffraction analysis, and the diffraction is analyzed by Figure The spectrum was measured. Film X-ray diffraction analysis was carried out using a film X-ray diffraction apparatus (Model: Xpert-MPD) manufactured by PANalytical, using a wide-angle method at a tube voltage-current: 45 kV to 40 mA, and a scanning speed of 0.025 deg/sec.

For the phosphorus-containing or fluorine-containing compound (B), an aqueous metal surface treatment agent may be applied to an aluminum plate (A1050P), dried at 80 ° C, and subjected to XPS analysis of the obtained sample film. XPS analysis using an XPS analyzer manufactured by Shimadzu Corporation (model: ESCA-850), excitation X-ray: Mg-Kα, output power: 8kV-30mA, measurement area: F1s, P2p, sputtering time: 2 minutes The depth direction is analyzed under the condition of (5 second interval).

The water-based resin (C) can be subjected to FT-IR analysis (manufactured by Thermo Fisher Scientific Co., Ltd., model: Nicolite S10, specular reflection method), or other materials, by using a stock solution of a water-based metal surface treatment agent or a sample diluted with water as needed. Analytical methods are used for measurement and identification.

(processing object)

The aqueous metal surface treatment agent is treated with a metal material as an object. Examples of the metal material include pure copper, copper alloy (also referred to as "copper material"), pure aluminum, aluminum alloy (also referred to as "aluminum material"), ordinary steel, and alloy steel (also they are also used). Known as "iron material"), pure nickel, nickel alloys (also referred to as "nickel materials"), pure zinc, zinc alloys (also referred to as "zinc materials").

The shape, structure, and the like of the metal material are not particularly limited, and examples thereof include a plate shape, a foil shape, and the like. Further, the metal material may be a material obtained by coating the above-mentioned copper material, aluminum material, iron material, nickel material, or zinc material in other metal materials or ceramics by, for example, electroplating, vapor deposition, metal clad, or the like. A material formed on a substrate such as a material or an organic material.

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

[Metal surface treatment film and method of forming the same]

The metal surface treatment film of the present invention is composed of the above-mentioned water-based metal surface The film formed by the treatment agent. The method for forming the same includes the steps of: applying a water-based metal surface treatment agent to the surface of the metal material (coating step), and drying the layer after the coating step without water washing to form a metal surface treatment film ( Film formation step). It should be noted that a pretreatment step of degreasing or pickling the metal material in advance may be employed.

(coating step)

The coating step is a step of applying an aqueous metal surface treatment agent to the surface of the metal material. The coating method of the coating step is not particularly limited, and coating can be carried out by, for example, spraying, dip coating, roll coating, curtain coating, spin coating, or a combination thereof.

In the coating step, the conditions of use of the aqueous metal surface treatment agent are not particularly limited. For example, when the aqueous metal surface treatment agent is applied, the temperature of the treatment agent and the metal material is preferably in the range of 10 ° C to 90 ° C, more preferably in the range of 20 ° C to 60 ° C. When the temperature is 60 ° C or less, the use of excess energy can be suppressed, which is preferable from the viewpoint of economy. In addition, the coating time can be appropriately set.

(drying step)

The drying step is a step of drying without washing with water after the coating step. From this step, a metal surface treatment film can be formed. As the drying conditions, the maximum reaching temperature is preferably in the range of 50 ° C or more and 250 ° C or less. When the highest reaching temperature is less than 50 ° C, the water metal surface treatment agent The evaporation of the solvent sometimes takes a long time and is not preferable in practical use. On the other hand, when the maximum reaching temperature exceeds 250 ° C, wasteful use of energy is caused, which is not economically considered. The drying method is not particularly limited, and a drying method such as a batch type drying furnace, a continuous hot air circulation type drying furnace, a conveyor type hot air drying furnace, or an electromagnetic induction heating furnace using an IH heater can be used. The air volume, wind speed, and the like set in the drying method can be arbitrarily set.

(metal surface treatment film)

The metal surface treatment film can be obtained by the above formation method. The amount of the film of the metal surface treatment film is preferably in the range of 5 mg/m ² or more and 5000 mg/m ² or less. When the amount of the film is less than 5 mg/m ² , the barrier property of the metal surface treatment film is lowered, and the durability of the metal surface treatment film and the laminate film and the corrosion resistance of the metal material may be insufficient. On the other hand, when the amount of the film exceeds 5,000 mg/m ² , many cracks may occur in the metal surface treatment film, and the initial adhesion between the metal surface treatment film and the laminated film and the corrosion resistance of the metal material may sometimes change. Not enough. A more preferable film amount for these characteristics is in the range of 10 mg/m ² or more and 3000 mg/m ² or less, and particularly preferably 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 preferred to contain an oxide. The presence or absence of the metal compound (A) can be confirmed by analyzing the metal material of the obtained metal surface-treated film by a film X-ray diffraction method. Specifically, it can be taken The metal surface treatment film was used as a measurement sample, and the measurement sample was measured by film X-ray diffraction (Xpert-MPD manufactured by PANalytical, wide-angle method, tube voltage current: 45 kV-40 mA, scanning speed: 0.025 deg/sec). The diffraction pattern confirms the presence or absence of the metal compound (A).

The average particle diameter 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. When the average particle diameter is less than 1 nm, the crystal size is small, and thus the crystallinity is low, and there is a possibility that it may exist in an amorphous state depending on the case. Therefore, as a result, the acid resistance is lowered, and the durability adhesion between the metal surface treatment film and the laminated film in the environment in which the acidic liquid is exposed is sometimes lowered. On the other hand, when the average particle diameter exceeds 500 nm, in the metal surface treatment film after film formation, the volume fraction of the portion of the metal compound (A) having no acid resistance increases, particularly in an environment in which an acidic liquid is contacted. The durability of adhesion between the metal surface treatment film and the laminate film is sometimes lowered. The average particle diameter is preferably in the range of 1 nm or more and 100 nm or less. The average particle diameter 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 is provided between the metal material and the laminate film, and the adhesion of the laminate film is improved, and the corrosion resistance of the metal material is improved.

[Metal material with metal surface treatment film]

As shown in FIG. 1, the metal surface treatment metal film 10 of the present invention has a metal material 1, and a metal surface provided on the surface thereof. Physical film 2. The metal material 10 is usually further provided with a laminated film 3 on which the laminated film 3 is provided. It should be noted that the laminated film 3 is optional, and the laminated film 3 may not be provided before the laminated film 3 is laminated. Such a metal material 10 is excellent in adhesion to the laminated film 3, and is excellent in corrosion resistance.

The laminated film 3 can be arbitrarily selected according to the use, and is not particularly limited, in view of adhesiveness, gas barrier properties, electrical conductivity or design properties, corrosion resistance of the metal material 10, and the like. Examples of the material of the laminated film 3 include polyester resin, polyethylene resin, polypropylene resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyamide resin, and polyvinyl acetate. Resin, epoxy resin, polyimide resin, etc. As the laminated film, a film formed of these resin materials is used and laminated on the metal surface treatment film 2.

Example

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. The invention is not limited to the following examples.

[metal substrate]

. "Al"...A1100P (pure aluminum, JISH4000: 1999), thickness 0.3mm

. "ADC"...ADC12 (Al-Si-Cu-based aluminum alloy, JISH5302:2006), thickness 2.0mm

. "Cu"...C1020P (oxygen-free copper plate, JISH-3100), thickness 0.3mm

. "Ni"...Pure nickel plate (purity of 99% by mass or more), thickness 0.3mm

. "SUS"...SUS board (austenitic stainless steel), thickness 0.3mm

. “EG”... electroplated galvanized steel sheet (thickness 0.8mm, galvanized thickness 20μm)

[1. Production of water-based metal surface treatment agent]

Using water as a solvent, a metal compound sol (A), a phosphorus-containing or fluorine-containing compound (B), an aqueous resin (C), and an additive (D) added as needed are combined with ammonia or acetic acid. 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 for pH adjustment. In addition, the "solid content ratio" in the table indicates the ratio (% by mass) of each of the above compounds to the total solid content of the aqueous metal surface treatment agent.

<Metal Compound Sol (A)>

The metal compound sol (A) used is as follows. In addition, the average particle diameter of the metal compound sol (A) is a value measured by the dynamic light scattering photometer (DLC-6500) manufactured by Otsuka Electronics Co., Ltd.

A1: zirconia (IV) sol (solid content: 20% by mass, average particle diameter: 30 nm)

A2: cerium (IV) oxide sol (solid content 15% by mass, average particle diameter 50 nm)

A3: titanium oxide (IV) sol (solid content: 6 mass%, average particle diameter: 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 diameter 20 nm)

A7: zirconia (IV) sol (solid content: 15% by mass, average particle diameter: 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 to 70% in terms of P ₂ O ₇ )

B4: ammonium fluoride [NH ₄ F]

B5: sodium fluorohydride [NaFHF]

B6: Phytic acid [C ₆ H ₁₈ O ₂₄ P ₆ ]

B7: hydroxyethylidene diphosphonic acid [C ₂ H ₈ O ₇ P ₂ ]

<Aqueous resin (C)>

(C1: polyester resin)

An anionic polyester resin (solid content (NVC.) 30%) was synthesized by a condensation reaction of the following alcohol component and the following acid component by the following method, and the alcohol component included ethylene glycol (90 mol%) and trishydroxyl Methylpropane (10 mol%), the aforementioned acid component includes isophthalic acid (40 mol%), terephthalic acid (41 mol%), sodium dimethyl isophthalate-5-sulfonate (2 mol%), and trimellitic anhydride ( 17 mol%). In a 1000 mL round bottom flask equipped with a Claisen tube and an air condenser, 1 mol of the entire acid component and 2 mol of the total alcohol component and the catalyst (calcium acetate: 0.25 g, n-butyl titanate: 0.1 g) were added. The system was purged with nitrogen and heated to 180 ° C to melt the contents. Then, the temperature of the bath was raised to 200 ° C, and the mixture was heated and stirred for about 2 hours to carry out an esterification or transesterification reaction. Next, the bath temperature was raised to 260 ° C, and after about 15 minutes, the pressure in the system was reduced to 0.5 mmHg, and the reaction was carried out for about 3 hours (polycondensation reaction). After completion of the reaction, the mixture was naturally cooled while introducing nitrogen gas, and the contents were taken out. An appropriate amount of ammonia water (for water, which is 25% by weight) is added to the removed content, and heated and stirred in an autoclave at 100 ° C for 2 hours. A polyester resin of an aqueous emulsion was obtained.

(C2: urethane resin)

Making polyester polyol (adipate/3-methyl-1,5-pentanediol, number average molecular weight: 1000, number of functional groups: 2.0, hydroxyl value: 112.2) 100 parts by mass, trimethylolpropane 3 mass The fraction, 25 parts by mass of dimethylolpropionic acid, and 85 parts by mass of isophorone diisocyanate were reacted in MEK to obtain a urethane prepolymer. Mixing triethylamine in the urethane prepolymer 9.4 parts by mass was placed in water, the urethane prepolymer was dispersed in water, and the prepolymer was chain extended by ethylenediamine to obtain a dispersion. Methyl ethyl ketone was distilled off to obtain an aqueous urethane resin dispersion containing 30% by mass of a nonvolatile component. The acid value of the carboxyl group-containing urethane dispersed in the obtained aqueous urethane resin dispersion was 49 (KOH mg/g).

(C3: polyolefin resin)

A propylene-ethylene-α-olefin copolymer (propylene component: 68 mol%, ethylene component: 8 mol%, butene component: 24 mol%, weight average molecular weight: 60,000) 100 parts by mass was placed in a four-necked flask. 10 parts by mass of maleic anhydride, 10 parts by mass of methyl methacrylate, and 1 part by mass of dicumyl peroxide were stirred at 180 ° C for 2 hours to cause a reaction. A modified polyolefin resin composition having a weight average molecular weight of 45,000 and a graft quality of maleic anhydride of 8.4% by 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 placed in a four-necked flask, and uniformly stirred at 100 ° C for 2 hours using a stirring blade. After stirring and melting, 300 parts by mass of ion-exchanged water at 90 ° C was added and stirring was continued for 1 hour to obtain an aqueous polyolefin resin having a pH of 8.0.

(C4: Acrylic resin 1)

An aqueous acrylic acid solution (nonvolatile content concentration of 15.0% by mass, viscosity of 3 Pa.s, pH = 3.5, Tg: 130 ° C, anion) was used. The acrylic resin aqueous solution is obtained by copolymerizing butyl acrylate, acrylamide, and hydroxyethyl acrylate as a monomer.

(C5: Acrylic resin 2)

A temperature control regulator, a cooling tube, and a stirring device were installed in a reaction vessel containing a separable four-necked flask, and 390 parts by mass of ion-exchanged water and 210 parts by mass of isopropyl alcohol were added at room temperature, and N-hydroxyl as an acrylic monomer. 120 parts by mass of methacrylamide and 30 parts by mass of acrylamide were 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 added to dissolve. Then, after the reaction vessel was purged with nitrogen, the temperature was raised to 65 ° C over 30 minutes, and the reaction was carried out at 65 ° C for 3 hours. The reaction product was cooled to room temperature and taken out by filtration. The obtained acrylic resin aqueous solution has a nonvolatile content concentration of 20% by mass and a viscosity of 2.86 dPa. s, pH = 3.5.

(C6: polyvinyl alcohol)

Saponification degree: 99%, viscosity: 12mPa. S, Ethyl hydrazide degree: 9.8%, average molecular weight: 50,000 Ethylene acetylated polyvinyl alcohol.

(C7: polyamidoximine resin)

In a flask equipped with a thermometer, a stirrer, and a cooling tube, 1106.2 g of trimellitic anhydride, 1455.8 g of 4,4-diphenylmethane diisocyanate, and 2562.0 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred while stirring in a nitrogen stream. The temperature was gradually raised to 130 ° C in about 2 hours. While paying attention to the rapid foaming of the carbon dioxide generated by the reaction, the temperature was maintained at 130 ° C, and heating was continued for about 6 hours in this state, and then the reaction was stopped to obtain a polyamidoximine resin solution. The non-volatile component (200 ° C - 2 h) of the polyamidoximine resin solution is about 50% by mass, and the viscosity (30 ° C) is about 85.0 Pa. s. Further, the polyamidolimine resin has a number average molecular weight of about 17,000, and the carboxyl group obtained by ring opening of a carboxyl group and an acid anhydride group has a total acid value of about 40. 2700 g of this polyamidoximine resin was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and gradually heated to 50 ° C while 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 at 50 ° C, ion-exchanged water was gradually added while stirring. Finally, ion-exchanged water was added to 1348.8 g (30% by mass), and a transparent and uniform heat-resistant polyamidoximine resin was obtained.

(C8: natural polysaccharides)

Glycerated chitosan (number average molecular weight: 10,000 to 100,000, degree of glycerylation: 1.1) of the following structural formula was used.

(C9: epoxy resin)

Polyethylene glycol diglycidyl ether (n=9, 2-functional, epoxy equivalent 268 WPE, viscosity 70 Pa.s) was used.

(C10: Elastomer 1)

An aqueous dispersion of acrylonitrile-butadiene-styrene gum 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) .

(C11: Elastomer 2)

An aqueous dispersion of styrene gum having a carboxyl group (solid content concentration: 48.5%, pH = 7.8, viscosity: 104 mPa.s, particle diameter: 170 nm, Tg: -5 ° C) was used.

(C12: Acrylic resin 3)

An aqueous acrylic acid solution (nonvolatile content: 20.0% by mass, viscosity: 300 mPa.s, particle diameter: 170 nm, pH = 4.0, anion) was used, and the aqueous acrylic acid solution was methyl methacrylate and N-methylol propylene. The guanamine is obtained by copolymerization of a monomer.

(C13: Elastomer 3)

烷過氧化氫0.1份、乙二胺四乙酸鈉0.07份、硫酸亞鐵七水合物0.05份、及甲醛次硫酸氫鈉0.15份，起始聚合。聚合轉化率達到60%時，添加二乙基羥胺，停止聚合。通過蒸氣氣提回收未反應的單體，得到了固體成分濃度為21%的含有二烯類樹膠的分散液。 200 parts of water, 4.5 parts of sodium rosinate, 66 parts of butadiene, 26 parts of styrene, 8 parts of acrylonitrile, and 0.3 parts of 3-stage dodecyl mercaptan were placed in a nitrogen-substituted polymerization vessel. Then, the temperature of the polymerization vessel was set to 5 ° C, and a pair as a polymerization initiator was added.

0.1 part of alkane hydrogen peroxide, 0.07 parts of sodium edetate, 0.05 parts of ferrous sulfate heptahydrate, and 0.15 parts of sodium formaldehyde sulfoxylate were initially polymerized. When the polymerization conversion ratio reached 60%, diethylhydroxylamine was added to terminate the polymerization. The unreacted monomer was recovered by steam stripping to obtain a diene-containing gum-containing dispersion having a solid concentration of 21%.

<Other additives (D)>

(D1: Isocyanate hardener 1)

A hexamethylene diisocyanate-acetonitrile ethyl acetate block was used.

(D2: epoxy hardener 1)

Ethylene glycol diglycidyl ether (n = 1, bifunctional, epoxy equivalent 113 WPE, viscosity 20 mPa.s) was used.

(D3: Isocyanate hardener 2)

Toluene diisocyanate-diethylene glycol monoethyl ether block.

(D4: epoxy hardener 2)

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

D5: monoethyl acetonacetone bis(ethyl acetonate) aluminum

D6: Titanium lactate

D7: N-methylol acrylamide

D8: dimethylol urea

D9: Polyglycerol (average molecular weight 750, hydroxyl value 890)

D10: triethylene glycol

[2. Production of test materials]

The metal substrates described in Examples 1 to 41 and Tables 3 to 15 shown in Tables 1 and 2 were made of Fine cleaner 359E (manufactured by Parkerizing Co., Ltd., Japan). The 2% aqueous solution of the alkali degreaser was spray-degreased at 50 ° C for 10 seconds, and then washed with water to clean the surface. Next, in order to evaporate the water on the surface of the substrate, it was dried by heating at 80 ° C for 1 minute. The water-based metal surface treatment agents of Examples 1 to 41 shown in Tables 1 and 2 and Comparative Examples 1 to 15 shown in Tables 1 and 2 were applied to the degreased metal by a bar coating method using a #8SUS Meyer rod. The surface of the substrate was dried at 180 ° C for 1 minute in a hot air loop drying oven to form a metal surface treatment film on the surface of the metal substrate. In addition, the metal base materials described in Comparative Examples 16 to 21 shown in Table 3 were subjected to degreasing, water washing, and then heat-dried in the same manner as described above, and were also used for the test. Tables 1 to 3 summarize the film formation amounts of the aqueous metal surface treatment agent used in each of the examples or the comparative examples and the obtained metal surface treatment film.

[3. Determination of average particle diameter of metal compound sol (A)]

The metal material of the metal surface-treated film obtained in Example 3, Example 6, and Example 13 was observed by a transmission electron microscope (TEM) to observe the average particle diameter of the metal compound (A). The average particle diameter of the metal compound (A) is about 100 nm, 30 nm, and 20 nm, respectively.

[4. Lamination performance evaluation]

Then, a laminated film was bonded to the metal surface treatment film of the metal substrate by the lamination method shown below.

(Layer 1)

On the surface of the metal substrate on which the metal surface treatment film was formed, a single-sided corona-treated polyester film (film thickness: 16 μm) was thermocompression-bonded at 250 ° C and a surface pressure of 5 MPa for 10 seconds to produce a film. A metal material having a metal film treated with a polyester film laminated thereon.

(Layer 2)

The dispersion of the acid-modified polypropylene was roll-coated on the surface of the metal substrate on which the metal surface treatment film was formed, and then dried in a hot air loop type drying oven at 200 ° C for 1 minute, thereby forming a thickness of 5 μm. Floor. Then, the adhesive layer and the polypropylene film having a thickness of 30 μm were thermocompression-bonded at 250 ° C and 0.1 MPa for 10 seconds, thereby producing a metal material having a metal surface-treated film laminated with a polypropylene film.

<4.1. Initial Adhesion>

For the metal material with a metal surface treatment film provided with the laminated film by lamination 1 and lamination 2, after extrusion 5 mm with an ERICHSEN test machine, a checkerboard tape peeling test (1 mm interval) was carried out, and the metal material was pressed. The initial adhesion of the laminated film was evaluated in the first to third grades.

3: The laminated film is not peeled at all.

2: Partial peeling of laminated film

1: The entire surface of the laminated film peeled off

<4.2. Durability Adhesion>

A press cooking test was performed on a metal material having a metal surface treatment film provided with a laminated film by lamination 1. The conditions were 125 ° C, 2 atmospheres, and 1 hour, using a commercially available sterilization device. Then, it was dried, cut into 15 mm, and subjected to 180° peel strength measurement. The adhesion between the laminated film and the metal material was evaluated in the following order of 1 to 9.

9: The peel strength is 10 N or more.

8: The peeling strength was in the range of 9 N or more and less than 10 N.

7: The peel strength was 8 N or more and the range of 9 N was not reached.

6: The peel strength was in the range of 7 N or more and less than 8 N.

5: The peel strength was 6 N or more and the range of 7 N was not reached.

4: The peel strength was 5 N or more and less than 6 N.

3: The peel strength was 3 N or more and less than 5 N.

2: The peeling strength was in the range of 1 N or more and less than 3 N.

1: The laminated film has been peeled off, or has not reached 1N.

<4.3. Corrosion resistance>

The metal material with a metal surface-treated film provided with the laminated film by lamination 2 was visually observed after performing the 24-hour CASS test in accordance with JIS H 8502, and was evaluated in the following order of 1 to 9.

9: The appearance is completely unchanged.

8: The area ratio of the peeling (floating) of the laminated film and the corrosion under the laminated film was more than 0% and 5% or less.

7: The area ratio of the peeling (floating) of the laminated film and the corrosion under the laminated film was more than 5% and 10% or less.

6: The area ratio of peeling (floating) of the laminated film and corrosion under the laminated film was more than 10% and 15% or less.

5: The area ratio of the peeling (floating) of the laminated film and the corrosion under the laminated film was more than 15% and 20% or less.

4: The area ratio of peeling (floating) of the laminated film and corrosion under the laminated 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: peeling (floating) of the laminated film and under the laminated film The area ratio of corrosion is more than 40% and is 60% or less.

1: The area ratio of peeling (floating) of the laminated film and corrosion under the laminated film was over 60%.

<4.4. Content tolerance 1>

A metal material coated with a metal surface-treated film having a polyester film laminated thereon is immersed in a simulated fruit juice (citric acid monohydrate: sodium chloride: deionized water = 5:5:990 (quality ratio)) After one week at 60 ° C, it was taken out and cut into 15 mm, and the 180° peel strength was measured. The adhesion between the laminated film and the metal material was evaluated in the following order of 1 to 9.

9: The peel strength is 10 N or more.

8: The peeling strength was in the range of 9 N or more and less than 10 N.

7: The peel strength was 8 N or more and the range of 9 N was not reached.

6: The peel strength was in the range of 7 N or more and less than 8 N.

5: The peel strength was 6 N or more and the range of 7 N was not reached.

4: The peel strength was 5 N or more and less than 6 N.

3: The peel strength was 3 N or more and did not reach the range of 5 N.

2: The peeling strength was in the range of 1 N or more and less than 3 N.

1: The laminated film has been peeled off, or has not reached 1N.

<4.5. Content tolerance 2>

The metal material of the metal surface-treated film having a polypropylene film laminated thereon was laminated in an electrolyte solution manufactured by Kishida Chemical Co., Ltd. (trade name: LBG-00015, electrolyte: 1M-LiPF ₆ , solvent: EC/ In DMC/DEC=1:1:1 (capacity ratio), it was placed in a thermostat at 60 ° C for 7 days. Then, the test material was taken out, immersed in ion-exchanged water for 1 minute, shake-washed, and dried in a hot air loop type drying oven at 100 ° C for 10 minutes. Then, it was cut into 15 mm, and 180 degree peeling strength measurement was performed. The adhesion between the laminated film and the metal material was evaluated in the following order of 1 to 9.

9: The peel strength is 10 N or more.

8: The peeling strength was in the range of 9 N or more and less than 10 N.

7: The peel strength was 8 N or more and the range of 9 N was not reached.

6: The peel strength was in the range of 7 N or more and less than 8 N.

5: The peel strength was 6 N or more and the range of 7 N was not reached.

4: The peel strength was 5 N or more and less than 6 N.

3: The peel strength was 3 N or more and less than 5 N.

2: The peeling strength was in the range of 1 N or more and less than 3 N.

1: The laminated film has been peeled off, or has not reached 1N.

〔result〕

The results are shown in Tables 4 to 6.

As shown in Tables 4 and 5, it was confirmed that the metal material of the metal surface-treated film obtained in Examples 1 to 41 was excellent in initial adhesion, durability, corrosion resistance, and the like after the formation of the laminated film. As shown in Table 6, the metal material of the metal surface-treated film obtained in Comparative Examples 1 to 15 was inferior to the examples in terms of initial adhesion, durability, corrosion resistance, and the like.

Industrial availability

The water-based metal surface treatment agent of the present invention, the metal surface treatment film formed of the water-based metal surface treatment agent, and the metal material with the metal surface treatment film are used in a wide range of fields such as home appliances, food, and construction, and are particularly applicable to aluminum. Metal materials such as magnesium, copper, iron, zinc, nickel or alloys of these metals. Therefore, it can be preferably used as a container for filling a content containing an organic acid such as acetic acid or citric acid or an inorganic acid such as sulfuric acid or hydrofluoric acid. Specifically, it can be preferably used for food containers and detergents. A container, a container for a lithium ion secondary battery, or the like.

1‧‧‧Metal materials

2‧‧‧Metal surface treatment film

3‧‧‧Laminated film

10‧‧‧Metal materials with metal surface treatment film

Claims (8)

An aqueous metal surface treatment agent characterized by containing at least a metal compound (A), a phosphorus-containing or fluorine-containing compound (B), and a water-based resin (C), the metal compound (A) being selected from zirconium, titanium or hafnium. One or two or more kinds of oxides, and the average particle diameter thereof is in the range of 1 nm or more and 500 nm or less, and the phosphorus-containing or fluorine-containing compound (B) is one selected from the group consisting of a phosphorus compound group and a fluorine compound group or Two or more kinds of the water-based resin (C) are selected from the group consisting of polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, and natural materials. One or more of a saccharide, an epoxy resin, and an elastomer. The aqueous metal surface treatment agent according to claim 1, wherein the content of the metal compound (A) is in a range of 5 mass% or more and 90 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 aqueous resin (C) is in a range of 5 mass% or more and 90 mass% or less based on the total solid content. The aqueous metal surface treatment agent according to claim 1 or 2, wherein the pH is in the range of 3 or more and 11 or less. The aqueous metal surface treatment agent of claim 1 or 2 for use in a laminated substrate. A metal surface treatment film treated with a water based metal surface The aqueous metal surface treatment agent contains at least a metal compound (A), a phosphorus-containing or fluorine-containing compound (B), and a water-based resin (C), and the metal compound (A) is an oxide selected from zirconium, titanium or hafnium. One or two or more of the above, and the average particle diameter thereof is in the range of 1 nm or more and 500 nm or less, and the phosphorus-containing or fluorine-containing compound (B) is one or two selected from the group consisting of a phosphorus compound group and a fluorine compound group. In the above, the aqueous resin (C) is selected from the group consisting of polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, and natural polysaccharides. One or two or more of an epoxy resin and an elastomer. A metal material with a metal surface treatment film having a metal material and a metal surface treatment film as claimed in claim 6 disposed on the surface of the metal material. The metal material of the metal surface treatment film of claim 7, further comprising a laminate film disposed on the metal surface treatment film.