KR20190076936A - Aqueous metal surface treatment agent, metal surface treatment coating film and metal material having a metal surface treatment coating film - Google Patents

Abstract

Provided are an aqueous metal surface treatment agent for forming a surface treatment coating film formed between a metal material and a laminate film to enhance adhesion between the metal material and the laminate film and to improve corrosion resistance of the metal material; and a metal surface treatment coating film. The objectives are achieved by an aqueous metal surface treatment agent which at least comprises: one or more metal compounds (A) selected from oxides of zirconium, titanium, or hafnium having an average particle diameter in the range of 1-500 nm; one or more phosphorus or fluorine-containing compounds (B) selected from a phosphorus compound group and a fluorine compound group; and one or more aqueous resins (C) selected from a polyester resin, a urethane 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.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal surface treatment agent, a metal surface treatment agent, a metal surface treatment agent, a water-based metal surface treatment agent, a metal surface treatment film,

The present invention relates to an aqueous metal surface treatment agent which is formed between a metal material and a laminate film to improve the adhesion of the laminate film and to form a surface treatment film capable of improving the corrosion resistance of the metal material, A metal surface treatment film formed of an aqueous metal surface treatment agent, and a metal material formed with the metal surface treatment film.

Various metal coating materials such as aluminum, magnesium, iron, copper, zinc, nickel or their alloys have been formed on the surface thereof for the purpose of improving their protective performance and designability. And containers for beverages and the like. Various properties are required for the metal materials used in these fields. Examples of the means for forming the resin coating layer include coating, film lamination and printing.

Among them, film laminate processing is a processing means for heating and pressing a resin film (hereinafter, referred to as a laminate film) to the surface of a metal material, and is a means for protecting the surface or for protecting the surface of a metal material As one of the coating methods for the coating layer. This film laminating process is advantageous compared to the method of forming a resin coating film in which a resin composition is dissolved or dispersed in a solvent and is dried and applied on the surface of a metal material to produce a waste gas such as a solvent or carbon dioxide, Less. For this reason, film laminate processing is preferably applied from the viewpoint of environmental preservation, and its application is expanded, for example, to produce a thin film of aluminum thin plate material, steel thin plate material, copper thin plate material, nickel plated copper thin plate material, aluminum foil for packing or stainless steel foil As a method for coating a laminate film on a construction material, a body for a food can or a covering material, a food container, or a battery container.

In the undercoating treatment of a metal material, chromate treatment using a surface treatment agent containing hexavalent chromium is inexpensive because it is inexpensive. In recent years, the use of harmful metals (compounds, ions) such as hexavalent chromium, lead, and cadmium in Europe has been regulated in Japan, PRTR (Environmental Pollutant Emission Transfer Registration System) In addition to its impact on the environment, trends aimed at preserving the global environment are increasing on a global scale. Under such circumstances, the perception of the danger of adversely affecting the human body and the environment has become very high, and a substitution technique of a hexavalent chromium-containing surface treatment agent generally used as a substrate treatment agent for metal materials, that is, Treatment is being proposed.

In recent years, development of a chrome-free treatment agent containing no trivalent chromium has also been desired. For example, Patent Document 1 discloses a chromium-free undercoating treatment agent for a laminate in which a specific amount of a water-soluble zirconium compound, a water-soluble or water-dispersible acrylic resin having a specific structure, and a water- . Also, in Patent Document 2, 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 is proposed. Patent Document 3 proposes a ground 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 not containing fluorine.

Japanese Patent Application Laid-Open No. 2002-265821 Japanese Patent Application Laid-Open No. 2003-313680 Japanese Laid-Open Patent Publication No. 2009-84516

As described above, the metal material on which the laminate film having the laminate film formed on the surface of the metal material is formed is widely used in many fields, and is used as a material for a container or a material for packaging that accommodates various contents. Particularly, in the field of food packaging such as food containers, the types of foods to be packed are various from the viewpoints of improvement of eating habits and simplicity, and various types of contents such as sauces, vinegar, animal fats, various spices, citrus beverages, The anger does not stop. Therefore, there is a demand for a material for a container or a material for packaging that does not deteriorate the adhesiveness of the laminated film or deteriorate the corrosion resistance of the metal material by the contained contents. In addition, the sterilization temperature of food is increased to 100 占 폚 (boiled food), 120 占 폚 (retort food) and 135 占 폚 (high retort food), and durability of container material or packing material at high temperature is required . In addition, the same performance is required in other industrial fields.

However, with respect to the undercoat treatment described in the above Patent Documents 1 to 3, it is desired that the durability of adhesion between the metal material and the laminate film is further improved, and the corrosion resistance of the metal material under a strict environment is further improved Is desired.

The object of the present invention is to provide a laminate film which is formed between a metal material and a laminate film to improve the adhesion of the laminate film and to provide a surface treatment capable of improving the corrosion resistance of the metal material An aqueous metal surface treatment agent for forming a film, a metal surface treatment film formed of the aqueous metal surface treatment agent, and a metal material having the metal surface treatment film formed thereon.

(1) The aqueous metal surface treatment agent according to the present invention for solving the above problems is characterized by comprising one or more metal compounds (A ), At least one phosphorus or fluorine-containing compound (B) selected from a phosphorus compound group and a fluorine compound group and at least one phosphorus compound selected from the group consisting of a polyester resin, a urethane resin, a polyolefin resin, an acrylic resin, a polyvinyl resin, , A polyimide resin, a natural polysaccharide, an epoxy resin and an elastomer (C).

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 aqueous metal surface treatment agent according to the present invention, it is preferable that 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.

In the aqueous metal surface treatment agent according to the present invention, it is preferable that the pH is in the range of 3 to 11 inclusive.

The aqueous metal surface treating agent according to the present invention is preferably used for laminating.

(2) The metal surface-treated film according to the present invention for solving the above-mentioned problems is characterized in that one or two or more kinds of metal compounds selected from oxides of zirconium, titanium or hafnium having an average particle diameter within a range of 1 nm to 500 nm ), At least one phosphorus or fluorine-containing compound (B) selected from a phosphorus compound group and a fluorine compound group and at least one phosphorus compound selected from the group consisting of a polyester resin, a urethane resin, a polyolefin resin, an acrylic resin, a polyvinyl resin, (C) selected from the group consisting of a polyimide resin, a natural polysaccharide, an epoxy resin and an elastomer.

(3) A metal material on which a metal surface treatment film according to the present invention for solving the above problems is formed is characterized by having a metal material and a metal surface treatment film according to the present invention formed on the surface of the metal material.

The metal material having the metal surface treatment film according to the present invention is further provided with a laminate film formed on the 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 can be formed between a metal material and a laminate film to improve the adhesion of the laminate film and improve the corrosion resistance of the metal material .

The metal surface treated film according to the present invention can be formed between the metal material and the laminate film to improve the adhesiveness of the laminate film and improve the corrosion resistance of the metal material.

The metal material on which the metal surface treatment film according to the present invention is formed has excellent adhesion between the metal material and the laminate film through the metal surface treatment film, and the corrosion resistance of the metal material is excellent.

1 is a schematic sectional view showing an example of a metal material on which a metal surface treatment film according to the present invention is formed.

Hereinafter, the aqueous metal surface treatment agent, the metal surface treatment film and the metal material on which the metal surface treatment film is formed according to the present invention will be described in detail. In addition, the present invention can be arbitrarily changed within the scope including its gist, and is not limited to the following embodiments.

[Water based metal surface treatment agent]

The aqueous metal surface treatment agent according to the present invention is characterized by containing one or more metal compounds (A) selected from oxides of zirconium, titanium or hafnium having an average particle size within a range of 1 nm to 500 nm, (B) selected from the group consisting of one or more phosphorus-containing or fluorine-containing compounds (B) 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, (C) selected from the group consisting of a resin and an elastomer.

Hereinafter, the components of the aqueous metal surface treatment agent and the object to be treated 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 within a range from 1 nm to 500 nm. Specific examples thereof include oxides of zirconium, oxides of titanium, and oxides of hafnium. 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, oxides of zirconium are particularly preferable.

The metal compound (A) is preferably used as a dispersion solution (for example, a sol or the like) in which the solid particles are dispersed in an aqueous solvent in advance. This dispersion solution is easier to handle than the solid particles themselves of the metal compound (A), and has an advantage of facilitating the production of the aqueous metal surface treatment agent.

The aqueous solvent means a solvent containing 50 mass% or more of water. Examples of the solvent other than water contained in the aqueous solvent include alkane-based solvents such as hexane and pentane; Aromatic solvents such as benzene and toluene; Alcohol solvents such as ethanol, 1-butanol and ethyl cellosolve; Ether solvents such as tetrahydrofuran and dioxane; Ester solvents such as ethyl acetate and butoxyethyl acetate; Amide solvents such as dimethylformamide and N-methylpyrrolidone; Sulfone solvents such as dimethyl sulfoxide; And phosphoric acid amide type solvents such as hexamethylphosphoric triamide. One kind of solvent other than these water may be used alone, or two or more kinds of solvents may be used in combination.

The above-mentioned method for preparing a dispersion solution can be carried out by, for example, a first method in which solid particles of a metal compound (A) are obtained or synthesized and then dispersed in an aqueous solvent using a dispersant, There is a second method for producing a dispersion of the metal compound (A) in an aqueous solvent using a water-soluble salt. Of these, the second method is preferably used.

Specifically, a second method is to add an alkali agent to an acidic aqueous solution of a water-soluble salt of zirconium, titanium or hafnium, and add a dispersant if necessary to produce an oxide of zirconium, titanium or hafnium in water, Is removed by separation. By this second method, a dispersion solution containing solid particles of an oxide of zirconium, titanium or hafnium can be prepared.

As water-soluble salts of zirconium, titanium or hafnium, conventionally known salts may be used. Specific examples thereof include zirconium chloride, zirconium oxychloride, titanium chloride, hafnium chloride, zirconium nitrate, titanium nitrate, hafnium nitrate, zirconium sulfate, titanium sulfate, hafnium sulfate, fluorozirconium acid, fluorotitanic acid, Zirconium, titanium acetate, hafnium acetate, zirconium lactate, titanium lactate, and hafnium lactate. These salts may be hydrates.

As the alkali agent, conventionally known alkali agents may be used. Specifically, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide can be used. In some cases, depending on the intended use of the sol, sodium or potassium may not be contained. In this case, ammonia, ammonium hydrogen carbonate or urea may be used.

As the above-mentioned dispersing agent, conventionally known dispersing agents can be used. Among them, hydroxycarboxylic acid is preferable, and specific examples thereof include citric acid, malic acid, tartaric acid, lactic acid, hydroxyvaleric acid, glyceric acid, tropic acid, benzylic acid and the like. Particularly, a hydroxycarboxylic acid having a divalent or higher valent carboxyl group such as citric acid, malic acid or tartaric acid can be preferably used since it can be dispersed with a small content.

The separation furnace described above includes a separation method using an ion exchange resin, a separation method using membrane filtration, and the like, but it is more preferable because the separation method using an ultrafiltration membrane 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 through the metal surface treated film is good, and in particular, high adhesion (durability) is obtained even in an environment in contact with an acidic liquid And also the corrosion resistance of the metal material can be improved.

The mechanism of action of the metal compound (A) is still unclear at this point. However, the metal compound (A) does not contain the metal compound (A), and instead a metal made of an aqueous metal surface treatment agent containing a water-soluble salt of zirconium, The inventors of the present invention have found that the performance of the surface treated film does not develop. The metal compound (A), which is an oxide of zirconium, titanium or hafnium, has a higher acid resistance than a water-soluble salt and does not dissolve even in contact with an acidic liquid or the like. It is considered that the metal surface-treated film thus produced has high durability.

It is preferable that the average particle diameter of the metal compound (A) dispersed in the aqueous metal surface treatment agent and dispersed in the aqueous metal surface treatment agent is 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 of adhesion between the metal surface treated film and the laminated film under an environment in contact with the acidic liquid is lowered. On the other hand, if the average particle diameter exceeds 500 nm, the volume ratio of the portion where the metal compound (A) having no acid resistance increases in the metal surface treated film after film formation increases, and particularly, the durability May be lowered. The average particle diameter 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 dynamic light scattering method, laser diffraction method, centrifugal sedimentation method and the like. Specifically, the measurement can be performed using a dynamic light scattering photometer (DLS-8000 series) manufactured by Otsuka Electronics Co., Ltd., and a laser diffraction / scattering type particle size distribution analyzer (LA-920) manufactured by Horiba Seisakusho Co., The average particle diameter of the metal compound (A) in the metal surface-treated film formed on the metal material having the metal surface-treated film to be described later is measured by directly observing the surface or cross-section of the metal surface-treated film with a transmission electron microscope can do.

(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 kind or two or more kinds selected from a phosphorus compound group and a fluorine compound group is used.

Examples of the phosphorus compound group include a group comprising a plurality of phosphorus-containing compounds such as phosphoric acids, phosphoric esters, and organic phosphonic acids. Concrete examples of phosphoric acid 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 and the like). In addition, metaphosphoric acid includes trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid and the like. Polyphosphoric acid is a chain type phosphoric acid condensate, including pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid and the like. Specific examples of the phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, Sodium salt, calcium salt, magnesium salt, lithium salt and the like) and riboflavin phosphate ester. Specific examples of the organic phosphonic acid include aminotrimethylenephosphonic acid, 1-hydroxyethylidene 1,1-diphosphonic acid, ethylenediamine tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and the like. have. 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 salts, potassium salts, ammonium salts, magnesium salts and lithium salts of condensed phosphoric acids including polyphosphoric acid (including pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid and the like); Sodium salts, potassium salts, ammonium salts, magnesium salts and lithium salts of phytic acid; Then, sodium salt of organic phosphonic acid (including aminotrimethylene phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid) It is preferable to use at least one member selected from a salt, a potassium salt, an ammonium salt, a magnesium salt and a lithium salt. These phosphorus-containing compounds may be used alone or in combination of two or more. Examples of the condensed phosphate include polyphosphates, metaphosphates, and ultraphosphoric acids, and the atomic ratio of the metal and phosphorus is Me ₂ O / P ₂ O ₅ (this is represented by R and Me is calculated by the monovalent metal) . The polyphosphate is in the case of 2 > R > 1, the metaphosphate is in the case of R = 1, and the ultraphosphate is in the case of R <

Since phytic acid or organic phosphonic acid has two or more phosphon groups in one molecule as compared with the phosphate, it is considered that the crosslinking density is increased and the durability of the film is enhanced. On the other hand, the condensed phosphate has a larger amount of the phosphone group per molecule as compared with the phosphate, but is relatively easily hydrolyzed and eventually becomes phosphate. Therefore, it is considered that the condensed phosphate is not as high in endurance adhesion as phytic acid or organic phosphonic acid in the range of comparing condensed phosphate with phytic acid or organic phosphonic acid.

Examples of the fluorine compound group include fluorine compounds such as hydrofluoric acid, hydrofluoric acid, sodium fluoride, potassium fluoride, ammonium fluoride, lithium fluoride, acidic sodium fluoride, potassium acid fluoride, ammonium fluoride, fluorozirconium acid, ammonium fluoro zirconium, And a fluorocarbon-containing compound such as ammonium fluorotitanate. These fluorine-containing compounds may be used alone or in combination of two or more.

Among them, it is preferable to use at least one selected from the group consisting of sodium salt, potassium salt, ammonium salt and lithium salt of hydrofluoric acid.

The content of the phosphorus or fluorine-containing compound (B) in the metal compound (A) is preferably in the range of 0.1 to 10 parts by weight based on the sum of the molar amounts of the metal atoms (zirconium atom, titanium atom, hafnium atom) (B / A) of the sum of the molar amounts of the constituent phosphorus atoms and fluorine atoms is in the range of 0.005 or more and 5.0 or less. The content of the phosphorus- or fluorine-containing compound (B) is preferably adjusted so that the above-mentioned ratio is in a range of 0.01 to 2.0 in terms of initial adhesion and durability, more preferably 0.02 or more and 0.5 or less So that it is particularly preferable to adjust it.

The action mechanism of the phosphorus-containing or fluorine-containing compound (B) is still unclear at present, but the phosphorus-containing compound and / or the fluorine-containing compound are dissolved in the aqueous metal surface treatment agent, The surface of the metal material is slightly etched with the phosphorus-containing compound or the fluorine-containing compound to form fine irregularities, and it is considered that the initial adhesion and the durability are improved by the anchor effect due to the fine irregularities. It is considered that the presence of the phosphorus-containing compound and the fluorine-containing compound in the metal surface-treated film lowers the permeability of the anion which is the corrosion factor, 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 particle surface of the metal compound (A) in the coating film and also function as a crosslinking agent. In particular, the phosphorus-containing compound is not easily broken when exposed to a chemical such as an acid, and the durability of the phosphorus-containing compound is considered to be higher than that of the fluorine-containing compound.

The anchoring effect due to fine unevenness is particularly effective when the average particle diameter of the metal compound (A) is within the range of 5 nm or more and 100 nm or less. If the average particle diameter of the metal compound (A) becomes too fine, the particles tend to get into the fine irregularities and the resin tends to come into contact with the substrate, so that the effect of improving the initial adhesion and the durability can be suppressed.

(Water-based resin)

As the water-based resin (C), conventionally known water-based resins can be applied. Specifically, one or more water-based resins selected from a polyester resin, a urethane 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 .

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

Examples of the polyester resin include polyester resins such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimeric acid, trimeric acid, isophthalic acid, terephthalic acid, Polybasic acids such as trimellitic acid, trimesic acid, pyromellitic acid and naphthalenedicarboxylic acid, and organic acids such as ethylene glycol, diethylene glycol, trimethylol propane, neopentyl glycol, 1,4-CHDM, A polyester polyol in which a polyol is condensed; Condensation resins obtained by condensation of the above polybasic acids with polyols such as polymer polyols, polycaprolactone polyols, polycarbonate diols, polybutadiene polyols, neopentyl glycol, and methylpentadiol.

It is also possible to use a monomer having three or more carboxyl groups such as trimellitic acid and pyromellitic acid as a part of the monomers and a water-based resin in which unreacted carboxylic acid is neutralized with an alkali to be solubilized or moisture- A water-based resin obtained by solubilization or moisture oxidation using a sulfonated monomer such as sulfophthalic acid may also be used.

Examples of the urethane resin include a urethane resin which is an axial polymer of a polyol such as a polyester polyol, a polyether polyol and a polycarbonate polyol, and an aliphatic polyisocyanate, an alicyclic isocyanate and / or an aromatic polyisocyanate compound, And polyurethanes obtained by using a polyol having a polyoxyethylene chain such as polypropylene glycol.

Such a polyurethane can be rendered water-soluble or water-soluble in a non-ionic state by increasing the introduction ratio of the polyoxyethylene chain. A urethane prepolymer having isocyanato groups at both ends is prepared from a polyisocyanate and a polyol. A carboxylic acid having two or more hydroxyl groups or a reactive derivative thereof is reacted with the urethane prepolymer to obtain a derivative having an isocyanate group at both ends Triethanolamine or the like is added thereto to prepare an ionomer (triethanolamine salt), the resulting ionomer is added to water to give an emulsion or dispersion, and further, if necessary, a diamine is added to extend the chain, Of urethane resin can be obtained.

The carboxylic acid and the reactive derivative used for producing the water-dispersible urethane resin having an 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 include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolalkanoic acid such as dimethylolhexanoic acid. Examples of the reactive derivative include hydrolyzable esters such as acid anhydrides.

As the polyolefin resin, polypropylene; Polyethylene; A modified polyolefin obtained by modifying a polyolefin such as a copolymer of propylene and ethylene and an? -Olefin with an unsaturated carboxylic acid (such as acrylic acid or methacrylic acid); And copolymers of ethylene and acrylic acid (methacrylic acid). These polyolefin resins may be further copolymerized with other ethylenically unsaturated monomers in a small amount. As means for hydration, a means for neutralizing the carboxylic acid introduced into the polyolefin resin with ammonia or an amine may be mentioned.

Examples of the acrylic resin include a single polymer or copolymer of an acrylic monomer, and further, a copolymer of an addition polymerizable monomer capable of copolymerizing with the acrylic monomer. Such an acrylic resin is not particularly limited as long as it can stably exist in an aqueous 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-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, Dodecyl acrylate, glycidyl methacrylate, sulfoethyl acrylate, and polyethylene glycol methacrylate. Examples of the addition-polymerizable monomer copolymerizable with the acrylic monomer include maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, diacetone acrylamide, styrene, acrylonitrile and vinylsulfonic acid.

The polymerization of the monomer is carried out in a solvent in the presence of an initiator in an inert gas stream at a temperature of 30 ° C or more and 80 ° C or less, preferably 40 ° C or more and 75 ° C or less, Lt; 0 > C or less. When the polymerization temperature is low, the polymerization may not proceed, and when the polymerization temperature is high, gel products may be formed.

The polymerization time is suitably in the range of 1 hour to 24 hours. The solvent is preferably water-soluble, and examples thereof include alcohols such as 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, triethylene glycol, triethylene glycol monoalkyl ether, triethylene glycol dialkyl ether, propylene glycol, and glycerin.

Of these, isopropyl alcohol having an action as a chain transfer agent can be preferably used. The isopropyl alcohol is used in an amount of 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 or less, Within the range. If the amount of isopropyl alcohol to be added is small, polymerization may not proceed, and if the amount of isopropyl alcohol is large, gelation during polymerization can not be suppressed, and gel products may be formed.

As the initiator, a water-soluble radical initiator is preferred. Examples of the polymerization initiator in the copolymerization step include azo compounds such as persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, hydrogen peroxide, and azo such as 2,2'-azobis-2-methylpropionamidine hydrochloride Aminidine compounds, cyclic azoamidine compounds such as 2,2'-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, and azonitriles such as 2-carbamoyl azoisobutyronitrile An azo type initiator such as a compound, and the like. At this time, an Fe (Ⅱ) salt such as an alkali metal sulfite such as sodium hydrogensulfite, a meta sulphite salt, a sodium hypophosphite, a morpholinium salt, sodium hydroxymethanesulfinate dihydrate, a hydroxylamine hydrochloride, thiourea, L-ascorbic acid (Salt), and erysorbic acid (salt) 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 initially mixed and dissolved in the reaction system at room temperature or may be dropped into the reaction system over several hours.

Examples of the polyvinyl resin include polyvinyl alcohol, partially saponified or fully saponified polyvinyl acetate, and polyvinyl pyrrolidone.

The above-mentioned polyvinyl alcohols include partially saponified and fully saponified polyvinyl acetate and partially saponified and fully saponified copolymers of vinyl acetate and other monomers. Further, a modified polymer obtained by introducing an anion group such as a carboxylic acid, a sulfonic acid, or a phosphoric acid into a polymer after polymerization; Or a modified polymer into which a functional group having cross-linking reactivity such as a diacetone acrylamide group, an acetoacetyl group, a mercapto group or a silanol group is introduced can be applied.

Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids and esters thereof such as maleic acid, fumaric acid, crotonic acid, itaconic acid, and (meth) acrylic acid; Olefins; Olefin sulfonic acids such as (meth) acryl sulfonic acid, ethylene sulfonic acid and sulfonic acid maleate; (Meth) allylsulfonate, sodium oleate sulfonate such as sodium ethylene sulfonate, sodium sulfonate (meth) acrylate, sodium sulfonate (monoalkyl maleate), and disulfonic acid sodium alkyl malate; Amide group-containing monomers such as N-methylol acrylamide and acrylamide alkylsulfonic acid alkali salts; N-vinylpyrrolidone, N-vinylpyrrolidone derivatives, and the like.

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

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

The chitosan derivative is a reaction product obtained by carboxylation, glucocation, tosylation, sulfation, phosphorylation, etherification or alkylation of hydroxyl group and / or amino group of chitosan. Specific examples thereof include chitosan, carboxymethyl chitosan, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, glyceryl chitosan and salts thereof with an acid. Also, a reaction product obtained by using a compound having a tertiary or quaternary amino group or both, and introducing the quaternized or quaternized amino group into chitosan; A so-called cationic chitosan having in its molecule both a tertiary or quaternary amino group directly alkylated with an amino group possessed by chitosan and directly quaternized or quaternized; And salts thereof with acids.

As the epoxy resin, an epoxy compound having two or more glycidyl groups; An epoxy resin obtained by cationization of an epoxy compound having two or more glycidyl groups by reacting with a diamine such as ethylenediamine; And nonionic epoxy resins obtained by adding polyethylene glycol to the side chains of an epoxy compound having two or more glycidyl groups.

Specific examples of the epoxy compound include succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic 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, triglycidylisocyanurate, diglycidyl isocyanurate, Trimethylolethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like. have. These may be used alone or in combination of two or more.

As the elastomer, conventionally known elastomers may be used. Specific examples include diene rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, acrylonitrile butadiene styrene rubber, and methacrylic methyl butadiene rubber; Those which can be dispersed in water include butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, chlorosulfonated rubber, chlorinated polyethylene, acrylic rubber, epichlorohydrin rubber and fluorine rubber. These elastomers may be used singly or in combination of two or more kinds. These elastomers may be modified with functional groups such as hydroxyalkyl groups such as amino groups, hydroxyl groups and methylol groups, carboxyl groups, sulfone groups, phosphone groups, epoxy groups, isocyanate groups and carbodiimide groups. Among 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 above-mentioned various water-based resins (C) may be used alone or in combination of two or more kinds.

The content of the water-based 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 within this range, the initial adhesion and durability of adhesion between the metal surface treated film and the laminate film are improved, and the corrosion resistance of the metallic material is further improved. The preferable content of the water-based resin (C) is in the range of 10% by mass or more and 90% by mass or less, more preferably in 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 this point, the presence of the water-based resin (C) in the metal surface-treated film increases the denseness of the metal surface- It is believed that it contributes to performance because of its high chemical resistance to acids and the like. It is also believed that it also plays a role of firmly fixing the metal compound (A) in the coating film.

(etc)

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 the metal material. As the solvent, specifically, for example, water; Alkane systems such as hexane and pentane; Aromatic systems such as benzene and toluene; Alcohols such as ethanol, 1-butanol and ethyl cellosolve; Ethers such as tetrahydrofuran and dioxane; Esters such as ethyl acetate and butoxyethyl acetate; Amides such as dimethylformamide and N-methylpyrrolidone; Sulfone solvents such as dimethyl sulfoxide; And phosphoric acid amides such as hexamethylphosphoric triamide. Among them, one kind of solvent may be used, or two or more kinds of solvents may be mixed and used.

In addition, a surfactant, a defoaming agent, a leveling agent, a crosslinking agent, a plasticizer, an antiseptic agent, a colorant, and the like may be added within the range that does not impair the object of the present invention and the coating performance.

The crosslinking agent is not particularly limited as long as it forms a strong film by bonding with the resin (C), and examples thereof include melamine-based, isocyanate-based, epoxy-based, and polyvalent metal ion-based resins. When a crosslinking agent is added, a curing catalyst may be appropriately 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 is out of the range of 3 or more and 11 or less, the metal compound (A) is partially dissolved in the aqueous metal surface treatment agent, and in particular, the durability of adhesion between the metal surface treated film and the laminate film There may be a case where it is lowered. A more preferable pH is within the range of 6 or more and 10 or less.

(Preparation of treatment agent)

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

(Component analysis)

The metal compound (A) can be measured, for example, by thin film X-ray diffractometry of a sample coating obtained by applying an aqueous metal surface treatment agent to an aluminum plate (A1050P) and drying at 80 캜 and analyzing the diffraction pattern thereof . The thin film X-ray diffraction analysis was performed using a thin film X-ray diffraction apparatus (model number: Xpert-MPD) manufactured by PANalytical under the conditions of a wide angle method, a tube voltage-current: 45 kV-40 mA, and a scan rate: 0.025 degree / .

The phosphorus- or fluorine-containing compound (B) can be measured by XPS analysis of a sample coating obtained by applying an aqueous metal surface treatment agent to an aluminum plate (A1050P) and drying at 80 캜. XPS analysis was performed using an XPS analyzer (model number: ESCA-850) manufactured by Shimadzu Corporation, and the excitation X-ray: Mg-K ?, power: 8 kV-30 mA, measurement area: F1s, P2p, sputtering time: (At intervals of 5 seconds).

The water-based resin (C) can be obtained by measuring the aqueous solution of the aqueous metal surface treatment agent or, if necessary, diluted with water, by FT-IR analysis (manufactured by ThermoFisher Scientific, model number: NicoletiS10, .

(Target)

The aqueous metal surface treatment agent is treated with a metal material as a target. 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, alloy steel ), Pure nickel, nickel alloys (these are also referred to as " nickel materials "), pure zinc, and zinc alloys (these are also referred to as " zinc materials ").

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

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

[Metal surface treatment coating and method for forming the same]

The metal surface treated film according to the present invention is a film formed from the above-mentioned aqueous metal surface treating agent. The forming method includes a step of applying an aqueous metal surface treatment agent to the surface of a metal material (coating step) and a step of forming a metal surface treated coating film by drying without water washing after the coating step (coating step). Further, the metal material may be pretreated in advance by degreasing or pickling.

(Coating step)

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

In this coating step, the use conditions 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 or higher and 90 ° C or lower, more preferably 20 ° C or higher and 60 ° C or lower. When the temperature is 60 占 폚 or lower, the use of useless energy can be suppressed, so that it is more preferable from the viewpoint of economy. In addition, the application time can be appropriately set.

(Drying step)

The drying step is a step of drying without washing with water after the application step. By this step, a metal surface treatment film can be formed. As the drying conditions, it is preferable that the maximum attained temperature is within the range of 50 占 폚 or higher and 250 占 폚 or lower. When the maximum reaching temperature is lower than 50 캜, a very long time is required for evaporation of the solvent in the aqueous metal surface treatment agent, which is not preferable for practical use. On the other hand, when the maximum attained temperature exceeds 250 DEG C, energy is used unnecessarily, which is not preferable from the economical point of view. The drying method is not specified, and a drying method using a batch type drying furnace, a continuous type 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 adopted. The air flow rate and wind speed set in the drying method are arbitrarily set.

(Metal surface treated film)

The metal surface treatment coating 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. When the coating amount is less than 5 mg / m < 2 >, the barrier property of the metal surface treated film is lowered, and the durability of adhesion between the metal surface treated film and the laminate film and the corrosion resistance of the metal material are sometimes insufficient. On the other hand, when the amount of the coating exceeds 5000 mg / m < 2 >, cracks often enter the surface of the metal surface treated film, have. A 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 a particularly preferable coating amount is in the range of 100 mg / m 2 or more and 2500 mg / m 2 or less.

The metal surface treated film thus obtained contains a metal compound (A). Among them, it is preferable that an oxide is contained. The presence or absence of the metal compound (A) can be confirmed by a thin film X-ray diffraction method for the metal material on which the obtained metal surface treatment film is formed. Specifically, a metal surface-treated film was taken as a measurement sample, and the measurement sample was subjected to thin film X-ray diffraction analysis (Xpert-MPD manufactured by PANalytica1, wide angle method, tube voltage: 45 kV- / Sec), the presence or absence of the metal compound (A) can be confirmed from the obtained diffraction pattern.

The average particle diameter of the metal compound (A) contained in the metal surface treated 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 crystallinity is low due to the small crystal size, and there is a possibility that the crystal is present in the amorphous state depending on the case. As a result, the acid resistance is lowered, and the durability of adhesion between the metal surface treated film and the laminated film under an environment in contact with the acidic liquid may be lowered. On the other hand, when the average particle diameter exceeds 500 nm, the volume ratio of the portion where the metal compound (A) having no acid resistance increases in the metal surface treated film after the film formation increases, The durability of the treated film and the laminated film may be deteriorated. The preferred average particle diameter is 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 treated film.

The metal surface-treated film thus obtained is formed between the metal material and the laminate film to improve the adhesiveness of the laminate film and improve the corrosion resistance of the metal material.

[Metal material having a metal surface treated coating film]

As shown in Fig. 1, the metal material 10 on which the metal surface treatment film according to the present invention is formed has the metal material 1 and the metal surface treatment film 2 formed on the surface thereof. In this metal material 10, usually, a laminate film 3 formed on the metal surface treated film 2 is further provided. The laminate film 3 is optional, and the laminate film 3 may be omitted for a period of time before the laminate film 3 is laminated. Such a metal material 10 is excellent in adhesion with the laminate film 3 and excellent in corrosion resistance.

The laminate film 3 is arbitrarily selected depending on the application in consideration of adhesiveness, gas barrier property, conductivity or decorative property, corrosion resistance of the metal material 10, and the like, and is not particularly limited. As the material of the laminate film 3, for example, a polyester resin, a polyethylene resin, a polypropylene resin, a polycarbonate resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, a polyamide resin, a polyvinyl acetate resin, , Polyimide resin, and the like. The laminate film is laminated on the metal surface treated film 2 by using a film made of these resin materials.

Example

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

[Metal substrate]

· "Al" ... A1100P (pure aluminum, JIS H 4000: 1999), 0.3 mm thickness

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

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

· "Ni" ... A pure nickel plate (purity of 99% by mass or more), a thickness of 0.3 mm

· "SUS" ... SUS304 plate (austenitic stainless steel), 0.3 mm thickness

· "EG" ... An electro-galvanized steel sheet (thickness: 0.8 mm, zinc-plated thickness: 20 탆)

[One. Preparation of aqueous metal surface treatment agent]

(A), the phosphorus or fluorine-containing compound (B), the water-based resin (C) and, if necessary, the additive (D), and further adding ammonia or acetic acid the pH of the aqueous metal surface treating agents of Examples 1 to 41 shown in Tables 1 and 2 and the aqueous metal surface treating agents of Comparative Examples 1 to 15 shown in Table 3 were prepared. The " solid content ratio " in the table indicates the ratio (mass%) of each of the above-mentioned compounds occupying the entire solid content of the aqueous metal surface treatment agent.

≪ Metal compound sol (A) >

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

A1; Zirconium oxide (IV) sol (solid content 20 mass%, average particle size 30 nm)

A2; Hafnium oxide (IV) sol (solid content 15 mass%, average particle diameter 50 nm)

A3; A 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 mass%)

A6; Copper (II) oxide sol (solid content 20 mass%, average particle diameter 20 nm)

A7; A zirconium oxide (IV) sol (solid content 15 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% as P ₂ O ₇ )

B4; Ammonium fluoride [NH ₄ F]

B5; Sodium acid fluoride [NaFHF]

B6; Fic 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)

(40 mol%), terephthalic acid (41 mol%), sodium dimethyl isosulphate (2 mol%), and an alcohol component composed of ethylene glycol (90 mol%) and trimethylol propane (NVC.) (30%) by the condensation reaction of an acid component composed of trimellitic anhydride (17 mol%) and anhydrous trimellitic acid (17 mol%) was synthesized by the following method. A total of 1 mol of an acid component, 2 mol of a total alcohol component, and a catalyst (0.25 g of calcium acetate and 0.1 g of N-butyl titanate) were placed in a 1000 ml round bottom flask equipped with a nitrogen inlet tube, Was purged with nitrogen, and the contents were melted by heating at 180 占 폚. Then, the temperature of the bath was raised to 200 캜 and the mixture was heated and stirred for about 2 hours to carry out an esterification reaction or an ester exchange reaction. Next, the bath temperature was raised to 260 占 폚, and after about 15 minutes, the inside of the system was reduced to 0.5 mmHg and reacted for about 3 hours (polycondensation reaction). After completion of the reaction, the mixture was allowed to cool under nitrogen introduction, and the contents were taken out. An appropriate amount of ammonia water (amount of water to give a solid content of 25%) was added to the extruded contents at a final pH of 6 to 7, and the mixture was heated and stirred in an autoclave at 100 占 폚 for 2 hours to obtain a polyester resin of an aqueous emulsion.

(C2 (urethane resin)

100 parts by mass of a polyester polyol (adipic acid / 3-methyl-1,5-pentanediol, number average molecular weight 1000, number of functional groups 2.0, and hydroxyl group 112.2), 3 parts by mass of trimethylolpropane, 25 parts by mass of dimethylolpropionic acid, 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 the mixture and the mixture was poured into water. The urethane prepolymer was dispersed in water and elongated with ethylenediamine to obtain a dispersion. Methyl ethyl ketone was distilled off to obtain an aqueous dispersion of a urethane resin containing 30 mass% of nonvolatile matter. The acid value of the carboxyl group-containing polyurethane dispersed in the obtained aqueous dispersion was 49 (KOH mg / g).

(C3; polyolefin resin)

100 parts by mass of a propylene-ethylene-? -Olefin copolymer (68 mol% of propylene component, 8 mol% of ethylene component, 24 mol% of butene component and 60,000 of mass average molecular weight), 10 parts by mass of maleic anhydride, 10 parts by mass of methyl acrylate, and 1 part by mass of dicumyl peroxide, and the mixture was stirred at 180 ° C for 2 hours and reacted. To obtain a modified polyolefin resin composition having a mass average molecular weight of 45,000 and a graft mass of maleic anhydride of 8.4% by mass. Subsequently, 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 added to a four-necked flask, and the mixture was homogeneously stirred and melted at 100 DEG C for 2 hours with a stirring blade And 300 parts by mass of ion-exchanged water at 90 DEG C were added and further stirred for 1 hour to obtain an aqueous polyolefin resin having a pH of 8.0.

(C4: acrylic resin 1)

(Nonvolatile content concentration: 15.0 mass%, viscosity: 3 Pa s, pH = 3.5, Tg: 130 캜, and the like) obtained by copolymerizing butyl acrylate, acrylamide and hydroxyethyl acrylate as monomers, Anion) was used.

(C5; acrylic resin 2)

A temperature control regulator, a cooling tube, and an agitator were placed in a reaction vessel made of a separable four-necked flask, and 390 parts by mass of ion-exchanged water at room temperature, 210 parts by mass of isopropyl alcohol and 30 parts by mass of N-methylol acrylamide 120 parts by mass, and 30 parts by mass of acrylamide were injected 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 dissolved and dissolved. Subsequently, the reaction vessel was purged with nitrogen, the temperature was raised to 65 캜 for 30 minutes, and the reaction was carried out at 65 캜 for 3 hours. The reaction product was cooled to room temperature, filtered and taken out. The obtained acrylic resin aqueous solution had a nonvolatile matter concentration of 20 mass%, a viscosity of 2.86 dPa.s, and a pH of 5.6.

(C6: polyvinyl alcohol)

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, The temperature was gradually raised over about 2 hours while stirring to raise it to 130 占 폚. The temperature was maintained at 130 占 폚 while paying attention to the sudden 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 matter (200 DEG C -2 h) of the polyamide-imide resin solution was about 50 mass% and the viscosity (30 DEG 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 carboxyl group and the carboxyl group which opened the ring of the acid anhydride group was about 40. 2,700 g of the polyamide-imide resin solution was placed in a flask equipped with a thermometer, a stirrer and a cooling tube, and the temperature was gradually elevated to 50 DEG C while stirring in a nitrogen stream in a dried state. When the temperature reached 50 占 폚, 447.1 g (4 equivalents) of triethylamine was added and sufficiently stirred while maintaining the temperature at 50 占 폚, followed by gradually adding ion-exchanged water while stirring. And finally added to 1348.8 g (30 mass%) of ion-exchanged water to obtain a transparent and uniform heat-resistant polyamide-imide resin.

(C8; natural polysaccharide)

Glycerylated chitosan of the following structural formula (number average molecular weight: 10,000 to 100,000, glycerylation: 11) was used.

[Chemical Formula 1]

(C9; epoxy resin)

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

(C10; elastomer 1)

(Solid content concentration: 47%, pH = 8, viscosity: 45 mPa,, Tg: 18 캜, specific gravity: 1.01) of acrylonitrile butadiene styrene rubber having a carboxyl group and a methylol group was used.

(C11; elastomer 2)

(Solid content concentration: 48.5%, pH = 7.8, viscosity: 104 mPa,, particle diameter: 170 ㎚, Tg: -5 캜) of a styrene butadiene rubber having a carboxyl group was used.

(C12; acrylic resin 3)

An aqueous acrylic resin solution (nonvolatile content concentration: 20.0 mass%, viscosity: 300 mPa,, pH = 4.0, anion) obtained by copolymerizing methyl methacrylate and N-methylol acrylamide as monomers was used .

(C13; elastomer 3)

200 parts of water, 4.5 parts of rosin soap, 66 parts of butadiene, 26 parts of styrene, 8 parts of acrylonitrile and 0.3 part of t-dodecyl mercaptan were injected into a nitrogen-purged polymerization vessel. Thereafter, the temperature of the polymerization vessel was set at 5 占 폚, and 0.1 part of p-mentholhydroperoxide as a polymerization initiator, 0.07 part of sodium ethylenediaminetetraacetate, 0.05 part of ferrous sulfate heptahydrate, and sodium formaldehyde sulfoxylate 0.15 part was added to initiate polymerization. When the polymerization conversion rate reached 60%, diethylhydroxyamine was added to terminate the polymerization. Subsequently, the unreacted monomers were recovered by steam stripping to obtain a dispersion liquid containing a diene rubber having a solid content concentration of 21%.

&Lt; Other additive (D) >

(D1: isocyanate-based curing agent 1)

Hexamethylene diisocyanate-ethyl acetoacetate block copolymer was used.

(D2; epoxy-based curing agent 1)

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

(D3; isocyanate-based curing agent 2)

Toluene diisocyanate-diethylene glycol monoethyl ether block was used.

(D4; epoxy-based curing agent 2)

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

D5; Aluminum monoacetylacetonate bis (ethylacetonate)

D6; Titanium lactate

D7; N-methylol acrylamide

D8; Dimethylolurea

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

D10; Triethylene glycol

[2. Production of Disclosure 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 immersed in a 2% aqueous solution of Fine Cleaner 359E (an alkali degreasing agent manufactured by Nippon Pakaranging Co., Ltd.) at 50 DEG C for 10 seconds After spray degreasing, the surface was cleaned by rinsing with water. Subsequently, in order to evaporate moisture on the surface of the metal substrate, it was heated and dried at 80 DEG C for 1 minute. On the surface of the degreased cleaned metal base, the aqueous metal surface treatment agents of Examples 1 to 41 and Comparative Examples 1 to 15 shown in Table 3 shown in Tables 1 and 2 were applied using a # 8 SUS Meyer bar and bar coats , And dried in a hot-air circulating drying oven at 180 DEG C for 1 minute to form a metal surface-treated film on the surface of the metal substrate. The metal substrates described in Comparative Examples 16 to 21 in Table 3 were degreased, washed with water and dried by heating as described above. Tables 1 to 3 summarize the film forming amounts of the aqueous metal surface treatment agent used in each of the Examples and Comparative Examples and the obtained metal surface treatment film.

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

The metal material on which the metal surface treated film obtained in Example 3, Example 6, and Example 13 was formed was subjected to cross-sectional observation with a transmission electron microscope (TEM) to measure the average particle diameter of the metal compound (A). The average particle diameters of the metal compound (A) were about 100 nm, 30 nm and 20 nm, respectively.

[4. Laminate Performance Evaluation]

Thereafter, a laminate film was laminated on the metal surface-treated film of the metal base by the following lamination method.

(Laminate 1)

A metal surface treatment film laminated with a polyester film was produced by thermocompression bonding a polyester film (thickness: 16 占 퐉) coronated on one side with a metal surface treatment film of a metal base at 250 占 폚 and a surface pressure of 5 MPa for 10 seconds To form a formed metal material.

(Laminate 2)

An adhesive layer having a thickness of 5 占 퐉 was formed by roll coating a dispersion of acid-denatured polypropylene on the surface of the metal substrate having the metal surface treatment film formed thereon and then drying it at 200 占 폚 for 1 minute in a hot air circulating drying furnace. Thereafter, the adhesive layer and a polypropylene film having a thickness of 30 占 퐉 were thermocompression-bonded at 250 占 폚 and 0.1 MPa for 10 seconds to produce a metal material having a metal surface-treated film laminated with a polypropylene film.

<4.1. Initial adhesion>

The metal material on which the laminate film was formed by the laminate 1 and the laminate 2 was extruded 5 mm by an Ericksen tester and subjected to a crosscut tape peeling test (1 mm pitch) to measure the initial state of the laminate film The adhesiveness was evaluated by Rank 1 to 3 below.

3: There is no peeling of the laminated film at all.

2: Part of the laminated film was peeled off.

1: The laminate film was entirely peeled off.

4.2. Endurance adhesion>

A pressure cooker test was conducted on the metal material on which the metal surface treatment film having the laminate film formed by the laminate 1 was formed. Conditions were 125 캜, 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 subjected to 180 degree peel strength measurement. The adhesion between the laminate film and the metal material was evaluated by the following ranks 1 to 9.

9: Peel strength is over 10 N.

8: Peel strength is in the range of 9 N to less than 10 N.

7: Peel strength is in the range of 8 N or more and 9 N or less.

6: Peel strength is in the range of 7 N to less than 8 N.

5: Peel strength is in the range of 6N to less than 7N.

4: Peel strength is in the range of 5 N to less than 6 N.

3: Peel strength is in the range of 3N to less than 5N.

2: Peel strength is in the range of 1 N or more and 3 N or less.

1: the laminate film is already peeled off, or less than 1 N

4.3. Corrosion resistance>

The metal material on which the laminated film was formed by the laminate 2 was subjected to CASS test for 24 hours in accordance with JIS H8502. The appearance of the metal material was visually observed and evaluated by the following ranks 1 to 9.

9: No change in appearance at all.

8: The area ratio of the occurrence of lamination film peeling (peeling) and under the laminate film is more than 0% and not more than 5%.

7: Occurrence of peeling (lift) of laminate film and corrosion under laminate film is more than 5% and not more than 10%.

6: Percentage of occurrence of peeling (lift-off) of laminate film and corrosion under laminate film is more than 10% and not more than 15%.

5: The area rate of occurrence of lamination film peeling (peeling) and under the laminate film is more than 15% and not more than 20%.

4: The area rate of occurrence of lamination film peeling (under extrusion) and under the laminated film is more than 20% and not more than 25.

3: Percentage of occurrence of lamination film peeling (lamination) and corrosion under laminate film is more than 25% and not more than 40%.

2: The area ratio of the occurrence of peeling (lamination) of the laminated film and the corrosion under the laminated film is more than 40% and not more than 60%

1: The area ratio of the occurrence of peeling (peeling) of the laminate film and the corrosion under the laminate film exceeded 60%.

4.4. Physical Properties 1>

The metal material having the metal surface-treated film formed by laminating the polyester film with the laminate 1 was immersed in a model juice (citric acid monohydrate: sodium chloride: deionized water = 5: 5: 990 (mass ratio)), After elapsed, it was taken out, cut into a width of 15 mm, and 180 degree peel strength measurement was carried out. The adhesion between the laminate film and the metal material was evaluated by the following ranks 1 to 9.

9: Peel strength is over 10 N.

8: Peel strength is in the range of 9 N to less than 10 N.

7: Peel strength is in the range of 8 N or more and 9 N or less.

6: Peel strength is in the range of 7 N to less than 8 N.

5: Peel strength is in the range of 6N to less than 7N.

4: Peel strength is in the range of 5 N to less than 6 N.

3: Peel strength is in the range of 3N to less than 5N.

2: Peel strength is in the range of 1 N or more and 3 N or less.

1: The laminate film is already peeled off or less than 1 N;

<4.5. Content Property 2>

(LBG-00015, electrolyte: 1M-LiPF ₆ , solvent: EC / DMC / DEC = 1, manufactured by Kishida Chemical Co., Ltd.) was applied to the metal material having the metal surface treatment film laminated with the polypropylene film by the laminate 2 / 1/1 (volume%)), and then the mixture was placed in a thermostatic chamber at 60 占 폚 for 7 days. Thereafter, the specimen was taken out, washed by swinging while immersed in ion-exchanged water for 1 minute, and then dried in a hot-air circulating drying oven at 100 ° C for 10 minutes. Thereafter, the film was cut into a width of 15 mm and subjected to a 180 ° peel strength measurement. The adhesion between the laminate film and the metal material was evaluated by the following ranks 1 to 9.

9: Peel strength is over 10 N.

8: Peel strength is in the range of 9 N to less than 10 N.

7: Peel strength is in the range of 8 N or more and 9 N or less.

6: Peel strength is in the range of 7 N to less than 8 N.

5: Peel strength is in the range of 6N to less than 7N.

4: Peel strength is in the range of 5 N to less than 6 N.

3: Peel strength is in the range of 3N to less than 5N.

2: Peel strength is in the range of 1 N or more and 3 N or less.

1: The laminate film is already peeled off or less than 1 N;

[result]

The results are shown in Tables 4-6.

As shown in Tables 4 and 5, it was confirmed that the metal material on which the metal surface treated film obtained in Examples 1 to 41 was formed had excellent initial adhesion, durability and corrosion resistance after the laminate film was formed. As shown in Table 6, the metallic materials on which the metal surface treatment coatings obtained in Comparative Examples 1 to 15 were formed had inferior initial adhesion, durability, corrosion resistance and the like as compared with the Examples.

Industrial availability

The aqueous metal surface treatment agent according to the present invention, the metal surface treatment film formed by the aqueous metal surface treatment agent, and the metal material having the metal surface treatment film are used in a wide range of fields such as home appliances, foods, Copper, iron, zinc, nickel, or an alloy thereof. In addition, it can be suitably applied as a contents filling container for containing an organic acid such as acetic acid or citric acid or an inorganic acid such as sulfuric acid or hydrofluoric acid, specifically, a food container, a detergent container or a container for a lithium ion secondary battery.

1: metal material
2: Metal surface treatment coating
3: Laminated film
10: Metal material with metal surface treatment coating

Claims (8)

(A), which is an oxide of titanium, having an average particle diameter in the range of 20 nm to 500 nm, one or more phosphorus or fluorine-containing compounds (B) selected from the group of phosphorus compounds and fluoride compounds, (C) selected from the group consisting of an ester resin, a urethane 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 Wherein the metal surface treatment agent is a water-based metal surface treatment agent. The method according to claim 1,
Wherein the content of the metal compound (A) is in the range of 5 mass% to 90 mass% with respect to the total solid content. 3. The method according to claim 1 or 2,
Wherein the content of the water-based resin (C) is in the range of 5 mass% to 90 mass% with respect to the total solid content. 4. The method according to any one of claims 1 to 3,
Aqueous metal surface treatment agent having a pH within the range of 3 to 11. 5. The method according to any one of claims 1 to 4,
Water based metal surface treatment agent used for laminating. (A), which is an oxide of titanium, having an average particle diameter in the range of 20 nm to 500 nm, one or more phosphorus or fluorine-containing compounds (B) selected from the group of phosphorus compounds and fluoride compounds, (C) selected from the group consisting of an ester resin, a urethane 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 Wherein the metal surface treatment agent is a coating formed of an aqueous metal surface treatment agent. A metal material having a metal surface treatment film, characterized by having a metal material and the metal surface treatment film according to claim 6 formed on the surface of the metal material. 8. The method of claim 7,
Wherein the metal surface treatment film further has a laminate film formed on the metal surface treatment film.

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