JP2015134957A - Aqueous metal surface treatment agent, metal surface treatment film and metal material having metal surface treatment film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous metal surface treatment agent for surface treatment film formation and a metal surface treatment film, provided between a metal material and a laminate film and capable of improving adhesion therebetween and the corrosion resistance of the metal material.SOLUTION: The aqueous metal surface treatment agent includes at least: one kind or two kinds or more of metal compounds (A) selected from oxides of zirconium, titanium or hafnium having an average particle size within a range of 1 nm or more and 500 nm or less; one kind or two kinds or more of phosphorus or fluorine containing compounds (B) selected from a phosphorus compound group and a fluorine compound group; and one kind or two kinds or more of aqueous resins (C) selected from a polyester resin, a urethane resin, a polyolefin resin, an acrylic resin, a polyvinyl based resin, a polyamide resin, a polyimide resin, a natural polysaccharide, an epoxy resin and an elastomer.

Description

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

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

  In particular, film laminating is a processing means for heat-pressing a resin film (hereinafter referred to as a laminate film) to the surface of a metal material, and is a metal intended to protect the surface or impart design properties. It is used in various fields as a method for coating the material surface. This film laminating process is a method of forming a resin coating film in which a resin composition dissolved or dispersed in a solvent is applied and dried on the surface of a metal material. There is little generation of greenhouse gas. Therefore, the film laminating process is preferably applied from the viewpoint of environmental conservation, and its use is expanded, for example, aluminum thin plate material, steel thin plate material, copper thin plate material, nickel-plated copper thin plate material, packaging aluminum foil or stainless steel foil, etc. It is used as a method for coating a laminate film on a building material made of the above, a body or lid of a food can, a food container, a dry battery container, or the like.

  In the base treatment of a metal material, a chromate base treatment using a surface treatment agent containing hexavalent chromium has been frequently used because it is inexpensive. In recent years, the use of harmful metals (compounds, ions) such as hexavalent chromium, lead, and cadmium in Europe, domestic PRTR (environmental pollutant emission and transfer registration system), or the release of the list of environmental hormone substances to the human body, etc. Trends aimed not only at impact but also at global environmental conservation are becoming even larger on a global scale. Under such circumstances, there has been a great increase in awareness of the danger of adverse effects on the human body and the environment, and an alternative technology for a hexavalent chromium-containing surface treatment agent that is generally used as a surface treatment agent for metal materials, namely hexavalent. Surface treatment agents that do not use any chromium have been proposed.

  Recently, it has been desired to develop a chromium-free treatment agent that does not contain trivalent chromium. For example, as a base treatment agent for a chromium-free laminate, in Patent Document 1, a specific amount of a water-soluble zirconium compound, a water-soluble or water-dispersible acrylic resin having a specific structure, a water-soluble or water-dispersible thermosetting crosslinking agent, There has been proposed a surface treating agent containing Patent Document 2 proposes a metal surface treatment agent comprising a water-soluble zirconium compound and / or a water-soluble titanium compound, an organic phosphonic acid compound, and tannin. Patent Document 3 proposes a base treatment agent that contains a basic zirconium compound and / or cerium compound, a carboxyl group-containing resin, and an oxazoline group-containing acrylic resin and does not contain fluorine.

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

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

  However, for the ground treatment described in Patent Documents 1 to 3 above, it is desired to further improve the durability adhesion between the metal material and the laminate film, and the metal material under severe conditions Further improvement in corrosion resistance is also desired.

  The present invention has been made in order to meet such a demand, and the object thereof is provided between a metal material and a laminate film, and can improve the adhesion of the laminate film. An aqueous metal surface treatment agent, a metal surface treatment film formed with the aqueous metal surface treatment agent, and a metal material with the metal surface treatment film for forming a surface treatment film capable of improving the corrosion resistance of the metal There is.

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

  In the aqueous metal surface treatment agent according to the present invention, the content of the metal compound (A) is preferably in the range of 5% by mass to 90% by mass with respect to the total solid content.

  In the aqueous metal surface treatment agent according to the present invention, the content of the aqueous resin (C) is preferably in the range of 5% by mass to 90% by mass with respect to the total solid content.

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

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

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

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

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

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

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

  The metal material with a metal surface treatment film according to the present invention is excellent in adhesion between the metal material and the laminate film through the metal surface treatment film, and is excellent in the corrosion resistance of the metal material.

It is typical sectional drawing which shows an example of the metal material with a metal surface treatment film | membrane which concerns on this invention.

  Hereinafter, the water-based metal surface treatment agent, metal surface treatment film, and metal material with metal surface treatment film according to the present invention will be described in detail. In addition, this invention can be arbitrarily changed in the range including the summary, and is not limited only to the following embodiment.

[Water-based metal surface treatment agent]
The aqueous metal surface treatment agent according to the present invention 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 nm to 500 nm, phosphorus, One or two or more phosphorus or fluorine-containing compounds (B) selected from a compound group and a fluorine compound group, and a polyester resin, urethane resin, polyolefin resin, acrylic resin, polyvinyl resin, polyamide resin, polyimide resin, natural poly 1 type, or 2 or more types of aqueous resin (C) chosen from saccharides, an epoxy resin, and an elastomer are contained at least.

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

(Metal compound)
Examples of the metal compound (A) include zirconium, titanium, and hafnium oxides having an average particle diameter in the range of 1 nm to 500 nm. Specifically, an oxide of zirconium, an oxide of titanium, an oxide of hafnium, and the like can be given. Specific examples thereof include zirconium (IV) oxide (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. Among these, zirconium oxide is particularly preferable.

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

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

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

  Specifically, in the second method, an alkali agent is added to an acidic aqueous solution of a water-soluble salt of zirconium, titanium, or hafnium, and a dispersant is added as necessary, so that an oxide of zirconium, titanium, or hafnium is added. In this method, it is generated in water, and then, excess impurity ions are 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 a water-soluble salt of zirconium, titanium, or hafnium, a conventionally known salt can be used. Specifically, zirconium chloride, zirconium oxychloride, titanium chloride, hafnium chloride, zirconium nitrate, titanium nitrate, hafnium nitrate, zirconium sulfate, titanium sulfate, hafnium sulfate, fluorozirconic acid, fluorotitanic acid, fluorohafnium acid, zirconium acetate , Titanium acetate, hafnium acetate, zirconium lactate, titanium lactate, hafnium lactate and the like. These salts may be hydrates.

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

  A conventionally well-known dispersing agent can be used as an above described dispersing agent. Of these, hydroxycarboxylic acids are preferable, and specific examples include citric acid, malic acid, tartaric acid, lactic acid, hydroxyvaleric acid, glyceric acid, tropic acid, and benzylic acid. In particular, hydroxycarboxylic acids having a divalent or higher valent carboxyl group such as citric acid, malic acid and tartaric acid can be preferably used because they can be dispersed with a small content.

  Examples of the separation described above include a separation method using an ion exchange resin, a separation method using membrane filtration, and the like, but a separation method using an ultrafiltration membrane is more 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 with respect to the total solid content. Although the upper limit of content of a metal compound (A) is not specifically limited, It is about 90 mass% with respect to the total solid. When the content of the metal compound (A) is within this range, the initial adhesion between the metal material and the laminate film via the metal surface treatment film is good, and particularly high adhesion even in an environment in contact with an acidic liquid. (Durable adhesion) can be obtained, and the corrosion resistance of the metal material can be improved.

  Although the mechanism of action of the metal compound (A) is still unclear at present, it does not contain the metal compound (A), but instead is made of an aqueous metal surface treatment agent containing a water-soluble salt of zirconium, titanium, or hafnium. It has been found by the inventor's examination that the metal surface treatment film thus obtained does not exhibit performance. The metal compound (A), which is an oxide of zirconium, titanium, or hafnium, has higher acid resistance compared to a water-soluble salt and is difficult to dissolve even when contacted with an acidic liquid. It is thought that the metal surface treatment film produced with the water-based metal surface treatment agent containing A) provides 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 to 500 nm. . When the average particle diameter is less than 1 nm, the acid resistance is low, and the durability adhesion between the metal surface treatment film and the laminate film in an environment in contact with the acidic liquid is 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 acid resistance does not exist in the metal surface-treated film after film formation increases. In some cases, the durability adhesion at the time may be reduced. 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 using 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., a laser diffraction / scattering particle size distribution analyzer (LA-920) manufactured by Horiba, Ltd., and the like. it can. In addition, the average particle diameter of the metal compound (A) in the metal surface treatment film provided in the metal material with the metal surface treatment film, which will be described later, is determined by measuring the surface or cross section of the metal surface treatment film with a transmission electron microscope (TEM). It can be measured by direct observation.

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

  Examples of the phosphorus compound group include a group consisting of a plurality of phosphorus-containing compounds such as phosphoric acids, phosphate esters, and organic phosphonic acids. Specific examples of phosphoric acids include condensed phosphoric acid including phosphoric acid (orthophosphoric acid), metaphosphoric acid, and polyphosphoric acid, and salts thereof (ammonium salt, sodium salt, calcium salt, magnesium salt, lithium salt, etc.). Can be mentioned. Metaphosphoric acid includes trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid and the like. Polyphosphoric acid is a chain phosphoric acid condensate and includes pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid and the like. Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, phytic acid and salts thereof (ammonium salt, sodium salt) , Calcium salts, magnesium salts, lithium salts, etc.), riboflavin phosphates and the like. Specific examples of the organic phosphonic acid include aminotrimethylenephosphonic acid, 1-hydroxyethylidene 1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and the like. A phosphorus containing compound may be used independently and may be used in combination of 2 or more type.

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

  Since phytic acid and organic phosphonic acid have two or more phosphonic groups in one molecule as compared with phosphate, it is considered that the crosslink density increases and the durability adhesion becomes higher. On the other hand, the condensed phosphate has a larger amount of phosphone groups per molecule than the phosphate, but it is relatively easily hydrolyzed and eventually becomes a phosphate. Therefore, in the range where the condensed phosphate is compared with phytic acid or organic phosphonic acid, it is considered that the condensed phosphate is not as durable as phytic acid or organic phosphonic acid.

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

  Especially, it is preferable to use 1 type, or 2 or more types chosen from the sodium salt of potassium hydrofluoric acid, potassium salt, ammonium salt, and lithium salt.

  The content of these phosphorus or fluorine-containing compounds (B) is phosphorus or fluorine-containing compounds (B) with respect to the total molar amount of metal atoms (zirconium atoms, titanium atoms, hafnium atoms) constituting the metal compound (A). It is preferable to adjust so that the ratio (B / A) of the sum of the molar amounts of phosphorus atoms and fluorine atoms constituting the carbon atom is in the range of 0.005 to 5.0. In addition, content of phosphorus or a fluorine-containing compound (B) can be adjusted so that an above-described ratio may exist in the range of 0.01 or more and 2.0 or less at the point of initial stage adhesiveness and durable adhesiveness. More preferably, it is particularly preferable to adjust to be within a range of 0.02 or more and 0.5 or less.

  The mechanism of action of the phosphorus or fluorine-containing compound (B) is still unclear at this time, but the phosphorus-containing compound and / or fluorine-containing compound is dissolved in the water-based metal surface treatment agent. When the surface treatment agent comes into contact with the metal material, the surface of the metal material is slightly etched with the phosphorus-containing compound or fluorine-containing compound to form fine irregularities, and the initial adhesion and durable adhesion due to the anchor effect by the fine irregularities It is thought that the property improved. In addition, the presence of a phosphorus-containing compound or a fluorine-containing compound in the metal surface treatment film reduces the permeability of the anion that is a corrosion factor, and as a result, the corrosion resistance of the metal material is considered to be improved. The phosphorus-containing compound and the fluorine-containing compound are chemically adsorbed on the particle surface of the metal compound (A) in the film and also act as a crosslinking agent. In particular, it is considered that a phosphorus-containing compound is difficult to be cross-linked when exposed to a chemical such as an acid, and has a higher durability adhesion than a fluorine-containing compound.

  The anchor effect by the fine unevenness is particularly effective when the average particle diameter of the metal compound (A) described above is in the range of 5 nm to 100 nm. When the average particle diameter of the metal compound (A) becomes too fine, the particles are likely to enter fine irregularities, and there is less room for the resin to come into contact with the base material, thereby suppressing the effect of improving the initial adhesion and durability adhesion. There is.

(Water-based resin)
As the aqueous resin (C), a conventionally known aqueous resin can be applied. Specifically, mention is made of one or more water-based resins selected from polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, natural polysaccharides, epoxy resins, and elastomers. Can do.

  The water-based resin (C) may be either water-soluble or water-dispersible (emulsion, dispersion). Further, the polarity of the aqueous resin (C) in the aqueous metal surface treatment agent may be any of cationic, nonionic, and anionic properties 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, azelaic acid, sebacic acid, dimer acid, trimer acid, isophthalic acid, terephthalic acid, trimellitic acid, Polybasic acids such as trimesic acid, pyromellitic acid and naphthalenedicarboxylic acid were condensed with polyols such as ethylene glycol, diethylene glycol, trimethylolpropane, neopentyl glycol, 1,4-CHDM and 1,6-hexanediol. Polyester polyol; condensation resin obtained by condensing the above-described polybasic acid and a polyol such as polymer polyol, polycaprolactone polyol, polycarbonate diol, polybutadiene polyol, neopentyl glycol, methylpentadiol; etc. It can be mentioned.

  Also, a water-based resin in which a monomer having three or more carboxyl groups such as trimellitic acid or pyromellitic acid is used as a part of the monomer, and the unreacted carboxylic acid is neutralized with an alkali to be solubilized or dispersed in water. Alternatively, an aqueous resin that is solubilized or dispersed in water using a sulfonated monomer such as sulfophthalic acid as a part of the monomer can also be used.

  The urethane resin is a urethane resin that is a polycondensation product of a polyol 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, Examples of the polyol include a polyurethane obtained by using a polyol having a polyoxyethylene chain such as polyethylene glycol or polypropylene glycol.

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

  The carboxylic acid and reactive derivative used when producing the water-dispersible urethane resin having an anionic property described above are used for introducing acidic groups into the urethane resin and for making the urethane resin water-dispersible. Examples of carboxylic acids include dimethylol alkanoic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolhexanoic acid. Examples of the reactive derivative include hydrolyzable esters such as acid anhydrides.

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

  Examples of the acrylic resin include homopolymers or copolymers of acrylic monomers, and copolymers with addition polymerizable monomers that can be copolymerized with these acrylic monomers. The polymerization form is not particularly limited as long as such an acrylic resin can be stably present in the 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- Examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, sulfoethyl acrylate, and polyethylene glycol methacrylate. Examples of the addition polymerizable monomer that can be copolymerized with the acrylic monomer include maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, diacetone acrylamide, styrene, acrylonitrile, vinyl sulfonic acid, and the like.

  Polymerization of the monomer is carried out in a solvent in the presence of an initiator and in an inert gas stream within a range of 30 ° C. to 80 ° C., preferably within a range of 40 ° C. to 75 ° C., more preferably 50 ° C. It can be performed within the range of 75 ° C. or lower. When the polymerization temperature is low, the polymerization may not proceed, and when the polymerization temperature is high, a gel may be generated.

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

  Among these, isopropyl alcohol having an action as a chain transfer agent can be preferably used. Isopropyl alcohol is in the range of 20 to 90 parts by weight, preferably in the range of 25 to 65 parts by weight, more preferably in the range of 30 to 60 parts by weight with respect to 100 parts by weight of water. Is within. If 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 a gel-like product may be formed.

  As the initiator, a water-soluble radical initiator is preferable. Examples of the polymerization initiator in the copolymerization step include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, and azoamidines such as hydrogen peroxide and 2,2′-azobis-2-methylpropionamidine hydrochloride. Compounds, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, azo initiators such as azonitrile compounds such as 2-carbamoylazoisobutyronitrile, etc. be able to. At this time, alkali metal sulfites such as sodium hydrogen sulfite, meta disulfites, sodium hypophosphite, Fe (II) salts such as molle salts, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride, thiourea , L-ascorbic acid (salt), erythorbic acid (salt) and other accelerators may be used in combination. From the viewpoint of hygiene, the water-soluble radical initiator is more preferably ammonium persulfate, sodium persulfate, or potassium persulfate. The radical initiator may be mixed and dissolved from the beginning 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, a partially saponified product or a completely saponified product of polyvinyl acetate, and polyvinylpyrrolidone.

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

  Examples of monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof, ethylene, propylene, and the like. α-olefin; olefin sulfonic acid such as (meth) acryl sulfonic acid, ethylene sulfonic acid, sulfonic acid malate; (meth) allyl sulfonic acid soda, ethylene sulfonic acid soda, sulfonic acid soda (meth) acrylate, sulfonic acid soda (mono Olefin sulfonic acid alkali salts such as alkyl malate) and sodium disulfonate alkyl malate; amide group-containing monomers such as N-methylol acrylamide and alkali acrylamide alkyl sulfonic acid salts; N-vinyl pyrrolidone and N-vinyl pyrrolidone derivatives; Etc.

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

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

  The above-mentioned chitosan derivative is a reaction product obtained by carboxylation, glycolation, tosylation, sulfation, phosphorylation, etherification or alkylation of the hydroxyl group and / or amino group of chitosan. Specific examples include chitosan, carboxymethyl chitosan, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, glycerylated chitosan and salts thereof with acids. In addition, a reaction product obtained by introducing a tertiary or quaternized amino group into chitosan using a compound having a tertiary or quaternary amino group or both; alkylating the amino group of chitosan directly with an alkylating agent A so-called cationized chitosan having a tertiary or quaternary amino group directly or quaternized, or both in the molecule; and salts thereof with acids.

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

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

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

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

  The content of the aqueous resin (C) is preferably in the range of 5% by mass to 95% by mass with respect to 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 adhesion between the metal surface treatment film and the laminate film are improved, and the corrosion resistance of the metal material is further improved. The preferable content of the water-based resin (C) is in the range of 10% by mass to 90% by mass, and the more preferable content is in the range of 30% by mass to 90% by mass.

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

(Other)
The aqueous metal surface treatment agent according to the present invention can contain various solvents as required from the viewpoint of workability when applied to 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; ethers such as tetrahydrofuran and dioxane. An ester system such as ethyl acetate and butoxyethyl acetate; an amide system such as dimethylformamide and N-methylpyrrolidone; a sulfone solvent such as dimethyl sulfoxide; and a phosphoric acid amide such as hexamethylphosphoric triamide; Among these, one kind of solvent may be used, or two or more kinds of solvents may be mixed and used.

  In addition to this, a surfactant, an antifoaming agent, a leveling agent, a crosslinking agent, a plasticizer, an antibacterial and antifungal agent, a coloring agent, and the like can be added within a range not impairing the gist and film performance of the present invention.

  The crosslinking agent is not particularly limited as long as it binds to the resin (C) and forms a strong film, and examples thereof include melamine-based, isocyanate-based, epoxy-based, and polyvalent metal ion-based materials. be able to. When a crosslinking agent is added, a curing catalyst may be further added as appropriate 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 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, and particularly in an environment where it comes into contact with an acidic liquid, The durability adhesion with the laminate film may be lowered. A more preferable pH is in the range of 6 or more and 10 or less.

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

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

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

  The water-based resin (C) is a stock solution of a water-based metal surface treatment agent, or a solution diluted with water as necessary. FT-IR analysis (ThermoFisher Scientific, model number: Nicoleti S10, specular reflection method) and other analyzes It can be measured and identified by the method.

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

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

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

[Metal surface treatment film and method for forming the same]
The metal surface treatment film according to the present invention is a film formed with the above-described aqueous metal surface treatment agent. The formation method includes a step of applying a water-based metal surface treatment agent to the surface of the metal material (application step), and a step of forming a metal surface treatment film by drying without washing after the application step (film formation step). And have. In addition, you may have the pre-processing process of degreasing or pickling a metal material previously.

(Coating process)
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 this coating process is not particularly limited, and for example, it can be applied by a method such as 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, the temperature of the treatment agent and the metal material when applying the aqueous metal surface treatment agent is preferably in the range of 10 ° C. or more and 90 ° C. or less, and in the range of 20 ° C. or more and 60 ° C. or less. Is more preferable. When the temperature is 60 ° C. or lower, use of useless energy can be suppressed, which is more preferable from an economical viewpoint. The application time can be set as appropriate.

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

(Metal surface treatment film)
The metal surface treatment film can be obtained by the above-described forming method. The amount 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 coating amount is less than 5 mg / m ² , the barrier property of the metal surface treatment film is lowered, and the durability adhesion between the metal surface treatment film and the laminate film and the corrosion resistance of the metal material may be insufficient. On the other hand, if the coating amount exceeds 5000 mg / m ² , many cracks may occur in the metal surface treatment film, and the initial adhesion and durability adhesion between the metal surface treatment film and the laminate film, and the metal material May have insufficient corrosion resistance. 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 particularly preferable coating amount is in the range of 100 mg / m ² or more and 2500 mg / m ² or less. .

  The obtained metal surface treatment film contains the metal compound (A). Among these, 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 obtained metal material with a metal surface treatment film. Specifically, a metal surface treatment film was collected as a measurement sample, and the measurement sample was subjected to thin film X-ray diffraction analysis (Xpert-MPD manufactured by PANalytical, wide angle method, tube voltage current: 45 kV-40 mA, scan rate: 0. 025 ° / sec), the presence or absence of the metal compound (A) can be confirmed from the obtained diffraction pattern.

  The average particle size of the metal compound (A) contained in the metal surface treatment film is preferably in the range of 1 nm to 500 nm. When the average particle size is less than 1 nm, the crystal size is small, so that the crystallinity is low, and in some cases, it may exist in an amorphous state. And as a result, acid resistance becomes low and the durable adhesiveness between the metal surface treatment film | membrane and laminate film in the environment which contacts acidic liquid may fall. On the other hand, when the average particle diameter exceeds 500 nm, the volume ratio of the portion where the metal compound (A) having acid resistance does not exist in the metal surface-treated film after film formation increases. The endurance adhesion between the metal surface treatment film and the laminate film may decrease. A preferable average particle diameter is in the range of 1 nm or more and 100 nm or less. The average particle 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 can improve the adhesion of the laminate film and also improve the corrosion resistance of the metal material.

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

  The laminate film 3 is arbitrarily selected depending on the application in consideration of adhesiveness, gas barrier properties, conductivity or design properties, corrosion resistance of the metal material 10, and is not particularly limited. Examples of the material of the laminate film 3 include polyester resin, polyethylene resin, polypropylene resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyamide resin, polyvinyl acetate resin, epoxy resin, and polyimide resin. The laminate film is laminated on the metal surface treatment film 2 using a film made of these resin materials.

  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 base material]
・ "Al" ... A1100P (pure aluminum, JISH4000: 1999), thickness 0.3mm
"ADC": ADC12 (Al-Si-Cu-based aluminum alloy, JISH5302: 2006), thickness 2.0 mm
・ "Cu" ... C1020P (oxygen-free copper plate, JISH-3100), thickness 0.3mm
・ "Ni" ... Pure nickel plate (purity 99 mass% or more), thickness 0.3mm
・ SUS: SUS304 plate (austenitic stainless steel), thickness 0.3mm
・ "EG" ... Electro-galvanized steel sheet (thickness 0.8mm, galvanization thickness 20μm)

[1. Preparation of aqueous metal surface treatment agent]
Using a solvent as water, a metal compound sol (A) shown below, a phosphorus or fluorine-containing compound (B), an aqueous resin (C) and, if necessary, an additive (D) are combined, and ammonia or acetic acid is further used. The pH was adjusted to prepare aqueous metal surface treatment agents of Examples 1 to 41 shown in Tables 1 and 2 and aqueous metal surface treatment agents of Comparative Examples 1 to 15 shown in Table 3. In addition, "solid content ratio" in a table | surface shows the ratio (mass%) of each above-mentioned compound which occupies the total solid content of a water-system metal surface treating agent.

<Metal compound sol (A)>
The metal compound sol (A) used is shown below. In addition, 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., Ltd.

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

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

<Water-based resin (C)>
(C1; polyester resin)
An alcohol component composed of ethylene glycol (90 mol%) and trimethylolpropane (10 mol%), isophthalic acid (40 mol%), terephthalic acid (41 mol%), sodium dimethyl-5-sulfonate (2 mol%) and tri An anionic polyester resin (solid content (NVC.) 30%) by a condensation reaction with an acid component consisting of merit acid (17 mol%) was synthesized by the following method. A 1000 mL round bottom flask equipped with a Claisen tube and an air cooler was charged with 1 mol of total acid component, 2 mol of total alcohol component and catalyst (calcium acetate 0.25 g, N-butyl titanate 0.1 g). Was replaced with nitrogen and heated to 180 ° C. to melt the contents. Then, the bath temperature was raised to 200 ° C., and the mixture was heated and stirred for about 2 hours to cause esterification or transesterification. 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 allowed to cool under nitrogen introduction, and the contents were taken out. Add an appropriate amount of ammonia water (water is an amount that gives a solid content of 25%) to the taken-out content and heat and stir at 100 ° C. for 2 hours in an autoclave. Obtained.

(C2: Urethane resin)
100 parts by mass of polyester polyol (adipic acid / 3-methyl-1,5-pentanediol, number average molecular weight 1000, functional group number 2.0, hydroxyl value 112.2), 3 parts by mass of trimethylolpropane, dimethylolpropionic acid 25 Mass parts and 85 parts by mass of isophorone diisocyanate were reacted in MEK to obtain a urethane prepolymer. To this, 9.4 parts by mass of triethylamine was mixed, put 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 urethane resin containing 30% by mass of nonvolatile content. The acid value of the carboxyl group-containing polyurethane dispersed in the obtained aqueous dispersion was 49 (KOH mg / g).

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

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

(C5; acrylic resin 2)
A temperature control regulator, a cooling tube and a stirring device are attached to a reaction vessel composed of a separable four-necked flask, and at room temperature, 390 parts by mass of ion-exchanged water, 210 parts by mass of isopropyl alcohol, and 120 parts by mass of N-methylolacrylamide as an acrylic monomer. Part and 30 parts by mass of acrylamide were charged and dissolved. Furthermore, 1.5 parts by mass of potassium persulfate, 0.06 parts by mass of sodium hydrogen sulfite and 1.5 parts by mass of anhydrous sodium acetate were charged and dissolved. Next, after the reaction vessel was purged with nitrogen, the temperature was raised to 65 ° C. in 30 minutes and reacted at 65 ° C. for 3 hours. The reaction product was cooled to room temperature and filtered out. The obtained acrylic resin aqueous solution had a non-volatile content concentration of 20% by mass, a viscosity of 2.86 dPa · s, and a pH = 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 50000 was used.

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

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

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

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

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

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

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

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

(D2: Epoxy curing agent 1)
Ethylene glycol diglycidyl ether (n = 1, 2 functional, epoxy equivalent 113 WPE, viscosity 20 mPa · s) was used.

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

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

D5: Aluminum monoacetylacetonate bis (ethylacetonate)
D6; Titanium lactate D7; N-methylolacrylamide D8; Dimethylolurea D9; Polyglycerin (average molecular weight 750, hydroxyl value 890)
D10; triethylene glycol

[2. Preparation of test material]
The metal base materials described in Examples 1 to 41 shown in Tables 1 and 2 and Comparative Examples 1 to 15 shown in Table 3 were 50% with a 2% aqueous solution of Fine Cleaner 359E (Nippon Parkerizing Co., Ltd. alkaline degreasing agent). After spray degreasing at 10 ° C. for 10 seconds, the surface was cleaned by washing with water. Then, in order to evaporate the water | moisture content on the surface of a metal base material, it heated and dried at 80 degreeC for 1 minute. The surface of the degreased and washed metal base material was coated with the water-based metal surface treatment agent of Examples 1 to 41 shown in Tables 1 and 2 and Comparative Examples 1 to 15 shown in Table 3 by bar coating using a # 8SUS Meyer bar. Then, it was dried at 180 ° C. for 1 minute in a hot-air circulating drying furnace to form a metal surface treatment film on the surface of the metal substrate. Moreover, what carried out the heat drying of the metal base material of Comparative Examples 16-21 of Table 3 after degreasing and water washing as mentioned above was also used for the test. Tables 1 to 3 summarize the water-based metal surface treatment agents used in each Example or each Comparative Example and the film formation amount of the obtained metal surface treatment film.

[3. Measurement of average particle diameter of metal compound sol (A)]
About the metal material with a metal surface treatment film obtained in Example 3, Example 6, and Example 13, cross-sectional observation was performed with a transmission electron microscope (TEM), and the average particle diameter of the metal compound (A) was estimated. . The average particle diameter of the metal compound (A) was about 100 nm, 30 nm, and 20 nm, respectively.

[4. Laminate performance evaluation]
Then, the laminate film was bonded together on the metal surface treatment film | membrane of a metal base material by the laminating method shown below.

(Laminate 1)
A metal film obtained by laminating a polyester film by thermocompression bonding a polyester film (film thickness: 16 μm) having a corona treatment on one side to a surface of a metal substrate at 250 ° C. and a surface pressure of 5 MPa for 10 seconds. A metal material with a surface treatment film was produced.

(Laminate 2)
A surface of the metal substrate with a metal surface treatment film formed thereon is roll-coated with a dispersion of acid-modified polypropylene, and then dried at 200 ° C. for 1 minute in a hot-air circulating drying oven to form an adhesive layer having a thickness of 5 μm. Formed. Thereafter, the adhesive layer and a polypropylene film having a thickness of 30 μm were thermocompression bonded at 250 ° C. and 0.1 MPa for 10 seconds to produce a metal material with a metal surface treatment film on which the polypropylene film was laminated.

<4.1. Initial adhesion>
A metal material with a metal surface treatment film provided with a laminate film by Laminate 1 and Laminate 2 was extruded 5 mm by an Erichsen test machine, and then subjected to a cross-cut tape peeling test (1 mm pitch). Evaluation was performed by ranks 1 to 3.

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

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

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

<4.3. Corrosion resistance>
About the metal material with a metal surface treatment film | membrane which provided the laminate film by the laminate 2, the external appearance after implementing the CASS test for 24 hours based on JISH8502 was observed visually, and the following ranks 1-9 evaluated.

9: No change in appearance.
8: Area ratio of occurrence of peeling (floating) of laminate film and corrosion under laminate film is more than 0% and 5% or less.
7: Area ratio of occurrence of peeling (floating) of laminate film and corrosion under laminate film is more than 5% and not more than 10%.
6: Area ratio of occurrence of peeling (floating) of laminate film and corrosion under laminate film is more than 10% and 15% or less.
5: Area ratio of occurrence of peeling (floating) of laminate film and corrosion under laminate film is more than 15% but not more than 20%.
4: The area ratio of occurrence of peeling (floating) of the laminate film and corrosion under the laminate film exceeds 20% and is 25 or less.
3: Area ratio of occurrence of peeling (floating) of laminate film and corrosion under laminate film is more than 25% and 40% or less.
2: The area ratio of occurrence of peeling (floating) of the laminate film and corrosion under the laminate film is more than 40% and 60% or less.
1: The area ratio of occurrence of peeling (floating) of the laminate film and corrosion under the laminate film exceeds 60%.

<4.4. Content resistance 1>
About the metal material with a metal surface treatment film which laminated the polyester film by the laminate 1, it was immersed in model juice (citric acid monohydrate: sodium chloride: deionized water = 5: 5: 990 (mass ratio)), 60 It was taken out after 1 week at 0 ° C., cut into a width of 15 mm, and measured for 180 ° peel strength. The adhesion between the laminate film and the metal material was evaluated by the following ranks 1 to 9.

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

<4.5. Content resistance 2>
About the metal material with a metal surface treatment film laminated with a polypropylene film by Laminate 2, an electrolytic solution (trade name: LBG-00001, electrolyte: 1M-LiPF ₆ , solvent: EC / DMC / DEC = 1 / After being immersed in 1/1 (volume%), it was put into a constant temperature bath at 60 ° C. for 7 days. Thereafter, the sample material was taken out, washed while rocking while being immersed in ion-exchanged water for 1 minute, and then dried at 100 ° C. for 10 minutes in a hot-air circulating drying furnace. Then, it cut out to 15 mm width and measured 180 degree peel strength. The adhesion between the laminate film and the metal material was evaluated by the following ranks 1 to 9.

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

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

  As shown in Tables 4 and 5, it was confirmed that the metal material with a metal surface treatment film obtained in Examples 1-41 was excellent in initial adhesion, durable adhesion, corrosion resistance, and the like after the laminate film was formed. It was. As shown in Table 6, the metal material with a metal surface treatment film obtained in Comparative Examples 1 to 15 was inferior in initial adhesion, durable adhesion, corrosion resistance and the like as compared with Examples.

  The aqueous metal surface treatment agent according to the present invention, the metal surface treatment film formed with the aqueous 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 architecture, The present invention is applicable to metal materials such as aluminum, magnesium, copper, iron, zinc, nickel, and alloys thereof. And a container for filling contents containing organic acids such as acetic acid and citric acid and inorganic acids such as sulfuric acid and hydrofluoric acid, specifically, food containers, detergent containers, lithium ion secondary battery containers, etc. Can be preferably applied.

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

Claims (8)

  One or more metal compounds (A) selected from zirconium, titanium or hafnium oxides having an average particle diameter in the range of 1 nm to 500 nm, and one selected from a phosphorus compound group and a fluorine compound group Alternatively, two or more phosphorus or fluorine-containing compounds (B) and one selected from polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, natural polysaccharides, epoxy resins, and elastomers Or the aqueous metal surface treating agent characterized by containing at least 2 or more types of aqueous resin (C).   2. The aqueous metal surface treatment agent 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.   The aqueous metal surface treatment agent according to claim 1 or 2, wherein the content of the aqueous resin (C) is in the range of 5 mass% or more and 90 mass% or less with respect to the total solid content.   The aqueous metal surface treatment agent according to any one of claims 1 to 3, wherein the pH is in the range of 3 or more and 11 or less.   The water-based metal surface treatment agent according to any one of claims 1 to 4, which is used for a laminate base.   One or more metal compounds (A) selected from zirconium, titanium or hafnium oxides having an average particle diameter in the range of 1 nm to 500 nm, and one selected from a phosphorus compound group and a fluorine compound group Alternatively, two or more phosphorus or fluorine-containing compounds (B) and one selected from polyester resins, urethane resins, polyolefin resins, acrylic resins, polyvinyl resins, polyamide resins, polyimide resins, natural polysaccharides, epoxy resins, and elastomers Or the metal surface treatment film | membrane characterized by being a film | membrane formed with the water-system metal surface treating agent which contains 2 or more types of water-system resin (C) at least.   A metal material with a metal surface treatment film, comprising: a metal material; and the metal surface treatment film according to claim 6 provided on a surface of the metal material. The metal material with a metal surface treatment film according to claim 7, further comprising a laminate film provided on the metal surface treatment film.

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