KR20170141748A - Surface treatment agents and metal materials for metal materials - Google Patents

Abstract

The object of the present invention is to provide a surface treatment agent for a metal material which is capable of forming a film having corrosion resistance and which is also excellent in liquid stability and a metal material having a metal surface treatment film formed by the surface treatment agent. (A) and a nitrate (component b) of an alkali metal salt of zirconium carbonate and one kind selected from urethane resin, epoxy resin, acrylic resin, phenol resin, polyester resin, polyvinyl resin, polyolefin resin and natural polymer Or a mixture of two or more kinds of organic polymers (component c) having a pH of more than 7 but not more than 12.

Description

Surface treatment agents and metal materials for metal materials

The present invention relates to a surface treatment agent for a metal material and a metal material having a metal surface treatment film formed by the surface treatment agent.

As a surface treatment agent capable of forming a film having corrosion resistance, conventionally, zirconium carbonate has been developed (see, for example, Patent Documents 1 and 2).

JP-A-1-149865 Japanese Patent Application Laid-Open No. 2007-204847

However, the above surface treating agent containing zirconium ammonium carbonate may have an increased viscosity over time, which may lower the liquid stability. It is therefore an object of the present invention to provide a surface treatment agent for a metal material which is capable of forming a film having corrosion resistance and which is also excellent in liquid stability and a metal material having a metal surface treatment film formed by the surface treatment agent.

As a result of intensive investigations to solve the above problems, the present inventors have found that a surface treating agent having an alkali metal salt of a zirconium carbonate and a nitrate salt and adjusting the pH to more than 7 but not more than 12, The present invention has been completed.

That is,

(1) a surface treatment agent for metal materials (excluding those containing fluorine) containing an alkali metal salt of zirconium carbonate (component a) and a nitrate salt (component b) and having a pH of more than 7 but not more than 12;

(Component (c)) further comprises at least one organic polymer selected from urethane resin, epoxy resin, acrylic resin, phenol resin, polyester resin, polyvinyl resin, polyolefin resin and natural polymer The surface treatment agent for a metal material according to (1) above;

(3) the surface treatment agent for metallic material according to (1) or (2), wherein the pH is not less than 7.5 and not more than 12;

(4) a metal material having a surface treatment film formed by contacting the surface treatment agent for a metal material according to any one of (1) to (3) with a metal material surface and then drying;

.

According to the present invention, it is possible to provide a surface treatment agent for a metal material which is capable of forming a film having corrosion resistance and which is also excellent in liquid stability and a metal material having a metal surface treatment film formed by the surface treatment agent.

Hereinafter, the surface treating agent for a metallic material according to the present invention (hereinafter simply referred to as " surface treating agent ") and the metallic material will be described in detail.

The surface treatment agent according to the present invention is in the form of an aqueous solution or an aqueous dispersion at the time of use, and the straight type used as it is and the high concentration type diluted with water at the time of use are included in the concept of the surface treatment agent of the present invention. Hereinafter, a straight type surface treatment agent will be described as an example.

The surface treatment agent contains an alkali metal salt (component a) and a nitrate salt (component b) of zirconium carbonate and does not contain fluorine and is not particularly limited as long as the pH is in the range of 7 to 12, And / or an additive for a known surface treatment agent. However, from the viewpoint of environmental measures, a surface treatment agent containing no chromium or vanadium is preferable. Further, a surface treatment agent containing no cobalt, cerium and silicon is preferable. In addition, in the specification and claims, the terms "not including" and "excluding" are used to denote inclusion of a trace amount, but are not necessarily completely included. Hereinafter, each component will be described.

Component a is an alkali metal salt of zirconium carbonate. Examples of the alkali metal in this salt include Li, Na, K and the like. The alkali metal salt of zirconium carbonate to be compounded in the surface treatment agent of the present invention may be used singly or in combination of two or more kinds.

Subsequently, component b is nitrate. Examples of the counter cation of nitric acid include a monovalent or divalent metal ion, an alkali metal ion, and an alkaline earth metal ion. Specific examples of the component b include, but are not limited to, sodium nitrate, potassium nitrate, lithium nitrate, ammonium nitrate, nickel nitrate, zirconium nitrate, magnesium nitrate, calcium nitrate, aluminum nitrate and the like. The nitrates to be added to the surface treatment agent of the present invention may be used alone or in combination of two or more.

The ratio [mass ratio = Mb / Ma] of the total mass (Ma) of Zr in the alkali metal salt of zirconium carbonate (component a) and the total mass (Mb) of nitrate ions in the nitrate salt (component b) More preferably 0.01 to 1.00, particularly preferably 0.04 to 0.94, and most preferably 0.04 to 0.7.

In the above description, the surface treatment agent containing only the component a and the component b in addition to the solvent has been described. However, as described above, the organic polymer may be further blended, and a known additive for the surface treatment agent may be further blended Or an organic polymer and an additive for a known surface treatment agent may be further blended.

The organic polymer (component c) is not particularly limited as long as it is a resin used for forming a film. Examples of the organic polymer include a urethane resin, an epoxy resin, an acrylic resin, a phenol resin, a polyester resin, a polyvinyl resin, Natural polymers, and the like, and can be appropriately selected according to the required performance. The organic polymer may be one having at least one functional group selected from the group consisting of an anionic group, a cationic group and a nonionic group, but it is preferable that the organic polymer can be stably present in the surface treatment agent of the present invention. The surface treatment agent containing the solvent and the organic polymer may be in the form of a dissolving liquid or a dispersion liquid such as an emulsion or a dispersion.

As the urethane resin, there is a urethane resin which is a condensation product of a polyol such as a polyether polyol and a polycarbonate polyol and a polyisocyanate such as an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound and / or an aromatic polyisocyanate compound, And polyurethanes obtained by using a polyol having a polyoxyethylene chain such as polyethylene glycol or polypropylene glycol as a part of the polyol. Such a polyurethane can be subjected to water-solubilization or water-oxidation by increasing the introduction ratio of the above-mentioned polyoxyethylene chain. The surface treatment agent according to the present invention may or may not include a polyester polyurethane resin having a structural unit derived from a polyester polyol in the molecule.

It is also possible to prepare a urethane prepolymer having isocyanato groups at both ends with a polyisocyanate and a polyol, to which a carboxylic acid having two or more hydroxyl groups or a reactive derivative thereof is allowed to react and a urethane prepolymer having isocyanato groups Triethanolamine or the like is added thereto to form an ionomer (triethanolamine salt), the ionomer is added to water to prepare an emulsion or a dispersion, and if necessary, a diamine is added to effect chain extension. By doing so, a water-dispersible urethane resin having an anionic property can be obtained.

The carboxylic acid and the reactive derivative used in the production of the anionic water-dispersible urethane resin are used for introducing an acidic group into the urethane resin and for dispersing the urethane resin in water. Examples of the carboxylic acid to be used 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 epoxy resin, an epoxy compound having two or more glycidyl groups, or an epoxy compound having a bisphenol structure such as bisphenol A or bisphenol F in its skeleton, is reacted with a diamine such as ethylenediamine, and then a cation Modified epoxy resin, or a nonionic epoxy resin obtained by adding a polyalkylene oxide to a side chain (e.g., hydroxyl group) of an epoxy compound having two or more glycidyl groups, and the like.

In addition, the epoxy resin may be an epoxy resin in which part or all of the glycidyl group in the epoxy resin having a bisphenol structure such as bisphenol A or bisphenol F as a unit in the skeleton is modified with phosphoric acid.

Examples of the epoxy resin having a bisphenol structure such as bisphenol A and bisphenol F as a unit in the skeleton include an epoxy resin obtained by subjecting epichlorohydrin and bisphenol A or bisphenol F to a dehydrochlorination reaction and then performing an addition reaction of an epoxy compound and a diamine Obtained by repeating the addition reaction of an epoxy compound having two or more, preferably two glycidyl groups with bisphenol (A, F).

Examples of the epoxy compound include diglycidyl ether of bisphenol (A, F), diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl ester of terephthalic acid, diglycidyl p-oxybenzoate Diglycidyl esters, hexahydrophthalic acid diglycidyl esters, succinic acid diglycidyl esters, adipic acid diglycidyl esters, sebacic acid diglycidyl esters, 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 , Trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-glycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane Wrigley upon the like ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol-alkylene oxide addition of water during triglycidyl ether. These may be used alone or in combination of two or more.

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

As the acrylic monomer, for example, there may be mentioned methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n- , 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, 2-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 copolymerizable with the acrylic monomer include maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, diacetone acrylamide, styrene, acrylonitrile and vinylsulfonic acid.

As the polyester resin, there may be mentioned, for example, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, isophthalic acid, terephthalic acid, trimellitic acid Diethyleneglycol, trimethylolpropane, neopentyl glycol, 1,4-CHDM (cyclohexanedimethanol), 1,6-hexanediol dimethanol, and the like. A polyester polyol in which a polyol such as hexanediol is condensed; A condensation resin obtained by condensing the above polybasic acid with a polyol such as a polymer polyol, polycaprolactone polyol, polycarbonate diol, polybutadiene polyol, neopentyl glycol or methylpentadiol; And the like. Further, it is also possible to use a water-based resin obtained by neutralizing a monomer (such as trimellitic acid or pyromellitic acid) having three or more carboxyl groups with a condensate of various polyols (having an unreacted carboxyl group) with an alkali and solubilizing or moisture- A water-based resin obtained by solubilizing or water-condensing a condensate of a monomer in which a sulfonic acid group is introduced by reacting a sulfonic acid such as phthalic acid and various polyols can also be used.

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

The polyvinyl resin includes those obtained by saponifying a polymer obtained by copolymerizing a vinyl acetate copolymerizable monomer. In the polyvinyl resin, a modified polymer obtained by introducing an anionic group such as a carboxylic acid, a sulfonic acid, or a phosphoric acid into a copolymerized or saponified polymer, and a crosslinked polymer such as a diacetone acrylamide group, an acetoacetyl group or a mercapto group A modified polymer into which a functional group having reactivity is introduced, and the like.

Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid and (meth) acrylic acid and esters thereof; ? -Olefins such as ethylene and propylene; Olefin sulfonic acid, which may have a carboxyl group, such as (meth) acrylic sulfonic acid, ethylene sulfonic acid, and sulfonic acid maleate; (Meth) acrylate sulfonate, which may have a carboxyl group and / or an alkoxycarbonyl group, such as sodium (meth) acrylate sulfonate, sodium ethylene sulfonate, sodium sulfonate (meth) acrylate, salt; Amide group-containing monomers such as N-methylol acrylamide and acrylamide alkylsulfonic acid alkali salts; Pyrrolidone group-containing monomers such as N-vinylpyrrolidone and N-vinylpyrrolidone derivatives; And the like.

Examples of the phenol resin include polycondensation products of phenols (phenol, naphthol, bisphenol, etc.) and formaldehyde, water-soluble resins having a low molecular weight, or emulsion resins. Among these, a resol-type phenol resin having a methylol group with magnetic-axis synthesis is preferable.

Examples of natural polymers include cellulose, starch, dextrin, inulin, xanthan gum, tamarind gum, tannic acid, and ligninsulfonic acid.

As the polyolefin-based resin, polypropylene; Polyethylene; Propylene or a copolymer of ethylene and an? -Olefin; , A modified polyolefin obtained by modifying the polyolefin with an unsaturated carboxylic acid (e.g., acrylic acid or methacrylic acid), and a copolymer of ethylene and acrylic acid (methacrylic acid). A small amount of another ethylenic unsaturated monomer may be copolymerized with these resins. As means for dissolving or dispersing these polyolefin resins in water, means for neutralizing the carboxyl groups contained in the polyolefin resins with ammonia or amines may be mentioned.

The number average molecular weight of the organic polymer is preferably from 1,000 to 1,000,000. In addition, the polymer resin may have a crosslinkable reactive functional group unless the effect of the present invention is impaired. The number average molecular weight can be measured by a GPC method (Gel Permeation Chromatography). More specifically, the difference in refractive index can be measured with a GPC apparatus (HLC-8220, manufactured by Tosoh Corporation) equipped with a differential refractometer (RI) detector and calculated in terms of polystyrene (the same applies hereinafter).

The content of the organic polymer (component c) contained in the surface treatment agent is preferably 95% or less, more preferably 90% or less, as the upper limit of the solid content conversion ratio with respect to the mass of the solid content in the surface treatment agent. On the other hand, the lower limit value is preferably 5% or more, more preferably 10% or more. By incorporating the organic polymer (component c) into the surface treatment agent in the range of this ratio, it is possible to improve the film formability of the far-off layer and to form a dense surface-treated film and to improve the corrosion resistance.

Examples of additives for the surface treatment agent include antifoaming agents, leveling agents, stabilizers, antirust agents, antimicrobial agents, antifungal agents, wetting agents and thickening agents, which are known additives, and one or more of them can be used have. Specifically, a surface treatment agent in which a defoaming agent, a leveling agent, a stabilizer, a rust inhibitor, an antimicrobial agent, an antifungal agent, a wetting agent or a thickening agent is blended, or a solvent and a component (a) Defoaming agents and leveling agents, defoamers and stabilizers, defoamers and rust inhibitors, defoamers and wetting agents, leveling and stabilizers, leveling and rust inhibitors, leveling and wetting agents, stabilizers and antirusting agents, in addition to component (b) , Stabilizers and wetting agents, rust inhibitors and wetting agents, antibacterial agents and antifungal agents, or stabilizers, antibacterial agents and antifungal agents.

As the antifoaming agent, for example, a mineral oil antifoaming agent, a fatty acid antifoaming agent, a silicone antifoaming agent and the like can be used. Further, both of them may be added to the surface treatment agent. As the leveling agent, for example, known compounds such as nonionic or cationic surfactants, adducts of polyethylene oxide or polypropylene oxide of polyacetylene glycol, and acetylene glycol compounds can be used. As the stabilizer, for example, known chelating agents such as ethanol amines, tartaric acid, citric acid, lactic acid, gluconic acid, glycolic acid and salts thereof may be used and they may be used alone or in combination of two or more kinds . Examples of the ethanolamine include monoethanolamine, diethanolamine, triethanolamine, and the like, but are not limited thereto. As the thickening agent, for example, sodium salt, potassium salt or ammonium salt such as hydroxyethyl cellulose, carboxymethyl cellulose and the like; Polyethylene glycol; Polyvinylpyrrolidone; Copolymers of vinylpyrrolidone and vinyl acetate; Polyvinyl alcohol partially saponified with polyvinyl acetate resin; Etc. may be used. The surface treatment agent may or may not include hindered amines which are radical scavengers. Herein, hindered amines mean compounds having a structure in which carbon atoms are bonded directly to the nitrogen atom of the piperidine ring or through an oxygen atom.

When the pH of the surface treatment agent is 7 or less, the oxidizing power of the nitrate ions becomes strong, and when the surface treatment agent is brought into contact with the metal material, the oxide film obtained on the surface of the metal material becomes thick and the adhesion between the surface treatment film and the surface of the metal material decreases, . Further, when the pH of the surface treatment agent is more than 12, the oxidizing power of nitrate ions is weakened, and when the surface treatment agent is brought into contact with the metal material, a dense oxide film is not obtained on the surface of the metal material, and corrosion resistance is lowered. Therefore, the pH of the surface treatment agent according to the present invention is adjusted from 7 to 12. Further, the pH of the surface treatment agent is preferably 7.5 or more and 12 or less, and more preferably 8 or more and 11 or less. In addition, the pH specified in the present specification and claims refers to a value measured at 25 占 폚.

(Method for producing surface treatment agent)

The method for producing the surface treatment agent according to the present invention is not particularly limited. For example, a mixture of an alkali metal salt of a zirconium carbonate (component a), a nitrate salt (component b), a solvent and, if necessary, an organic polymer (component c) and / or other additives, And then sufficiently mixing them.

The solvent is not particularly limited, but an aqueous solvent is preferred. The aqueous solvent means that it contains 50 mass% or more of water based on the mass of the total solvent. The term " solvent " does not mean a solvent having a narrow meaning of dissolving all the components, and includes a dispersoid that may be dispersed in some components. Examples of the solvent 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; 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; Phosphoric acid amide type solvents such as hexamethylphosphoric triamide; And the like. These solvents other than water may be used alone, or two or more solvents may be used in combination. Further, only water as a solvent may be used.

(Metal material)

Next, a method of manufacturing the metal material according to the present invention will be described. The method includes a step of contacting a surface treatment agent to a surface of a metal material (a contact step) and a step of drying a surface of the metal material to which the surface treatment agent is contacted (a drying step). In general, the method includes a degreasing step and a washing step before the contacting step. Further, in the method, after the drying step, a step of bringing a known top coating material into contact with a coating film formed by the surface treatment agent so as to form an upper coating film (coating film) may be performed.

As a method for contacting the surface treatment agent, a conventional method can be applied, and for example, it can be carried out by a roll coat, a curtain flow coat, an air spray, an airless spray, an immersion, a bar coat, a brush application or the like.

The surface of the metal material with which the surface treatment agent is brought into contact can be dried by a conventional method, for example, heat drying or air drying. The drying temperature is not particularly limited as long as the surface of the metal material can be dried, but the maximum attainable temperature (PMT) of the metal material is in the range of 40 to 200 占 폚, and more preferably in the range of 60 to 150 占 폚. By drying within the range of 60 占 폚 to 150 占 폚, the adhesion between the coating formed by the surface treatment agent and the metallic material or the top coating film can be improved.

In addition, the metal material to be subjected to the heat treatment may be selected from the group consisting of cold-rolled steel sheet, hot-rolled steel sheet, hot-dip galvanized steel sheet, galvanized steel sheet, galvannealed steel sheet, Steel plates such as alloy-coated steel plates, stainless steel plates, and the like; Aluminum material; Aluminum alloy material; Copper material; Copper alloy material; Titanium material; Titanium alloy material; Magnesium material; Magnesium alloys, and other commonly known metallic materials and plating materials. Among them, an aluminum material or an aluminum alloy material is preferable. The metallic material to be brought into contact with the surface treatment agent according to the present invention may be a mixture of plural kinds of materials. These metal materials may be subjected to ordinary treatments such as basting or alkali degreasing before the surface treatment with the surface treatment agent.

Next, the metallic material on which the coating is formed by the surface treatment will be described. First, it is preferable that the film mass of the formed film is in the range of 0.01 to 1 g / m 2 (dry mass). When the film mass is within this numerical value range, the adhesion can be improved. A more preferred range is within the range of 0.02 g / m 2 to 0.5 g / m 2.

Next, a method (use) of using the metallic material on which the coating with the surface treatment agent is formed will be described. First, by processing the metal material into a desired shape, various metal products can be obtained. Examples of the metal products include galvanized steel sheets for household appliances, precoated steel sheets for residential use, aluminum fin members for air conditioners, and various metal parts for automobiles. The top coat formed on the coating film is not particularly limited. Examples of the top coat film include an electrodeposited coating film, a solvent coating film, a powder coating film and a special coating film such as a hydrophilic coating film, a lubricating organic coating film, And the like.

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 material]

The metal materials used as the substrate are shown below.

Aluminum plate (A1050P; JIS H 4000-2014)

Cold rolled steel sheet (SPCC-SD; JIS G 3141-2011)

Hot-dip galvanized steel sheet [GI: zinc adhering amount 60 g / m < 2 > JIS G 3302-2012]

[Surface treatment agent]

As shown in Tables 1 to 3, each of the surface treating agents used for producing the specimens of Examples 1 to 31 and Comparative Examples 1 to 9, 11 to 18 and 20 to 24 was produced. In addition, water was used as a solvent. The pH was adjusted using ammonia or acetic acid. "Component C concentration" in each table represents the nonvolatile component concentration (% by mass) of the component C with respect to the mass of the solid component in the surface treatment agent. The symbols shown in the column of "Component A", "Component B" and "Component C" in the respective tables represent the following substances, respectively. "MB / MA" in each table represents the mass ratio of the total mass (MA) of Zr in component A to the total mass (MB) of anions in component B combined with the surface treatment agent. The solid content concentration of each surface treatment agent was appropriately adjusted so that the amount of the coating formed by the surface treatment agent was 50 mg / m 2.

[Component A]

A1: Zirconium carbonate sodium

A2: Lithium zirconate carbonate

A3: Potassium zirconate carbonate

A4: Zirconium carbonate ammonium

[Component B]

B1: Sodium nitrate

B2: Potassium nitrate

B3: Ammonium nitrate

B4: Sodium sulfate

B5: Sodium Phosphate

[Component C (organic polymer)]

(Component C1: urethane resin - anionic)

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, hydroxyl value: 112.2), trimethylolpropane 3 parts by mass, dimethylolpropionic acid 25 And 85 parts by mass of isophorone diisocyanate were reacted in MEK (methyl ethyl ketone) to obtain a urethane prepolymer. This reaction mixture was mixed with 9.4 parts by mass of triethylamine, dispersed in water and elongated with ethylenediamine. Thereafter, methyl ethyl ketone was distilled off to obtain an urethane resin aqueous dispersion containing 30 mass% of nonvolatile matter. The acid value of the carboxyl group-containing polyurethane in the obtained urethane resin aqueous dispersion was 49 (KOH mg / g).

(Component C2: epoxy resin - anionic)

To 85 g of orthophosphoric acid and 140 g of propylene glycol monomethyl ether, 425 g of a bisphenol A type epoxy resin having an epoxy equivalent of 250 was added little by little and the mixture was reacted at 80 DEG C for 2 hours. After completion of the reaction, 150 g of a 29 mass% ammonia aqueous solution was added little by little at 50 캜 or lower and 1150 g of water was further added to obtain an ammonia neutralized product of a phosphoric acid modified epoxy resin having an acid value of 35 (KOH mg / g) and a solid content concentration of 25 mass% ≪ / RTI >

(Component C3: acrylic resin-nonionic)

20 parts by mass of methyl methacrylate (molecular weight: 100), 40 parts by mass of butyl acrylate (molecular weight: 128), 10 parts by mass of 2-hydroxypropyl methacrylate (molecular weight: 144) : 104) and 20 parts by mass of N, N-dimethylaminopropyl methacrylate (molecular weight: 175) were used. The synthesis of component C3 was carried out as follows. A 10 mass% emulsifier aqueous solution (S-1 (trade name)) was prepared by mixing 6: 4 of a reactive emulsifier " ADEKA LIEROSEOP NE-20 " (manufactured by ADEKA KABUSHIKI KAISHA) and a nonionic emulsifier " EMULGEN 840S " ), The above monomers were mixed and emulsified at 5000 rpm for 10 minutes using a homogenizer to obtain a monomer emulsion (ER). Subsequently, while maintaining the temperature at 40 to 50 ° C, a 5 mass% aqueous solution of ammonium persulfate (50 parts) and a monomer emulsion (ER) were added dropwise to 150 parts of the emulsifier aqueous solution (S-1) over about 2 hours. Thereafter, the temperature was raised to 60 캜 and stirred for about 1 hour. Subsequently, the mixture was cooled to room temperature while stirring to obtain an acrylic resin emulsion solution.

(Component C4: polyester resin - anionic)

(40 mol%), terephthalic acid (41 mol%), sodium dimethyl isophthalate-5-sulfonate (2 mol%), and anhydrous trimellitic anhydride were mixed with an alcohol component containing ethylene glycol (90 mol%) and trimethylol propane Anionic polyester resin (solid content (NVC.) 30%) obtained by condensation reaction of an acid component containing phosphoric acid (17 mol%) was synthesized as follows. Under a nitrogen atmosphere, a mixture of 1 mol of a total 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) was heated to 180 캜 and melted. Thereafter, the mixture was heated to 200 占 폚 and stirred with heating for about 2 hours to effect esterification or ester exchange reaction. Further, after heating at 260 DEG C for 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 in a nitrogen atmosphere. To the reaction product, ammonia water (water is added in an amount of 25% solids) was added to adjust the pH to 6 to 7, and the mixture was heated and stirred at 100 占 폚 for 2 hours to obtain a polyester resin of an aqueous emulsion.

(Component C5: polyvinyl alcohol-nonionic)

Acetacetylated polyvinyl alcohol having a saponification degree of 99%, a viscosity of 12 mPa 占 퐏, an acetacetylation degree of 9.8% and a number average molecular weight of 50,000 was used.

[Production of the disclosure material]

Each substrate was degreased by spraying a 3% aqueous solution of Fine Cleaner 359E (an alkali degreasing agent manufactured by Nihon Parkerizing Co., Ltd.) at 65 DEG C for 1 minute, and then the surface was washed with water. Subsequently, in order to evaporate moisture on the surface of the substrate, it was heated and dried at 80 DEG C for 1 minute. Each surface treatment agent was coated on the surface of the degreased cleaned substrate using a # 3 SAS Meyer bar by a bar coating method and dried at 115 ° C for 30 seconds in a hot air circulation type drying furnace to form a surface treatment film on the surface of the substrate . Thereafter, using a # 5 SAS Meyer bar, a coating material containing an acrylic-modified epoxy resin was applied by a bar coating method so as to have a coating amount of 1.7 g / m 2 and dried at 255 캜 for 20 seconds in a hot air circulating drying furnace, And made a public material. The specimens of Comparative Examples 10, 19 and 25 shown in Tables 1 to 3 were produced by degreasing each substrate as described above, followed by washing with water and drying by heating (untreated plate).

[Performance evaluation]

The liquid stability of each surface treatment agent and the corrosion resistance of each of the test materials were evaluated as follows. The results are shown in Tables 1 to 3.

(Evaluation of liquid stability)

300 g of a drug was introduced into a 1,300 ml toll beaker (opening area: 0.31 cm 2), and stirring was continued under the open condition while maintaining the liquid temperature at 70 캜. In order to maintain the solid concentration during stirring, the replenishment of pure water was carried out at intervals of 30 minutes, and the time until thickening was measured, and the liquid stability was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: 5 hours or more, ×: less than 5 hours

(Corrosion resistance)

When the metal material is an aluminum plate, crosscutting is performed on each of the substrates, and then an aqueous solution of 5 wt% of sodium chloride adjusted to pH 3.0 to 3.1 with acetic acid is used to conduct an acetic acid acid salt spray test at 300 DEG C Time. Thereafter, it was exposed for 96 hours under a constant temperature and humidity environment of 80 占 폚 and 70%, and the maximum length of the generated rust rust was measured and the corrosion resistance was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

6 points: maximum rust length 0 mm, 5 points: maximum rust length exceeding 0 mm and less than 1 mm, 4 points: maximum rust length greater than 1 mm to 2 mm, 3 points: maximum rust length exceeding 2 mm 3 mm or less, 2 points: maximum firing rust length greater than 3 mm to less than 6 mm, 1 point: maximum firing rust length greater than 6 mm to less than 10 mm

In the case where the metal material is a cold-rolled steel sheet, cross-cuts are made on each of the test pieces, and then a salt spray test is carried out with a 5 wt% sodium chloride solution at 35 ° C. until the maximum rust width at one side of the cut portion reaches 3 mm And the corrosion resistance was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

6 points: 480 hours or more, 5 points: 400 hours or more 480 hours or less, 4 points: 320 hours or more 400 hours or less, 3 points: 240 hours or more 320 hours or less, 2 points: 0 hours to less than 120 hours

In the case where the metal material is a hot-dip galvanized steel sheet, the cross-cut is performed on each of the test pieces, and then a salt spray test is performed with a 5 wt% sodium chloride solution at 35 캜. When the maximum rust width at one side of the cut portion reaches 3 mm Was measured, and the corrosion resistance was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

6 points: more than 720 hours, 5 points: less than 640 hours, less than 720 hours, 4 points: less than 660 hours, more than 560 hours, 3 points: less than 460 hours, less than 560 hours, 2 points: less than 240 hours, less than 480 hours, More than 0 hours and less than 240 hours

The specimens of Examples 1 to 17 of Table 1, Examples 18 to 26 of Table 2, and Examples 27 to 31 of Table 3 were confirmed to have excellent corrosion resistance. The surface treatment agents used in Examples 1 to 17 of Table 1, Examples 18 to 26 of Table 2, and Examples 27 to 31 of Table 3 used for the preparation of the sealant were not increased even after 72 hours in the liquid stability evaluation And the liquid stability was very excellent.

Claims (4)

A surface treating agent for metallic materials (excluding those containing fluorine), which contains an alkali metal salt of zirconium carbonate (component a) and a nitrate salt (component b) and has a pH of more than 7 but not more than 12. The resin composition according to claim 1, which comprises one or more organic polymers (component c) selected from a urethane resin, an epoxy resin, an acrylic resin, a phenol resin, a polyester resin, a polyvinyl resin, a polyolefin resin and a natural polymer Wherein the surface treatment agent is a metal surface treatment agent. The surface treatment agent for metallic material according to claim 1 or 2, wherein the pH is 7.5 to 12. A metal material having a surface treatment film formed by bringing the surface treatment agent for a metal material according to any one of claims 1 to 3 into contact with a surface of a metal material and drying the surface treatment agent.