Method for producing metal material having film

Abstract

Provided is a method for producing a metal material having a coating film, with which it is possible to form a coating film having excellent corrosion resistance and hydrophilicity on the surface of a metal material or on the surface of the metal material. The method for producing a metal material having a coating film comprises: a step in which a metal surface treatment agent containing a water-soluble or water-dispersible resin (A) and a compound (B) having a nitrile group and an amino group is brought into contact with the surface or on the surface of a metal material; the ratio [BM / AM] of the mass (BM) of the compound (B) to the mass (AM) of the resin (A) is within the range of 0.03-1.50; and a step for drying the metal surface treatment agent that has been in contact with the surface of the metal material or on the surface of the metal material within a range of 2-1800 seconds in which the maximum temperature (PMT) of the metal material is within a range of 100-200 DEG C.

Description

[0001] This application is a divisional application of the invention patent application with application number 202080081648.X, the original application being filed on November 11, 2020, and entitled "Metal Surface Treatment Agent and Metal Material with Film and Manufacturing Method thereof". Technical Field

[0002] This invention relates to a metal surface treatment agent, a method for manufacturing a metal material with a film using the metal surface treatment agent, and a metal material with a film obtained using the manufacturing method. Background Technology

[0003] For a long time, people have been developing metal surface treatment agents for forming a corrosion-resistant film on metallic materials. For example, Patent Document 1 discloses an aqueous solution containing a specific zwitterionic polymer and a crosslinking agent, wherein the crosslinking agent contains a water-soluble compound of chromium. Patent Document 2 discloses a resin-containing solution containing a specific carboxyl-containing resin, vinyl monomer, persulfate ions or hydrogen peroxide in a specified amount and with a pH of 1.5 to 3.0.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 8-206594;

[0007] Patent Document 2: Japanese Patent Application Publication No. 54-142253. Summary of the Invention

[0008] The problem the invention aims to solve

[0009] However, the corrosion resistance of the film formed by the aqueous solution described in Patent Document 1 is insufficient, and superior performance is required. Furthermore, the hydrophilicity of the film formed by the resin-containing liquid described in Patent Document 2 is insufficient, and superior performance is required. Therefore, the object of the present invention is to provide a metal surface treatment agent capable of forming a film with excellent corrosion resistance and hydrophilicity on the surface of a metal material, a method for manufacturing a metal material with a film using the metal surface treatment agent, and a metal material with a film obtained using the manufacturing method.

[0010] Solution for solving the problem

[0011] In order to solve the above problems, the inventors conducted in-depth research and found that by using an agent containing a water-soluble or water-dispersible resin and a compound having a nitrile group and an amino group, it is possible to form a film with excellent corrosion resistance and hydrophilicity on the surface of a metal material, thus completing the present invention.

[0012] That is, the present invention relates to the following:

[0013] [1] A metal surface treatment agent comprising a water-soluble or water-dispersible resin (A) and a compound having a nitrile group and an amino group (B);

[0014] [2] According to the metal surface treatment agent described in [1] above, wherein the mass (B) of the above compound (B) M ) and the mass of the above resin (A) (A) M The ratio of [B] M / A M Within the range of 0.03 to 1.50;

[0015] [3] The metal surface treatment agent according to [1] or [2] above, wherein the resin (A) is a resin having at least one functional group selected from amino, amide, carboxyl and hydroxyl groups;

[0016] [4] The metal surface treatment agent according to any one of [1] to [3] above, wherein the molecular weight of the compound (B) is 1000 or less;

[0017] [5] The metal surface treatment agent according to any one of [1] to [4] above, comprising at least one inorganic compound (C) selected from chromium compounds, vanadium compounds, titanium compounds and zirconium compounds, wherein the mass (B) of the compound (B) M The mass (C) of the inorganic compound (C) mentioned above. M The ratio of [B] M / C M Within the range of 0.10 to 5.00;

[0018] [6] A method for manufacturing a metal material having a film, comprising the following steps: a step of contacting the metal surface treatment agent described in any one of [1] to [5] with the surface of the metal material or on the surface of the metal material, and a step of drying the metal surface treatment agent that has been in contact with the surface of the metal material or on the surface of the metal material;

[0019] [7] A metallic material having a coating, which is obtained by the manufacturing method described above [6].

[0020] Invention Effects

[0021] The present invention provides a metal surface treatment agent, a method for manufacturing a metal material with a film using the metal surface treatment agent, and a metal material with a film obtained by using the manufacturing method. The metal surface treatment agent can form a film with excellent corrosion resistance and hydrophilicity on the surface of the metal material. Detailed Implementation

[0022] The following describes the metal surface treatment agent of this embodiment, the manufacturing method of the metal material with a film using the metal surface treatment agent, and the metal material with a film obtained using the manufacturing method.

[0023] (Metal surface treatment agent)

[0024] The metal surface treatment agent of this embodiment comprises a resin (A) and a compound (B) having nitrile and amino groups (hereinafter referred to as "compound (B)"). By using this metal surface treatment agent, a film with excellent corrosion resistance and hydrophilicity can be formed on the surface of a metal material.

[0025] <Resin (A)>

[0026] As for resin (A), there are no particular limitations as long as it is water-soluble or water-dispersible, and examples include polyurethane resins, polyvinyl alcohol resins, polyamide resins, epoxy resins, acrylic resins, amine resins, phenolic resins, and polyvinylpyrrolidone resins. Furthermore, resin (A) can be a homopolymer of polyurethane resin, polyvinyl alcohol resin, polyamide resin, epoxy resin, phenolic resin, polyvinylpyrrolidone resin, etc.; it can also be a modified product by modifying the side chains of the homopolymer with other compounds; or it can be a copolymer combining two or more of these resins and modifiers. Among these, resins having functional groups such as amino, amide, carboxyl, and hydroxyl groups are preferred, and more specifically, resins having functional groups that are directly bonded to carbon atoms are preferred. Furthermore, as for the weight average molecular weight of resin (A), there are no particular limitations as long as it is 2000 or more, preferably 4000 or more, more preferably 10000 or more. The upper limit is preferably 1,000,000 or less. Resin (A) may have one or more of these groups. Furthermore, these resins may be mixed in one form to manufacture a metal surface treatment agent, or in combination with two or more forms to manufacture a metal surface treatment agent.

[0027] <Compound (B)>

[0028] As for compound (B), there are no particular limitations as long as it has a nitrile group and an amino group and is different from resin (A). Examples include: aminocyanide, aminoacetonitrile, 3-aminopropionitrile, dicyandiamide, 3-aminocrotonitrile, 2-amino-1,1,3-tricyano-1-propene, 2-aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile, 2-aminophenylacetonitrile, 4-aminophenylacetonitrile, 2-amino-5-bromobenzonitrile, 2-amino-5-nitrobenzenitrile, 4-amino-3-bromobenzonitrile, 2-amino-4-chlorobenzonitrile, 2-amino-5-chlorobenzonitrile, 2-amino-4,5-diacetonitrile-1H-imidazolium, 4-(aminomethyl)benzonitrile, etc. Furthermore, the molecular weight of compound (B) is preferably 1000 or less, more preferably 800 or less, and particularly preferably 500 or less. Moreover, as for compound (B), it is preferable that it is not a polymer having a repeating structure.

[0029] In this embodiment, the mixing ratio of resin (A) to compound (B) in the metal surface treatment agent is not particularly limited, and the mass (B) of compound (B) is not limited. M The quality of resin (A) and its components (A) M The ratio of [B] M / A M The preferred concentration is in the range of 0.03 to 1.50, more preferably in the range of 0.10 to 1.00, and particularly preferably in the range of 0.10 to 0.50. Furthermore, when the metal surface treatment agent contains two or more resins (A) or two or more compounds (B), it is preferable to use the ratio [B] calculated based on their total mass. M / A M Within the aforementioned range.

[0030] <Other Ingredients>

[0031] The metal surface treatment agent of this embodiment may consist only of resin (A) and compound (B) except for an aqueous medium, or it may further contain other components. Examples of other components include inorganic compounds (C) and surfactants. Furthermore, the metal surface treatment agent of this embodiment may contain hydrogen peroxide or persulfate, or it may not contain them.

[0032] Examples of inorganic compounds (C) include chromium compounds, vanadium compounds, titanium compounds, and zirconium compounds. For chromium compounds, there are no particular restrictions on the type containing chromium, and examples include chromium sulfate, chromium nitrate, chromium dihydrogen phosphate, chromium fluoride, chromium acetate, chromium formate, chromic anhydride, and dichromic acid. For vanadium compounds, there are no particular restrictions on the type containing vanadium, and examples include vanadium pentoxide, ammonium metavanadate, sodium metavanadate, vanadium trichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetylacetonate, vanadium acetylacetonate, vanadium trichloride, vanadium phosphomolybdic acid, and vanadium sulfate. As for titanium compounds, there are no particular limitations as long as they contain the element titanium. Examples include titanium oxysulfate, titanium oxynitrate, titanium nitrate, nickel titanium chloride, titanium dioxide sol, titanium oxide, potassium titanium oxalate, titanium lactate, titanium tetraisopropoxide, titanium acetylacetonate, titanium diisopropyl diacetylacetonate, titanium fluoride or its salts, metatitanic acid obtained by hot hydrolysis of an aqueous solution of titanium oxysulfate, and orthotitanic acid or its salts obtained by neutralization with an alkali. As for zirconium compounds, there are no particular limitations as long as they contain the element zirconium. Examples include zirconium nitrate, zirconium oxynitrate, zirconium oxyacetate, zirconium oxysulfate, zirconium ammonium oxycarbonate, potassium zirconium oxycarbonate, sodium zirconium oxycarbonate, zirconium oxide sol, zirconium fluoride or its salts, and zirconic acid or its salts obtained by ion exchange of an aqueous solution of a water-soluble zirconium salt or by neutralization with an alkali. In metal surface treatment agents, these inorganic compounds can contain one or more of these compounds.

[0033] In this embodiment, when the metal surface treatment agent contains an inorganic compound (C), the mixing ratio of compound (B) to inorganic compound (C) in the metal surface treatment agent is not particularly limited, and the mass (B) of compound (B) is not limited. M The mass of inorganic compound (C) and its mass (C) M The ratio of [B] M / C M The preferred concentration is in the range of 0.10 to 5.00, more preferably in the range of 0.20 to 4.00, and particularly preferably in the range of 0.30 to 3.00. Furthermore, when the metal surface treatment agent contains two or more compounds (B) or two or more inorganic compounds (C), it is preferable to use the ratio [B] calculated based on their total mass. M / C M Within the aforementioned range.

[0034] As surfactants, cationic, anionic, amphoteric, and nonionic surfactants can be used. Examples include: cationic surfactants such as alkylamine salts and alkyltrimethylammonium halides; anionic surfactants such as alkyl sulfonates, polyoxyethylene alkylphenyl ether sulfates, sodium dodecyl diphenyl ether disulfonate, and sodium dodecyl sulfate; amphoteric surfactants such as alkylaminopropionates and alkyldimethyl betaine; and nonionic surfactants such as polyoxyethylene alkylphenyl ethers, polyoxyalkylene fatty acid esters, fatty acid glycerides, sorbitan fatty acid esters, polyoxyethylene glycerol fatty acids, and polyoxyethylene propylene glycol fatty acid esters. They can be used alone or in combination of two or more.

[0035] <Aqueous Media>

[0036] As an aqueous medium, there are no particular restrictions as long as it contains more than 50% water by mass. It can be a medium composed solely of water or a mixture containing water and a water-miscible organic solvent. As for water-miscible organic solvents, there are no particular limitations as long as they are miscible with water. Examples include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. These water-miscible organic solvents can be mixed with one or more types of water.

[0037] (Manufacturing method of metal surface treatment agent)

[0038] The metal surface treatment agent of this embodiment can be manufactured, for example, by mixing a predetermined amount of resin (A) and compound (B) in an aqueous medium, as well as other components added as needed.

[0039] (Metallic materials with a coating and their manufacturing methods)

[0040] The method for manufacturing a metal material with a film according to this embodiment (hereinafter referred to as "the manufacturing method of this embodiment") includes: a contact step, in which the aforementioned metal surface treatment agent is brought into contact with the surface of a metal material; and a drying step, in which the metal surface treatment agent that has been in contact with the surface of the metal material is dried. This manufacturing method yields a metal material with a film exhibiting excellent corrosion resistance and hydrophilicity on its surface. Furthermore, the manufacturing method of this embodiment may include a degreasing step and / or a chemical conversion treatment step prior to the contact step.

[0041] <Metallic Materials>

[0042] The shape and structure of the metallic material forming the coating are not particularly limited, and examples include, for example, plates and foils. The type of metallic material is not particularly limited, and examples include, for instance, steel materials (e.g., cold-rolled steel plates, hot-rolled steel plates); coating materials, such as zinc-plated materials (e.g., electro-galvanized, hot-dip galvanized, aluminum-zinc plating, electro-galvanized, zinc-nickel plating, zinc-cobalt plating, vapor-galvanized, etc.), zinc alloy coating materials (e.g., alloyed hot-dip galvanized, Zn-Al alloy plating, Zn-Al-Mg alloy plating, electro-galvanized alloy plating, etc.), aluminum-plated materials, nickel-plated materials, tin-plated materials, chromium-plated materials, chromium alloy plating materials (e.g., Cr-Ni alloy plating, etc.); aluminum materials or aluminum alloy materials (e.g., 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series, aluminum castings, aluminum alloy castings, die-casting materials, etc.); copper materials or copper alloy materials; titanium materials or titanium alloy materials; magnesium materials or magnesium alloy materials, etc.

[0043] <Contact Process>

[0044] Examples of contact methods include, but are not limited to, spraying, dipping, roller coating, bar coating, curtain coating, spin coating, or combinations thereof. The contact temperature and contact time can be appropriately set according to the composition and concentration of the metal surface treatment agent. Generally, the contact temperature is within the range of 10°C to 45°C, and the contact time is within the range of 5 seconds to 600 seconds, but these are not limited to.

[0045] <Drying Process>

[0046] There are no particular limitations on the drying method; examples include drying methods using known drying equipment, such as batch drying ovens, continuous hot air circulation drying ovens, conveyor belt hot air drying ovens, and electromagnetic induction heating ovens using induction heating heaters. The drying temperature and drying time can be appropriately set according to the type of metal material and the composition or amount of the metal surface treatment agent in contact with it. There are no particular limitations on the drying temperature; preferably, the maximum reach temperature (PMT) of the metal material is in the range of 100°C to 200°C, more preferably in the range of 130°C to 170°C. There are also no particular limitations on the drying time; it is in the range of 2 seconds to 1800 seconds.

[0047] <Degreasing process>

[0048] As a degreasing method, any method that can remove grease and dirt adhering to the surface of the metal material can be used, including known methods such as solvent degreasing and degreasing with alkaline or acidic agents. Furthermore, if a contact process or chemical conversion treatment is performed after the degreasing process, a water washing process can be performed on the surface of the metal material after the degreasing process and before the contact process or chemical conversion treatment, or this process can be omitted. If water washing is performed, the surface of the metal material can be dried afterward, or drying can be omitted.

[0049] <Chemical Conversion Process>

[0050] The chemical conversion treatment process is not particularly limited as long as it forms a chemical conversion film; examples include zirconium chemical conversion treatment, titanium chemical conversion treatment, hafnium chemical conversion treatment, phosphate chemical conversion treatment, and chromate chemical conversion treatment. A washing process with water on the surface of the metal material may or may not be performed after the chemical conversion treatment process and before the contact process. If water washing is performed, the surface of the metal material may or may not be dried. Furthermore, in the case of a phosphate chemical conversion treatment process using zinc phosphate, a surface conditioning treatment process to improve the reactivity of the phosphate chemical conversion treatment may be performed on the metal material between the degreasing process and the phosphate chemical conversion treatment process. Known methods can be used as this surface conditioning treatment method.

[0051] Chemical conversion treatment is performed by bringing a chemical conversion agent into contact with the surface of a metallic material. Examples of chemical conversion agents include, but are not limited to, zirconium, titanium, hafnium, phosphate, and chromate agents. Known methods for contacting the chemical conversion agent include, but are not limited to, impregnation, spraying, rinsing, or combinations thereof. In various chemical conversion treatment processes, the temperature or contact time of the chemical conversion agent can be appropriately set according to the type of chemical conversion treatment process and the concentration of the chemical conversion agent.

[0052] <Membrane>

[0053] The amount of film formed on the surface of a metal material by the metal surface treatment agent is not particularly limited, as long as it can achieve the performance of the present invention; for example, it is preferably 0.05 g / m³. 2 Above and 1.5g / m 2 Within the following range, more preferably within 0.1 g / m 2 Above and 1.0g / m2 Within the following range. Furthermore, a chemically converted coating obtained through the aforementioned chemical conversion treatment process can be further present between the metal material and the coating.

[0054] Example

[0055] The present invention will be further described in detail with reference to embodiments and comparative examples. However, the present invention is not limited to the following embodiments.

[0056] (Preparation of metal surface treatment agents)

[0057] As shown in Table 1, water-soluble or water-dispersible resin, nitrile compound, and inorganic compound were sequentially added to deionized water in specified amounts, followed by the addition of a surfactant (ADEKA Pluronic (registered trademark) L-61, manufactured by ADEKA Corporation) to achieve a final concentration of 10 g / L. Then, deionized water was added to bring the total mass of the water-soluble or water-dispersible resin, nitrile compound, inorganic compound, and surfactant to 100 g / L, thereby producing the metal surface treatment agents of Examples 1-11 and Comparative Examples 1-5. Furthermore, the components listed under "Type" in Table 1 are as follows.

[0058] [Table 1]

[0059]

[0060] <Water-soluble or water-dispersible resins>

[0061] A1: Polyvinyl alcohol (Kuraray Poval PVA-103, manufactured by Kuraray Corporation)

[0062] A2: Polyacrylic acid (Aqualic DL-40S, manufactured by Nippon Shokubai Co., Ltd.)

[0063] A3: Polyacrylamide (Polystlon 387-20, manufactured by Arakawa Chemical Industry Co., Ltd.)

[0064] <Nitrile Compounds>

[0065] B1: Dicyandiamide (manufactured by Carbide Industries, Ltd., Japan)

[0066] B2: Aminopropionitrile (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0067] B3: Propanenitrile (manufactured by Yoneyama Pharmaceutical Co., Ltd.)

[0068] B4: Acrylonitrile-butadiene latex (1571C2, manufactured by Zeon Corporation, Japan)

[0069] <Inorganic Compounds>

[0070] C1: Chromium sulfate

[0071] C2: Vanadium oxysulfate

[0072] (Evaluation of the production of samples No. 1 to 16)

[0073] An aluminum plate (1050, thickness: 0.6 mm) was used as the test material. It was immersed in an alkaline degreasing agent (FINE CLEANER 315E (manufactured by Parkerizing Co., Ltd., Japan) dissolved in water to a mass concentration of 2%) at 60°C for 2 minutes to perform degreasing treatment. Then, the surface of the test material was washed with water.

[0074] The degreased and washed test materials were immersed in a zirconium-based chemical conversion agent [Palcoat 3762 (manufactured by Parkerizing Co., Ltd., Japan) dissolved in water to a concentration of 5% and adjusted to pH 4.0] for 2 minutes at 60°C to perform chemical conversion treatment. After chemical conversion treatment, the surface of the test materials was washed with water.

[0075] Test materials with a chemically converted film formed by chemical conversion treatment were immersed in various metal surface treatment agents (metal surface treatment agents of Examples 1-11 and Comparative Examples 1-5) at 25°C for 10 seconds, and then dried at 150°C for 6 minutes using a blower dryer, thereby producing test materials with a film (evaluation samples No. 1-16).

[0076] (Evaluation of the production of samples No. 17-32)

[0077] A 55% aluminized-zinc coated steel sheet (thickness: 0.35 mm) was used as the test material. It was degreased by immersing it in an alkaline degreasing agent (FINE CLEANER 6404 (manufactured by Parkerizing Co., Ltd., Japan) dissolved in water at a concentration of 2% for 30 seconds at 60°C. The surface of the test material was then washed with water.

[0078] The test materials, which had undergone degreasing and washing, were immersed in each metal surface treatment agent (the metal surface treatment agents of Examples 1-11 and Comparative Examples 1-5) at 25°C for 10 seconds, and then dried at 150°C for 6 minutes using a blower dryer, thereby producing test materials with a film (evaluation samples No. 17-32).

[0079] (Corrosion Resistance Evaluation Method)

[0080] <Neutral saline spray test: SST>

[0081] Based on the salt spray test method (JIS-Z-2371: 2015), after 240 hours of salt spray, calculate the area ratio (%) of white rust generated on the surface of the evaluation sample, and evaluate the corrosion resistance (SST) according to the following evaluation criteria. In addition, those with an evaluation result of B or above are considered qualified.

[0082] <Acetic acid acidic salt spray test: AASST>

[0083] Based on the salt spray test method (JIS-Z-2371: 2015), after spraying an aqueous solution adjusted to pH 3.0 with acetic acid and containing copper(II) chloride for 240 hours, calculate the area ratio (%) of white rust generated on the surface of the evaluation sample, and evaluate the corrosion resistance (AASST) according to the following evaluation criteria.

[0084] <Evaluation criteria>

[0085] A: The area ratio is less than 10%.

[0086] B: The area ratio is 10% or more and less than 20%.

[0087] C: The area ratio is 20% or more.

[0088] (Initial hydrophilicity evaluation method)

[0089] Drop 1 drop of water on the surface of the evaluation sample, measure the contact angle at the moment of dropping with a contact angle measuring device, and evaluate the initial hydrophilicity according to the following evaluation criteria.

[0090] <Evaluation criteria>

[0091] A: The contact angle is less than 10°.

[0092] B: The contact angle is 10° or more and less than 30°.

[0093] C: The contact angle is 30° or more.

[0094] (Durable hydrophilicity evaluation method)

[0095] After drying the surface of the evaluation sample immersed in water for 96 hours, drop 1 drop of water on its surface, measure the contact angle at the moment of dropping with a contact angle measuring device, and evaluate the durable hydrophilicity according to the following evaluation criteria.

[0096] <Evaluation criteria>

[0097] A: The contact angle is less than 20°.

[0098] B: The contact angle is 20° or more and less than 40°.

[0099] C: The contact angle is 40° or more.

[0100] (Method for evaluating sealing property)

[0101] On the surface of the evaluation sample, while pressing a wet gauze with a load of 500 g, reciprocally rub it within a specified range. Measure the number of reciprocations until peeling occurs, and evaluate the initial sealing property according to the following evaluation criteria. In addition, after drying the surface of the evaluation sample immersed in water for 96 hours, while pressing a wet gauze with a load of 500 g, reciprocally rub it within a specified range. Measure the number of reciprocations until peeling occurs, and evaluate the durability sealing property according to the following evaluation criteria.

[0102] <Evaluation criteria>

[0103] A: The number of reciprocations is 20 or more

[0104] B: The number of reciprocations is 10 or more and less than 20

[0105] C: The number of reciprocations is less than 10

[0106] (Method for evaluating water resistance)

[0107] After drying the surface of the evaluation sample immersed in water for 96 hours, measure the mass (E M ) of the evaluation sample, and calculate the change rate [(1 - E M / S M )×100] relative to the mass (S M ) of the evaluation sample before immersion in water, and evaluate the water resistance according to the following evaluation criteria.

[0108] <Evaluation criteria>

[0109] A: The change rate is 10% or less

[0110] B: The change rate is greater than 10% and 25% or less

[0111] C: The change rate is greater than 25%

[0112] (Color fastness)

[0113] Based on the salt spray test method (JIS-Z-2371: 2015), after 72 hours of neutral salt spray, calculate the area ratio (%) of blackening generated on the surface of the evaluation sample, and evaluate the color fastness according to the following evaluation criteria. In addition, consider the evaluation result of B or above as qualified.

[0114] <Evaluation criteria>

[0115] A: The area ratio is 10% or less

[0116] B: The area ratio is greater than 10% and less than or equal to 30%

[0117] C: The area ratio is greater than 30%

[0118] The corrosion resistance evaluation results, hydrophilicity evaluation results, sealing performance evaluation results, water resistance evaluation results, and color fastness to water evaluation results of each evaluation sample are shown in Table 2 and Table 3 respectively. In addition, those with evaluation results of B or above are considered qualified.

[0119] [Table 2]

[0120]

[0121] [Table 3]

[0122]

[0123] In addition, although the present invention has been described in detail with reference to specific embodiments, it is obvious that those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention.

Claims

1. A method for manufacturing a metallic material with a coating, comprising: A process of bringing a metal surface treatment agent into contact with the surface of a metal material or onto the surface, wherein the metal surface treatment agent contains a water-soluble or water-dispersible resin (A) and a compound (B) having a nitrile group and an amino group, wherein the mass (B) of the compound (B) is... M ) and the mass (A) of the resin (A) M The ratio of [B] M / A M Within the range of 0.03 to 1.50; A process of drying the surface of the metal material or the metal surface treatment agent on the surface in contact with the metal material within a range of 100°C to 200°C at the maximum reach temperature (PMT) of the metal material and within a range of 2 seconds to 1800 seconds.

2. The method for manufacturing a metallic material with a coating according to claim 1, wherein, The resin (A) is a resin having at least one functional group selected from amino, amide, carboxyl and hydroxyl groups.

3. The method for manufacturing a metallic material with a coating according to claim 1 or 2, wherein, The molecular weight of compound (B) is less than 1000.

4. The method for manufacturing a metallic material with a coating according to claim 1 or 2, wherein, The metal surface treatment agent further comprises at least one inorganic compound (C) selected from chromium compounds, vanadium compounds, titanium compounds, and zirconium compounds, wherein the mass (B) of the compound (B) M The mass (C) of the inorganic compound (C) M The ratio of [B] M / C M It is in the range of 0.10 to 5.

00.

5. The method for manufacturing a metallic material with a coating according to claim 1 or 2, wherein, The amount of the film formed on the surface of the metallic material is 0.05 g / m. 2 Above and 1.5g / m 2 Within the following range.

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