JP6619978B2 - Chemical conversion treatment agent, film manufacturing method, film-coated metal material and painted metal material - Google Patents

Description

  A chemical conversion treatment agent for forming a chemical conversion film on the surface of a metal material, a method for producing a chemical conversion film on the surface of a metal material using the chemical conversion treatment agent, and a metal material with a film having a chemical conversion film produced by the method on the surface, The present invention also relates to a coated metal material having a coating film on the chemical conversion film.

  Conventionally, chromate-based, zinc phosphate-based, zirconium-based and other treatment agents have been used as chemical conversion treatment agents. Recently, treatment agents containing bismuth have been proposed. For example, Patent Document 1 contains Bi ions of 10 to 1000 ppm and trivalent Fe ions of 100 to 2000 ppm, [2 × Bi ion concentration + trivalent Fe ion concentration] is 500 to 3000 ppm, and Bi and Fe are acceptable. A metal surface treatment solution that is an aqueous solution having a pH of 3 to 14 containing a chelating agent and a surfactant sufficient for solubilization has been proposed. According to this technique, in addition to being able to perform surface cleaning treatment (degreasing) and coating ground treatment in the same process, excellent coating film adhesion and corrosion resistance can be achieved in the coating process after the treatment. .

JP 2011-26661 A

  The present invention relates to a chemical conversion treatment agent capable of forming a chemical conversion film excellent in revolving properties, corrosion resistance and paint adhesion on the surface of a metal material, and to produce a chemical conversion film on the surface of the metal material using the chemical conversion treatment agent. It is an object of the present invention to provide a method, a coated metal material having a chemical conversion film produced by the method on its surface, and a coated metal material having a coating film on the chemical conversion film.

  As a result of intensive studies to solve the above problems, the present inventors have found that a soluble bismuth component, a soluble organic acid component having a sulfonic acid group, and at least one functional group selected from a carboxyl group and a hydroxyl group. The present inventors have found that a chemical conversion treatment agent containing a soluble organic compound component having a group can form a chemical conversion film having excellent coating coverage, corrosion resistance, and coating adhesion, thereby completing the present invention.

That is, the present invention
(1) A chemical conversion treatment agent for forming a film on the surface of a metal material, wherein at least one functional group selected from a soluble bismuth component, a soluble organic acid component having a sulfonic acid group, a carboxyl group and a hydroxyl group A chemical conversion treating agent comprising: a dissolved organic compound component having:
(2) A method for producing a film on the surface of a metal material, the method comprising a contact step of bringing the chemical conversion treatment agent according to (1) into contact with the surface;
(3) The method according to the above (2), further comprising a coating step of coating the surface contacted with the chemical conversion treatment agent;
(4) A film-coated metal material having a chemical conversion film obtained by the contact step according to (2) on the surface;
(5) A coated metal material having a coating film formed by the coating process according to (3) above on the surface of the coated metal material according to (4) above;
Etc.

  ADVANTAGE OF THE INVENTION According to this invention, the chemical conversion treatment agent which can form on the surface of a metal material the chemical conversion film excellent in the revolving property with coating, corrosion resistance, and coating adhesion, The chemical conversion film on the surface of a metal material using this chemical conversion treatment agent , A coated metal material having a chemical conversion film produced by the method on the surface, and a coated metal material having a coating film on the chemical conversion film.

The chemical conversion treatment agent in the present invention,
A dissolved bismuth component;
A soluble organic acid component having a sulfonic acid group;
A dissolved organic compound component having at least one functional group selected from a carboxyl group and a hydroxyl group;
It is a chemical conversion treatment agent containing. Hereinafter, the said chemical conversion treatment agent (component, composition, liquid property), the manufacturing method of the said chemical conversion treatment agent, the usage method of the said chemical conversion treatment agent, etc. are demonstrated in order.

≪Chemical conversion treatment agent≫
<Ingredient>
(Dissolved bismuth component)
The dissolved bismuth component according to the present invention may be in any form as long as it is dissolved in the agent. For example, bismuth ion form, other components (typically dissolved organic acid having a sulfonic acid group) The form which formed the complex with the component and / or the soluble type organic compound component which has at least 1 functional group selected from a carboxyl group and a hydroxyl group can be mentioned.

(Dissolved organic acid component having a sulfonic acid group)
The dissolved organic acid component having a sulfonic acid group according to the present invention may be in any form as long as it is dissolved in the agent, for example, non-dissociated state, ionic form, other components (typically May be a form in which a complex or soluble compound (such as an ester) is formed with a soluble bismuth component).

(Dissolved organic compound component having at least one functional group selected from a carboxyl group and a hydroxyl group)
The dissolved organic compound component having at least one functional group selected from a carboxyl group and a hydroxyl group according to the present invention may be in any form as long as it is dissolved in the agent, for example, non-dissociated state, ion And a form in which a complex or a soluble compound (for example, ester) is formed with another component (typically, a dissolved bismuth component).

<Liquid>
The pH of the chemical conversion treatment agent according to the present invention is not particularly limited, but is preferably 2.0 or more and 9.0 or less, and more preferably 2.5 or more and 6.5 or less. . When the pH is within the above range, it is possible to form a film having better coating-around property, corrosion resistance, and coating adhesion. Here, pH in this specification is the value measured about the agent in 25 degreeC using the pH meter.

<Long-term liquid stability>
It is preferable that the chemical conversion treatment agent in the present invention is stable and does not decompose for a long period (at least 30 days). In particular, since chloride ions and sulfate ions are also contained in general tap water and groundwater, it is desirable that even if they are mixed, the liquid does not decompose and is stable for a long period of time.

  As a method for confirming the liquid stability, chloride ions and sulfate ions are added to the treatment agent, and after a certain period of time (at least 30 days), the liquid properties (for example, visually confirm that precipitates are not formed). A method for evaluating the above (an anion-resistant component evaluation test) is suitable.

≪Method for producing chemical conversion treatment agent≫
The chemical conversion treating agent according to the present invention includes, for example, a soluble bismuth component source, a soluble organic acid component source having a sulfonic acid group, and a soluble organic compound having at least one functional group selected from a carboxyl group and a hydroxyl group Although it can manufacture by mix | blending a component source with a liquid medium, you may mix | blend another component as needed.

<Raw material>
(Dissolved bismuth source)
The dissolved bismuth source is not particularly limited as long as it contains bismuth atoms. For example, bismuth oxide, bismuth hydroxide, bismuth chloride, bismuth chloride oxide, bismuth sulfate, bismuth methanesulfonate, ethanesulfonic acid Examples thereof include bismuth ions, bismuth iodide, bismuth sulfide, bismuth tellurate, bismuth titanate, bismuth oxynitrate, and bismuth nitrate that can form bismuth ions or bismuth complex ions in the chemical conversion treating agent. A plurality of these components may be used.

(Source of dissolved organic acid component having a sulfonic acid group)
The source of the soluble organic acid component having a sulfonic acid group is, as such, when the component is water-soluble, as it is, when the component is poorly water-soluble or insoluble, a water-soluble salt {cationic pair that forms the salt As the ions, for example, metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, etc. may be used. The source of the soluble organic acid component having a sulfonic acid group is not particularly limited as long as it contains one or more sulfonic acid groups. For example, alkylsulfonic acid, hydroxyalkylsulfonic acid, fluoromethanesulfonic acid , Trifluoromethanesulfonic acid, vinylsulfonic acid, taurine and other low molecular weight compounds (with a molecular weight of 2000 or less), or salts thereof (for example, alkali metal salts (sodium salt, potassium salt, lithium salt, etc.), alkaline earths Metal salts such as metal salts (magnesium salt, calcium salt, barium salt), ammonium salts, etc. can be mentioned}. Particularly suitable organic acids are low molecular weight compounds such as alkyl sulfonic acids and hydroxyalkyl sulfonic acids (having a molecular weight of 2000 or less) or salts thereof (for example, alkali metal salts (sodium salts, potassium salts, lithium salts, etc.), Metal salts such as alkaline earth metal salts (magnesium salts, calcium salts, barium salts), ammonium salts, etc.}, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2- Propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, 1-pentanesulfonic acid, 2-pentanesulfonic acid, 3-pentanesulfonic acid, 1-hexanesulfonic acid, 2-hexanesulfonic acid, 3-hexanesulfone Acid, hydroxymethanesulfonic acid, 2-hydroxyethane-1-sulfonic acid (a Thionic acid), 2-hydroxypropane-1-sulfonic acid, 1-hydroxypropane-2-sulfonic acid, 3-hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 4-hydroxybutane-1 -Sulfonic acid, 2-hydroxypentane-1-sulfonic acid, 5-hydroxypentane-1-sulfonic acid, 2-hydroxyhexane-1-sulfonic acid, 6-hydroxyhexane-1-sulfonic acid, etc., or salts thereof { Examples include metal salts such as alkali metal salts (sodium salt, potassium salt, lithium salt, etc.), alkaline earth metal salts (magnesium salt, calcium salt, barium salt), ammonium salts, etc.}. A plurality of these components may be used.

(Dissolved organic compound component source having at least one functional group selected from a carboxyl group and a hydroxyl group)
As a source of a soluble organic compound component having at least one functional group selected from a carboxyl group and a hydroxyl group, when the component is water-soluble, it remains as it is, and when the component is poorly water-soluble or insoluble, it is water-soluble. Salt {Cationic counterions forming the salt include, for example, metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, etc. Can be used}. The soluble organic compound component source having at least one functional group selected from a carboxyl group and a hydroxyl group is one containing one or more carboxyl groups and / or one or more hydroxyl groups and having a sulfonic acid group It is not particularly limited as long as it is not, for example, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, alanine, arginine, aspartic acid, etc. An organic compound having one or more carboxyl groups; an organic compound having one or more hydroxyl groups such as ascorbic acid or erythorbic acid; and one or more hydroxyl groups such as lactic acid, gluconic acid, heptogluconic acid, galactonic acid, glyceric acid, or glycolic acid; Organic compound having one carboxyl group; malic acid, tartaric acid, citric acid, isocitric acid Organic compounds having one or more hydroxyl groups and two or more carboxyl groups such as fumaric acid; low molecular weight compounds such as those having a molecular weight of 2000 or less, or salts thereof (for example, alkali metal salts (sodium salt, potassium salt, Lithium salts, etc.), metal salts such as alkaline earth metal salts (magnesium salts, calcium salts, barium salts), ammonium salts, etc.}. A plurality of these components may be used.

  The chemical conversion treating agent of the present invention is a complexing agent other than a soluble organic acid component source having a sulfonic acid group and a soluble organic compound component source having at least one functional group selected from a carboxyl group and a hydroxyl group. Is substantially unnecessary.

(Liquid medium)
The chemical conversion treatment agent of the present invention is an aqueous surface treatment agent. As used herein, “aqueous” refers to a solvent using water alone or a mixed solvent of water and a water-soluble solvent (for example, dimethyl sulfoxide, pyridine, alcohols, etc.), but a saturated aliphatic alcohol. Specifically, it is preferable to use a solvent that does not contain a water-soluble solvent such as saturated aliphatic monoalcohol, saturated aliphatic dialcohol, saturated aliphatic trialcohol, particularly a solvent containing only water. That is, it is preferable that the chemical conversion treatment agent of the present invention does not contain the water-soluble solvent of the saturated aliphatic alcohol. In the case of a mixed solvent, 50% by mass or more of the solvent content is preferably water.

<Composition>
The dissolved bismuth source to be blended in the chemical conversion treating agent according to the present invention is preferably 5 to 2000 ppm, more preferably 10 to 500 ppm as a bismuth-converted mass concentration. The source of the soluble organic acid component having a sulfonic acid group is preferably 3 to 500 mol times, more preferably 10 to 300 mol times bismuth in the chemical conversion treatment agent. The dissolved organic compound component source having at least one functional group selected from a carboxyl group and a hydroxyl group is preferably 1 to 300 mol times, more preferably 5 to 200 mol times bismuth in the chemical conversion treatment agent. When the above-mentioned various components are within the above ranges, it becomes possible to form a film having more excellent paintability, corrosion resistance, and paint adhesion.

  In the production of the chemical conversion treatment agent of the present invention, as described above, other components may be blended. Other components include, for example, surfactants, etching components, metal components (for example, iron, aluminum, zinc, etc .; metals having a higher standard redox potential than bismuth, such as gold, silver, copper, etc.); 71, rare earth elements such as scandium and yttrium; etc.), a pH adjuster, a compound having organosilane as a main chain, a resin (an organic compound having a repeating structure with a molecular weight exceeding 2000), and the like. Metals, rare earth elements, compounds having organosilane as the main chain, resins, etc. having a standard oxidation-reduction potential higher than that of bismuth may be inevitably mixed without being added to the chemical conversion treatment agent. In the case of metals and rare earth elements having a standard oxidation-reduction potential nobler than bismuth, the lower limit of quantification is determined in ICP emission spectroscopic analysis, and in the case of compounds and resins having organosilane as the main chain, in liquid chromatography analysis. May be about 50 times as large.

(Surfactant)
Examples of surfactants include, but are not limited to, polyoxyethylene alkyl ethers. In addition, it is preferable that the chemical conversion treatment agent of this invention contains 400 mg or less of surfactant with the actual use density | concentration with respect to 1 kg of said chemical conversion treatment agents. In general, the chemical conversion treatment includes a degreasing process for removing rust preventive oil from the steel sheet as a pre-process. However, in the actual degreasing process, the rust preventive oil may remain without being completely removed. By including the surfactant, it is possible to remove the remaining rust preventive oil, so that a bismuth film can be stably formed.

(Etching component)
Examples of etching components include hydrofluoric acid, ferric chloride, hydroxylammonium sulfate, and iodine compounds that can form iodine ions when dissolved in a liquid medium, but are not limited thereto. is not. In addition, these etching components may be used alone or in combination of two or more.

(Metal component)
Examples of the metal component include iron, aluminum, zinc and the like; metals having a higher standard redox potential than bismuth such as gold, silver and copper; elements having an atomic number of 57 to 71; rare earth elements such as scandium and yttrium; However, it is not limited to these. In addition, as above-mentioned, these components may be mix | blended with the chemical conversion treatment agent of this invention, and do not need to mix | blend.

  Among metal components, regarding metal components such as iron, aluminum, and zinc, if the chemical conversion treatment agent of the present invention is continuously used in a predetermined metal material, it may be accumulated in the chemical conversion treatment agent of the present invention by etching. However, you may mix | blend these metal components intentionally. Examples of sources of these metal components include ferrous sulfate, ferric sulfate, ferric nitrate, ferric citrate, ferrous lactate, ferrous gluconate, zinc oxide, zinc hydroxide. Zinc sulfate, zinc nitrate, aluminum hydroxide, aluminum nitrate, aluminum sulfate and the like. A plurality of these components may be used. Of the above three metal components, the iron component is particularly useful in that it can form a film having more excellent corrosion resistance by being blended with a certain amount or more of the chemical conversion treatment agent of the present invention. When an iron component is added to the chemical conversion treating agent of the present invention, the supply source of the iron component is an iron equivalent mass concentration, preferably 1 ppm or more, more preferably 10 ppm or more. There is no particular upper limit to this concentration, but it is preferable that the initial concentration be 100 ppm or less. If the chemical conversion treatment agent of the present invention is continuously used, a metal component accumulates from a predetermined metal material by etching, and thus the iron equivalent mass concentration may exceed 100 ppm. In this case, there is no particular upper limit to the iron equivalent mass concentration, but it is preferable to control the iron equivalent mass concentration to 20000 ppm or less.

(PH adjuster)
As the pH adjuster, for example, sodium hydroxide, potassium hydroxide, aqueous ammonia and the like can be used as the pH raising agent. Moreover, methanesulfonic acid, ethanesulfonic acid, sulfuric acid, nitric acid, etc. can be used as a pH lowering agent. A plurality of these pH adjusters may be used.

(Environmental impact component free)
The chemical conversion treatment agent of the present invention has an environmental load element (non-metallic elements such as fluorine, nitrogen, phosphorus and boron, metallic elements such as nickel, chromium and tin) and It is preferable not to contain an environmentally hazardous substance [thiourea compound (including thiourea. Means a compound having a structure of N—C (═S) —N <)]. In this case, since there is inevitable contamination, there is a trace amount, for example, about 50 times the lower limit of quantification in the ICP emission spectroscopic analysis method for environmentally hazardous elements and liquid chromatographic method for environmentally hazardous substances. There may be.

≪How to use chemical conversion treatment agent≫
<Applicable object>
The metal material that can be used in the present invention is not limited, but a base metal having a standard oxidation-reduction potential is more preferable than bismuth, for example, iron (for example, cold rolled steel sheet, hot rolled steel sheet, high tensile steel sheet , Tool steel, alloy tool steel, spheroidal graphite cast iron, gray cast iron, etc.), plating materials, for example, galvanized materials (eg, electrogalvanized, hot dip galvanized, alloyed galvannealed, electrogalvanized alloy plated, etc.), Examples thereof include aluminum materials (for example, 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series, aluminum castings, aluminum alloy castings, die cast materials, etc.).

<Process (film production method)>
The method for producing a film in the present invention is a method for producing a film on the surface of a metal material, and includes a contact step of bringing the chemical conversion treatment agent of the present invention into contact with the surface of the metal material. Examples of the contact method include an electrolytic treatment method performed by passing an electric current, or a treatment method performed without flowing an electric current, such as an immersion treatment method, a spray treatment method, and a pouring treatment method.

  The contact temperature between the metal material and the chemical conversion treatment agent is preferably 10 ° C. or more and less than 60 ° C., more preferably 20 ° C. or more and less than 50 ° C., but is not limited to these temperatures. Further, the contact time between the metal material and the chemical conversion treatment agent is preferably 30 to 300 seconds, more preferably 60 to 180 seconds, but the treatment time is not limited thereto.

  There may be a post-process in the chemical conversion treatment step of the metal material in the present invention. For example, a pickling process, an alkali washing process, a water washing process, a chromate chemical conversion treatment, a zinc phosphate chemical conversion treatment step, a zirconium chemical conversion treatment step, a phosphorous iron chemical conversion treatment step, a drying step and the like can be mentioned. Further, there may be a plurality of these post processes.

  In the method for producing a film in the present invention, a pre-process may be performed before the contact process. Examples of the previous process include a pickling process, a degreasing process, an alkali washing process, a chromate chemical conversion treatment process, a phosphate chemical conversion treatment process using zinc phosphate, iron phosphate, a zirconium chemical conversion treatment process, and a titanium chemical conversion treatment process. , Hafnium chemical conversion treatment process, vanadium chemical conversion treatment process, drying process and the like. A plurality of these pre-processes may be performed in combination. More specifically, a phosphate chemical conversion treatment step is performed as a first chemical conversion treatment step before the contact step, followed by a chromate chemical conversion treatment step, a zirconium chemical conversion treatment step, a titanium chemical conversion treatment step, and a hafnium chemical conversion treatment. You may perform 2nd chemical conversion pretreatment processes, such as a process and a vanadium chemical conversion treatment process.

  In the method for producing a film in the present invention, a coating step using a paint may be performed after the contact step, after the post step, or after the second chemical conversion treatment step. The coating method is not particularly limited, and conventionally known methods such as rolling coating, electrodeposition coating (for example, cationic electrodeposition coating), spray coating, hot spray coating, airless spray coating, electrostatic coating, roller coating, curtain flow Methods such as coating, brushing, and bar coating can be applied.

  Examples of the paint used for the above-mentioned painting include oil-based paints, fibrin derivative paints, phenol resin paints, alkyd resin paints, aminoalkyd resin paints, urea resin paints, unsaturated resin paints, vinyl resin paints, acrylic resin paints, and epoxy resins. Examples thereof include paints, polyurethane resin paints, silicon resin paints, fluororesin paints, rust preventive paints, antifouling paints, powder paints, cationic electrodeposition paints, anionic electrodeposition paints, and water-based paints. A plurality of these may be used or combined.

  Examples of methods for curing and drying the paint include natural drying, reduced pressure drying, convective heat drying (for example, natural convection heat drying, forced convection heat drying), and radiation drying (for example, near infrared drying, far infrared radiation). Drying), ultraviolet curing drying, electron beam curing drying, vapor curing and the like. A plurality of these may be used or combined.

  The coating film obtained by the above coating process may be a single layer or multiple layers. When it is a multilayer, the obtained coating film may be different coating means, paints, and curing and drying means.

  In addition, when applying the electrodeposition coating method using an electrodeposition paint as the said coating process, the said contact process, the said post process (especially various chemical conversion treatment processes), or the said 2nd process which is the front process. It is preferable to control the sodium ion concentration in the chemical conversion treatment agent used in the chemical conversion treatment step to less than 500 ppm on a mass basis. Moreover, when the manufacturing method of the membrane | film | coat in this invention includes a some process, after each process, the water washing process may be included, respectively, but one part or all the water washing process may be abbreviate | omitted.

≪Metal material with coating and painted metal material≫
The metal material with a film according to the present invention can be produced by bringing the chemical conversion treatment agent of the present invention into contact with the surface of the metal material. Dry weight of the chemical conversion coating formed by chemical conversion treatment agent of the present invention is that it is less than 40 mg / ^{m 2} or more 800 mg / ^{m 2} as the bismuth content is preferably less than 100 mg / ^{m 2} or more 400 mg / ^{m 2} More preferred.

  The amount of bismuth in the chemical conversion film formed by the chemical conversion treatment agent of the present invention is measured by dissolving the chemical conversion film in concentrated nitric acid and measuring it by atomic absorption analysis or ICP emission spectral analysis, or by measuring each metal material by fluorescent X-ray analysis. It can be measured by the technique to do. In particular, the fluorescent X-ray analysis is preferable because the operation is simple. In addition, X-ray fluorescence analysis can measure the amount of bismuth at a plurality of locations on the same specimen by narrowing down the measurement region (for example, measurement region 10 mmΦ). Available to:

  The metal material with a film of the present invention has a chromate chemical film, a phosphate chemical film, a zirconium chemical film, a titanium chemical film, a hafnium chemical film, or a vanadium chemical film on or under the chemical film. Moreover, you may have 2 or more types of membrane | film | coats among these.

  The coated metal material of the present invention comprises a surface of the metal material with a film, that is, the chemical conversion film, or a chromate chemical conversion film, a phosphate chemical conversion film, a zirconium chemical conversion film, a titanium chemical conversion film formed on the chemical conversion film. A coating film is provided on the coating film, the hafnium chemical conversion film, or the vanadium chemical conversion film. In addition, this coating film can be formed by the coating process using the said coating material.

<Metal material>
The metal materials are cold-rolled steel plate (hereinafter abbreviated as “CRS material”), alloy galvanized steel plate (zinc basis weight 45 g / m ² ; both sides are hereinafter abbreviated as “GA material”), and A6061 aluminum alloy plate (Hereinafter abbreviated as “AL material”). These metal materials were manufactured by Partec Co., Ltd.

<Reagents, raw materials>
In this example, bismuth nitrate, bismuth nitrate pentahydrate, bismuth oxide, bismuth oxide (III), ascorbic acid, L-Ascorbic Acid, citric acid, and anhydrous citric acid as bismuth nitrate. , L (+)-tartaric acid as tartaric acid, sodium 2-hydroxyethanesulfonate as isethionic acid, polyoxyethylene alkyl (including C12 and C13 alkyl groups) ether (HLB14.0) as surfactant And ferrous sulfate heptahydrate were used as ferrous sulfate, respectively.

<Production of chemical conversion treatment agent>
Using the above-described reagents and raw materials, as shown in Table 1, after blending each component in a predetermined amount, the chemical conversion treatment agent of each Example and each Comparative Example is adjusted by adjusting to a predetermined pH with sodium hydroxide. Produced. In Table 1, “organic acid (sulfonic acid)” is an organic acid component source containing a sulfonic acid group, and “organic compound” is an organic compound component having at least one functional group selected from a carboxyl group and a hydroxyl group. Each source is indicated.

<Manufacture of metal material with bismuth film (metal material with bismuth film)>
Rust preventive oil was removed by spraying a degreasing agent (FC-E2001 manufactured by Nihon Parkerizing Co., Ltd.) at 43 ° C. for 120 seconds on the surface of each metal material. Thereafter, the remaining degreasing agent was removed by spray water washing for 30 seconds. Subsequently, each metal material was immersed in the chemical conversion treatment agent of each example and each comparative example at 35 ° C. for 120 seconds to form a bismuth film on the entire surface of each metal material. The obtained metal material having a bismuth film was washed in order of tap water and deionized water, and dried at 40 ° C.

<Bi adhesion measurement and uniformity evaluation>
Peaks corresponding to bismuth of each metal material having a bismuth film produced by the above method in a region of 10 mmΦ using fluorescent X-rays (wavelength dispersive X-ray fluorescence analyzer: ZSX Primus II manufactured by Co., Ltd.) The integral value was measured. Then, the bismuth adhesion amount of each metal material which has a bismuth film | membrane was calculated | required using the relational expression of the metal material which has a known bismuth adhesion amount, and the obtained peak integral value. In addition, the bismuth adhesion amount was calculated | required by measuring 10 places of each metal material which has a bismuth film | membrane at random, and calculating the average value. Further, the maximum value of the bismuth adhesion amount in each metal material having a bismuth film was divided by the minimum value of the bismuth adhesion amount, and the uniformity of the metal material was evaluated according to the following evaluation criteria. Table 2 shows the results of bismuth adhesion and uniformity of each metal material having a bismuth film.
(Evaluation criteria)
◎: 1.0 or more and less than 1.2 ○: 1.2 or more and less than 1.5 ×: 1.5 or more −: Not measurable (because bismuth adhesion amount is below the limit of quantification)

<Cation electrodeposition coating>
A coating film was obtained by cathodic electrolysis using an electrodeposition paint (GT-100V manufactured by Kansai Paint Co., Ltd.) using each metal material having a bismuth film produced by the above method as a cathode. Cathodic electrolysis was performed at an applied voltage of 180 V and a liquid temperature of 30.0 ± 0.5 ° C. Further, the amount of electricity was adjusted so that the coating thickness was 15.0 ± 1.0 μm, and cathode electrolysis was performed. After the electrodeposition, the surface of the coating film was washed with deionized water and baked at 180 ° C. for 26 minutes to prepare each metal material (each test piece) having the coating film.

<Corrosion resistance test 1 (salt spray test)>
Each test piece was cross-cut using a cutter, and a salt spray test was performed for 1000 hours in accordance with JIS Z 2371. The maximum rust width on both sides from the cut after the salt spray test was measured, and corrosion resistance 1 was evaluated according to the following evaluation criteria. The test results are shown in Table 2.
(Evaluation criteria)
A: 0.0 mm or more and less than 2.0 mm B: 2.0 mm or more and less than 4.0 mm x: 4.0 mm or more

<Corrosion resistance test 2 (salt warm water immersion test)>
Each test piece was cross-cut using a cutter, immersed in a 5.0 mass% aqueous solution of sodium chloride (special grade made by Junsei Kagaku) at 55 ° C. for 240 hours, followed by washing and drying. Then, the tape peeling test using a cello tape (trademark) was performed with respect to the cut part, the both-sides maximum peeling width from a cut part was measured, and corrosion resistance 2 was evaluated according to the evaluation criteria shown below. The test results are shown in Table 2.
(Evaluation criteria)
◎: 0.0 mm or more and less than 2.0 mm ○: 2.0 mm or more and less than 4.5 mm x: 4.5 mm or more

<Coating adhesion test>
Each test piece was immersed in deionized water at 40 ° C. for 240 hours, followed by washing and drying. Thereafter, 11 parallel lines at 1 mm intervals were drawn vertically and horizontally using a cutter on the coating surface to produce 100 grids. Next, a tape peeling test using cello tape (registered trademark) was performed on the grid area, and the number of pieces peeled off from the test piece was measured. The coating results were evaluated for the coating results according to the following evaluation criteria. The results are shown in Table 2.
(Evaluation criteria)
◎: 0 or more and less than 5 ○: 5 or more and less than 15 ×: 15 or more

<Anion-resistant component evaluation test of chemical conversion treatment agent>
Pure chemical special grade sodium chloride and pure chemical special grade sodium sulfate were added to the chemical conversion treatment agents of each Example and each Comparative Example, and stirred so that the chloride ion was 100 mg / kg and the sulfate ion was 100 mg / kg. . After stirring, the appearance of each chemical conversion treatment agent was visually observed, and the resistance to anion components (anion resistance) was evaluated according to the following evaluation criteria. The results are shown in Table 2.
(Evaluation criteria)
A: No precipitate was formed after standing at 25 ° C. for 888 hours. ○: No precipitate was formed when left standing at 25 ° C. for 168 hours, but a precipitate was left when left standing for 888 hours. Δ: A precipitate was not formed immediately after the preparation of the chemical conversion treatment agent, but a precipitate was formed when left standing at 25 degrees for 168 hours. X: A precipitate was formed immediately after the preparation of the chemical conversion treatment agent. Had

<Roundness test with paint>
According to a throwing power test method using a four-sheet box (see, for example, paragraphs 0085 to 0090 of Japanese Patent Application Laid-Open No. 2010-90409, etc.), a paint-around test method was performed. In implementation, a 70 × 150 × 0.5 mm stainless steel plate (SUS304) having one surface (the opposite surface to the surface facing the four boxes) sealed with an insulating tape was used as the counter electrode. Further, the liquid level of the paint (“GT-100V” manufactured by Kansai Paint Co., Ltd.) was adjusted to a position where the metal material having the bismuth film and the counter electrode were immersed by 90 mm. The temperature of the paint was kept at 30 ° C., and the paint was stirred with a stirrer.

In such a state, a coating film was electrolytically deposited on the surface of a metal material having a bismuth film in a 4-box by a cathodic electrolysis method using a counter electrode as an anode.
Specific electrolysis conditions were cathodic electrolysis using a rectifier at a predetermined voltage for 180 seconds. The voltage was adjusted so that the coating thickness of the surface facing the counter electrode of the metal material having the bismuth film closest to the counter electrode of the four-sheet box was 20 μm. Subsequently, each metal material having a bismuth film was washed with water and then baked at 180 ° C. for 26 minutes to form a coating film.

And the film thickness of the coating film formed on the counter electrode side of the metal material having the bismuth film farthest from the counter electrode is measured by an electromagnetic film thickness meter (when the metal material is SPC or GA) or an eddy current film thickness meter. (When the metal material is AL). The thickness of the coating film formed on the counter electrode side of the metal material having the bismuth film farthest from the counter electrode was obtained by measuring the film thickness at 10 randomly selected locations and calculating the average value. . Using the obtained coating film thickness, the wrapping property with coating was evaluated according to the following evaluation criteria. The results are shown in Table 2.
(Evaluation criteria)
A: 9 μm or more ○: 5 μm or more and less than 9 μm x: Less than 5 μm

Claims (5)

A chemical conversion treatment agent for forming a film on the surface of a metal material,
A dissolved bismuth component;
A soluble organic acid component having a sulfonic acid group;
A dissolved organic compound component having at least one functional group selected from a carboxyl group and a hydroxyl group;
Iron components,
Chemical conversion treating agent containing. A method for producing a film on the surface of a metal material,
A method comprising a contact step of bringing the chemical conversion treatment agent according to claim 1 into contact with the surface.   The method according to claim 2, further comprising a coating step of coating the surface contacted with the chemical conversion treatment agent.   The metal material with a film | membrane which has the chemical conversion film obtained by the contact process of Claim 2 on the said surface.   The coating metal material which has the coating film formed by the coating process of Claim 3 on the surface on the metal material with a film of Claim 4.