WO2012157758A1

WO2012157758A1 - Liquid for forming microstructure film on metal surface

Info

Publication number: WO2012157758A1
Application number: PCT/JP2012/062821
Authority: WO
Inventors: 明塩澤; 恒夫楯; 佐藤　幸弘; 川村　緑; 剛白鳥; 聡白鳥
Original assignee: Shiozawa Akira; Tate Tsuneo; Sato Yukihiro; Kawamura Midori; Shiratori Tsuyoshi; Shiratori Satoshi
Priority date: 2011-05-18
Filing date: 2012-05-18
Publication date: 2012-11-22
Also published as: CN103597116A; JP6006475B2; JP2012241215A; CN103597116B

Abstract

The purpose of the present invention is to provide a liquid for forming a microstructure film on a metal surface with which, by the simple immersion of a metal product in the liquid or the application or spraying of the liquid onto the metal product, it is possible to completely remove rust from the surface of the metal product, form a microstructure film having crystals or irregularities of 1 µm or smaller on the surface of the metal product such that the surface area is increased, impurities are prevented from penetrating inside the crystals, and the film easily imitates deformation of the metal substrate. The liquid for forming a microstructure film on a metal surface comprises, as the essential components, phosphoric acid, an inorganic acid, a nonionic fluorine surfactant, and water, and contains 2 to 60 mass% of phosphoric acid, 0.02 to 5 mass% of an organic acid, and 0.005 to 0.2 mass% of a nonionic fluorine surfactant.

Description

Liquid for forming microstructural film on metal surface

The present invention relates to a microstructure forming liquid on a metal surface, and more specifically, relates to a microstructured film forming liquid on a metal surface capable of forming a film having a fine uneven structure on the metal surface.

At present, it is estimated that in Japan, 1 ton of iron per minute, that is, about 500,000 tons per year rusts. (Noboru Masuko, Professor Emeritus, The University of Tokyo, published by the Japanese Standards Association).
Degradation of materials that cause failures in equipment, structures, piping systems, etc. that use metal materials can be broadly divided into three types: corrosion, embrittlement, and fatigue. The cause of the failure is a lot of corrosion embrittlement and corrosion fatigue, and the failure caused by “rusting” of the metal material often generates many chain reactions, which often leads to a larger loss.

In order to prevent the above loss, it is necessary to carry out rust prevention processing to the metal, and about 60% of rust prevention measures are performed by painting. In the case of most of the painting of the components performed indoors, pretreatment is performed. As the method, for example, in Japanese Patent Application Laid-Open No. 11-6076 (Patent Document 1), at least one selected from the group consisting of water-insoluble zinc phosphate, zinc calcium phosphate and calcium phosphate in advance is used. A method for phosphate treatment of steel materials is described in which treatment is performed with a surface conditioning solution containing essential components, followed by treatment with a phosphate treatment solution containing calcium ions as essential components. In addition, the Parkerizing method, in which rust is removed with dilute hydrochloric acid, washed, and neutralized, is typically used. Currently, as a rust-preventing method, a polymer of aniline or a derivative thereof is interposed between zinc phosphate layers. A method for forming a rust-preventing composition by containing a calated composite has been developed.

However, after removing the metal rust as described above, it is necessary to go through an acid removal step, a water washing step, a neutralization step, and an alkali treatment step in order to perform rust prevention plating. Also, in the painting process, it is necessary to go through many processes such as acid removal process, neutralization process, alkali rust prevention process, rust prevention process, rust removal liquid removal process and washing process. And the work efficiency is very bad. And this situation has not improved even now.

Even when a solution neutralized with dilute hydrochloric acid or dilute sulfuric acid used for cleaning is discarded, the solution is toxic and cannot be discarded unless it is diluted with water in large quantities. is doing. Furthermore, since the usual rust remover is toxic, it needs to be washed with water. However, if the metal surface is not subjected to rust prevention treatment, the metal is immediately rusted by the water used for washing. In addition, there is a problem that rust is generated in a short time outdoors even if the metal surface is subjected to rust prevention treatment.

Currently, surface treatments such as painting and plating account for about 85% of the “rust prevention” measures for iron. At present, stainless steel developed to prevent rust is also struggling to prevent moray rust.
Various types of rust removing agents and rust preventive agents used for removing metal rust are known. For example, there are those described in Japanese Patent No. 3858047 (Patent Document 2). Patent Document 2 discloses a rust removing / rust preventive agent having an effect of removing rust and preventing rust with a single solution. However, in this patent, it is a rust removing / rust preventing agent using acetic acid or fatty acid, and there is no disclosure or suggestion about the structure formed on the metal surface by such a liquid, and it was used as a coating ground treatment. The coating performance and rust prevention effect are not sufficient.

Japanese Patent Laid-Open No. 11-6076 Japanese Patent No. 3858047

The object of the present invention has been made in view of the above-mentioned problems, and is to provide a microstructured film-forming liquid on a metal surface, which can form a film with a fine uneven shape on the metal surface.
It is another object of the present invention to provide a microstructured film forming liquid capable of removing rust from a metal member in which rust has been generated and capable of forming a microstructured film on a metal surface.
Specifically, the rust on the surface of the metal product can be completely removed by immersing the metal product in the liquid of the present invention, or simply applying and spraying the liquid on the metal product, and the diameter ( Forms a crystal or irregular structure with a size of approximately 1 μm or less, such as the maximum diameter or average diameter or cross-sectional area) and dimensions (long axis or average axis, etc.), increases the surface area, and impurities in the crystal Disclosed is a liquid for forming a fine-structure film on a metal surface, which can form a fine-structure film that is difficult to penetrate and can easily follow the deformation of a metal substrate.

In addition to phosphoric acid, organic acid and water, the present invention contains a nonionic fluorosurfactant, and by containing these in a specific blending ratio, without containing acetic acid, fatty acid, alcohol or silicon The inventors have found that the above problems can be solved.
That is, the microstructured film-forming liquid on the metal surface of the present invention contains phosphoric acid, organic acid, nonionic fluorine-based surfactant, and water as essential components, and the phosphoric acid is contained in an amount of 2 to 60 masses. %, 0.02 to 5% by mass of the organic acid, and 0.005 to 0.2% by mass of the nonionic fluorosurfactant.

Preferably, the fine structure forming liquid on the metal surface of the present invention further contains 0.01 to 5% by mass of sodium dihydrogen phosphate dihydrate.

More preferably, in the microstructural film-forming liquid on the metal surface of the present invention, the nonionic fluorosurfactant contains a perfluoroalkylethylene oxide adduct, a fluorine-containing group / hydrophilic group / lipophilic group. It is at least one compound selected from the group consisting of oligomers (perfluoroalkyl sulfonic acid compounds and perfluoroalkyl oxide adducts).

In the present invention, the “fine structure” means an electron microscope (for example, a high-resolution field emission scanning electron microscope S4800 (manufactured by Hitachi, Ltd.), or a high-resolution scanning electron microscope with a three-dimensional analysis function ERA. -8900 (manufactured by Elionix Co., Ltd.)), crystals or irregularities with diameters (maximum diameter or average diameter or cross-sectional area) and dimensions (major axis or average axis etc.) of about 1 μm or less It refers to the crystal structure possessed.

By applying the fine film forming liquid on the metal surface of the present invention by immersing or coating the metal member on the metal member, it becomes possible to easily form a fine crystal or uneven structure on the metal surface.
In addition, when rust is generated in the metal member applied to the microstructure film forming solution of the present invention, the rust can be removed and a microstructure can be formed on the surface of the metal product. .
As described above, since a fine-structured film can be formed on the metal surface, the surface area is increased. Therefore, a metal surface having a film on which a fine structure is formed and a material applied thereon, for example, a paint, are formed. The contact area increases and the adhesion becomes stronger.
In addition, the fine structure makes it difficult for impurities to enter the metal.

Specifically, when a metal product having a microstructure film formed by the microstructure coating liquid of the present invention is coated, a so-called anchor effect is obtained in which the coating enters the microstructure and the adhesion to the metal product is increased. Therefore, it can be applied as an excellent paint base film. Furthermore, since the film is fine, a sufficient anchor effect can be obtained even with a thin film, and the adhesion is enhanced.
Further, since the fine structure formed by the present invention is a dense crystal structure, foreign matter such as crystallization water hardly stays inside the crystal, and can be applied as a coating base film having excellent thermal resistance such as heat cycle property.

The film formed according to the present invention is fine, and even if it is thin, a sufficient film thickness can be realized because a sufficient effect is exhibited. And since thin metal film | membrane can fully follow even if a metal product deform | transforms etc., the tolerance with respect to a deformation | transformation, extension, etc. of a metal product is high.
Since the surface area of the metal is increased because the structure formed by the present invention is fine, the metal product subjected to the film treatment with the present microstructured film forming liquid has excellent current-carrying characteristics. Therefore, when electrodeposition coating is performed, the coating can be performed at a low voltage.
Since the effect can be obtained even if the formed film is very thin, it can be applied to the case where dimensional accuracy is required or the use in which the increase in the thickness of the material is restricted by the film.

In addition to the above effects, the microstructural film-forming liquid containing sodium dihydrogen phosphate dihydrate works more powerfully as an auxiliary to form an ultrafine-structured film and has a rust prevention function and coating. Further improvement in the effect as the undercoat, anchor effect, and current-carrying characteristics can be expected.
In particular, the above-described effects can be achieved particularly effectively by suitably using a perfluoroalkylethylene oxide adduct and / or a perfluoroalkyl oxide adduct as the nonionic fluorine-based surfactant.

2 is a SEM (electron microscope) photograph of the surface of a steel member of Example 1. 3 is a SEM (electron microscope) photograph of the surface of a steel member of Example 2. 3 is a SEM (electron microscope) photograph of the surface of a steel member of Example 3. 4 is a SEM (electron microscope) photograph of the surface of a steel member of Example 4. 6 is a SEM (electron microscope) photograph of the surface of a steel member of Example 5. 7 is a SEM (electron microscope) photograph of the surface of an aluminum member of Example 6. Example 7 is a SEM (electron microscope) photograph of the surface of a magnesium alloy member. 10 is a SEM (electron microscope) photograph of the surface of a SUS410 member of Example 8. 10 is a SEM (electron microscope) photograph of the surface of a SUS304 member of Example 9. It is a SEM (electron microscope) photograph of the steel member surface of Example 10. 2 is a SEM (electron microscope) photograph of the surface of a steel member of Example 11. It is a SEM (electron microscope) photograph of the steel member surface of Example 12. It is a SEM (electron microscope) photograph of the steel member surface of Example 13. It is a SEM (electron microscope) photograph of the steel member surface of Example 14. It is a SEM (electron microscope) photograph of the steel member surface of Example 15. It is a SEM (electron microscope) photograph of the steel member surface of Example 16. It is a SEM (electron microscope) photograph of the steel member surface of Example 17. It is a SEM (electron microscope) photograph of the steel member surface of Example 18. 2 is a SEM (electron microscope) photograph of the surface of an iron member of Comparative Example 1. 4 is a SEM (electron microscope) photograph of the surface of an iron member of Comparative Example 2. 10 is a SEM (electron microscope) photograph of the surface of a steel member of Comparative Example 3. 10 is a SEM (electron microscope) photograph of the surface of a steel member of Comparative Example 4. It is a photograph of the cylindrical bending test result (φ20 mm cylindrical mandrel) of Example 1. It is a photograph of the cylindrical bending test result (φ20 mm cylindrical mandrel) of Example 2. It is a photograph of the cylindrical bending test result (φ20 mm cylindrical mandrel) of Example 3. It is a photograph of the cylindrical bending test result (φ20 mm cylindrical mandrel) of Comparative Example 1. It is a photograph of the cylindrical bending test result (φ25 mm cylindrical mandrel) of Comparative Example 1.

Hereinafter, although this invention is demonstrated in detail using a suitable example, it is not limited to these.
The microstructure film-forming liquid of the present invention comprises phosphoric acid, an organic acid, a nonionic fluorosurfactant, and water as essential components, 2 to 60% by mass of the phosphoric acid, and the organic acid. 0.02 to 5% by mass, and 0.005 to 0.2% by mass of the nonionic fluorosurfactant.
By having such a structure, a fine structure film can be formed on the metal surface and the above-mentioned effectiveness can be exhibited. Further, when rust is generated on the metal member, the rust generated on the surface of the metal member is removed and the fine structure film is formed. The forming liquid of the present invention does not contain acetic acid, fatty acid, alcohol or silicon.

The phosphoric acid used in the microstructured film forming liquid of the present invention is not particularly limited, and orthophosphoric acid, condensed phosphoric acid, and polymerized phosphoric acid (polyphosphoric acid) can be used.
The amount of phosphoric acid is 2 to 60% by mass, preferably 5% by mass or more, and more preferably 40 to 60% by mass in the forming liquid of the present invention.
The more phosphoric acid is added, the shorter the time required to remove rust, but when the phosphoric acid content is less than 2% by mass, the time required to remove rust is too long. If the work efficiency deteriorates and exceeds 60% by mass, the time required to remove rust is shortened, but the surface of the metal product becomes dark, which is not preferable.

In addition, examples of the organic acid used in the microstructured film forming liquid of the present invention include malic acid (DL-malic acid), tartaric acid, citric acid, formic acid, methanesulfonic acid and the like.
The mixing ratio of the organic acid is 0.02 to 5% by mass, preferably 0.1 to 1.0% by mass in the forming liquid.
The more organic acid is added, the more effective the rust prevention effect can be. However, if the ratio is less than 0.02% by mass, the rust prevention effect is hardly exhibited, and if it exceeds 5% by mass, the economic effect is poor. It is not preferable.
By containing the organic acid in the microstructured film forming liquid of the present invention, a metal complex is locally formed to promote the elution of the metal, and phosphate ions react with the eluted metal complex to form fine crystals. This is considered to contribute to the formation of the structure.

Further, as the surfactant used in the microstructured film forming liquid of the present invention, a nonionic and fluorosurfactant is used.
Even when a surfactant other than the nonionic fluorine-based surfactant is used, a fine structure can hardly be formed on the metal surface.

Fluorine-based surfactants are those in which hydrogen atoms in the alkyl chain are replaced with fluorine atoms, are physicochemically stable, have a lower surface tension than surfactants that do not contain fluorine atoms, By using a nonionic surfactant, it is considered that a fine structure is formed on the metal surface due to the structure of the hydrophilic portion, and a better rust prevention effect is exhibited. By adding a nonionic fluorosurfactant, the permeability can be promoted and a microstructured film can be formed on the surface of the metal member. Therefore, it is possible to achieve a long-term rust prevention effect.
The fluorosurfactant used in the present invention is (1) strong acid, (2) has a surface tension reducing effect with a small amount, (3) leveling property, low foaming property, (4) added to liquid When dissolved, it can be dissolved uniformly and (5) has an action of being permeable to metals and can be used appropriately in the present invention.

The nonionic fluorosurfactant is not particularly limited, but is a perfluoroalkylethylene oxide adduct, a fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer (for example, perfluoroalkylsulfonic acid compound and perfluoroalkyl). Examples thereof include at least one compound selected from the group consisting of oxide adducts).
As the nonionic surfactant, commercially available compounds can be used. For example, Novec FC-4430, FC-4432 (both are 3M companies), Surflon S241, S242, S243, S286, for example. (All are AGC Seika Chemical Co., Ltd.), Footent 251 (Neos Co., Ltd.), MegaFuck F410, F444, EXP. Examples thereof include TF-2066 (all of which are DIC Corporation), Unidyne DS401, DS403, and the like.

The blending ratio of the nonionic fluorosurfactant is 0.005 to 0.2% by mass, preferably 0.01 to 0.1% by mass in the forming liquid.
If the blending ratio is less than 0.005% by mass, the effect is thin, and if it exceeds 0.2% by mass, the economic effect is poor, which is not preferable.

Furthermore, although the microstructure film forming liquid of the present invention is an aqueous solution and water is an essential component, for example, fresh water such as tap water can be used, and preferably has an electrical conductivity of 20 μS from the viewpoint of preventing corrosion. The following is desirable.
For example, when the phosphoric acid, organic acid, or nonionic fluorine-based sea surface active agent is diluted and used as an aqueous solution, the water may be water contained in the aqueous solution.

Preferably, the microstructured film forming liquid of the present invention contains sodium dihydrogen phosphate dihydrate.
Sodium dihydrogen phosphate dihydrate works more powerfully as an auxiliary agent to form a micro-structure film, and can be expected to further improve the effect as a rust preventive function, paint base film, anchor effect, and current-carrying characteristics, The preferred mixing amount is 0.01 to 5% by mass, preferably 0.02 to 0.5% by mass in the forming liquid of the present invention.

The fine-structure film-forming liquid of the present invention comprises the phosphoric acid, organic acid, nonionic fluorine-based surfactant and water, and further, if necessary, sodium dihydrogen phosphate dihydrate. Can be prepared.
The forming liquid can be formed as one liquid, or can be used by forming a separate liquid. Specifically, a phosphoric acid liquid and an organic acid liquid are separately prepared. The nonionic fluorosurfactant may be put in a phosphoric acid solution, in an organic acid solution, or in both methods.
In this case, the metal may be immersed in the organic acid aqueous solution after being immersed in the phosphoric acid aqueous solution, or the metal may be immersed in the phosphoric acid aqueous solution after being immersed in the organic acid aqueous solution. The inventive microstructured film is formed.

The metal that can be applied to the microstructured film forming liquid of the present invention is not particularly limited, and examples thereof include iron, copper, aluminum, stainless steel, alloys thereof, and magnesium alloys.
By immersing, coating or spraying these metals in the forming liquid of the present invention (room temperature to 60 ° C.), a fine crystal uneven structure can be formed on the surface of the metal member.
Particularly preferably, an organic acid aqueous solution containing a nonionic fluorine-based surfactant is first applied to a metal, sprayed, immersed, etc., and then phosphoric acid containing a nonionic fluorine-based surfactant is applied. This is because an extremely fine crystal uneven structure film can be obtained by such a method.
After immersing the metal member in the forming liquid of the present invention, post-treatment such as washing is not particularly necessary, and it is dried as it is, for example, natural drying or hot air drying, or the remaining liquid is removed with a cloth or the like. Wiping off is enough.
In addition, when rust is generated on the metal to be applied, the rust generated on the metal member can be completely removed by applying the metal member on which the rust is generated to the forming liquid, and then on the metal surface. A fine-structured film is formed.
Further, the forming liquid of the present invention can be used after being diluted or heated depending on the state of occurrence of rust. For example, the liquid dilution ratio is 2 to 10 times, and the liquid temperature is from room temperature to It can be used at 60 ° C.

As described above, the microstructural film forming liquid of the present invention removes rust generated on the metal surface by using it in a metal product, and at the same time forms a microstructural film on the metal surface, and is strong for a long time. Will continue to exhibit a good anti-rust function.
Note that, as described above, the microstructure formed in the present invention is a crystal or unevenness having a diameter (maximum diameter or average diameter or cross-sectional area conversion) or size (major axis or average axis, etc.) of 1 μm or less. The above-described various effects of the present invention are exhibited by having a very fine structure as compared with the following conventional examples.

The present invention is illustrated by the following examples and comparative examples, but is not limited thereto.
(Materials used)
-Phosphoric acid aqueous solution: Nippon Chemical Industry Co., Ltd. Orthophosphoric acid 85% Phosphoric acid-Organic acid (malic acid): Fuso Chemical Co., Ltd. Food additive Malic acid fuso-Organic acid (tartaric acid): Showa Kako Co., Ltd. Reagent-organic Acid (citric acid): manufactured by Tanabe Seiyaku Co., Ltd. Reagent / organic acid (formic acid): manufactured by Kishida Chemical Co., Ltd. reagent / organic acid (methanesulfonic acid): manufactured by Kishida Chemical Co., Ltd. reagent / zinc phosphate solution: manufactured by Partec Co., Ltd. Zinc phosphate-treated steel sheet, nonionic fluorosurfactant (perfluoroalkylethylene oxide adduct): Megafac F-444 manufactured by DIC Corporation
Nonionic fluorinated surfactant (fluorinated group / hydrophilic group / lipophilic group-containing oligomer): Megafac F-444 manufactured by DIC Corporation
・ Sodium dihydrogen phosphate hydrate: manufactured by Nippon Kagaku Kogyo Co., Ltd. Reagents ・ Anionic fluorine surfactant: manufactured by DIC Corporation
・ Water: Tap water ・ Steel material: JIS G3141 100 × 70 × 0.8mmt
Copper member: JIS C1100 100 × 70 × 0.8mmt
Aluminum member: JIS H4000, A1050 100 × 70 × 0.8mmt
Magnesium alloy member: JIS H4201, AZ31 100 × 70 × 0.8 mmt
Stainless steel member A: JIS G4305, SUS410 100 × 70 × 0.8 mmt
Stainless steel member B: JIS G4305, SUS304 100 × 70 × 0.8 mmt

Example 1
10% by mass of the phosphoric acid aqueous solution, 0.1% by mass of the malic acid, 0.03% by mass of the perfluoroalkylethylene oxide adduct (nonionic fluorosurfactant), and water as the balance. These were mixed to prepare a film-forming solution.
Subsequently, the member in which rust was generated on the surface of the steel member was immersed in the obtained film forming liquid (40 ° C.) for 20 minutes. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
The surface of the steel member having the coating is photographed by SEM at 3000 times and 10,000 times using a high resolution field emission scanning electron microscope Model ERA-8900 (manufactured by Elionix Co., Ltd., electron beam three-dimensional roughness analyzer with EDX). The results are shown in FIGS. 1 (a) and 1 (b), respectively.
It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 2
Except for using the fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer (nonionic fluorosurfactant) instead of the perfluoroalkylethylene oxide adduct (nonionic fluorosurfactant), In the same manner as in Example 1, the steel member in which rust was generated was immersed in a film forming solution. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
The surface of the steel member having the coating was SEM photographed at 3000 times and 10,000 times using a high resolution field emission scanning electron microscope Model S-4800 (manufactured by Hitachi, Ltd.), and the results are shown in FIG. ) And FIG. 2 (b).
It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 3
The steel member in which rust was generated was immersed in the film forming solution in the same manner as in Example 1 except that the tartaric acid was used instead of the malic acid. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, SEM photographs of fine structures were taken, and the results are shown in FIGS. 3 (a) and 3 (b), respectively. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 4
The steel member in which rust was generated was immersed in the film forming solution in the same manner as in Example 1 except that the citric acid was used instead of the malic acid. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, SEM photographs of fine structures were taken, and the results are shown in FIGS. 4 (a) and 4 (b), respectively. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 5
A microstructured film was formed on the surface of the copper material in the same manner as in Example 1 except that the copper member was used instead of the steel member.
In the same manner as in Example 2, SEM photographs of fine structures were taken, and the results are shown in FIGS. 5 (a) and 5 (b), respectively. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 6
A microstructure film was formed on the surface of the aluminum member in the same manner as in Example 1 except that the aluminum member was used instead of the steel member.
In the same manner as in Example 2, SEM photographs of fine structures were taken, and the results are shown in FIGS. 6 (a) and 6 (b), respectively. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 7
A microstructured film was formed on the surface of the magnesium alloy member in the same manner as in Example 1 except that the magnesium alloy was used instead of the steel member.
In the same manner as in Example 2, SEM photographs of fine structures were taken, and the results are shown in FIG. 7 (a) (5,000 times) and FIG. 7 (b) (10,000 times), respectively. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 8
A microstructure film was formed on the surface of the SUS410 member in the same manner as in Example 1 except that the SUS410 member was used instead of the steel member.
In the same manner as in Example 2, SEM photographs of fine structures were taken, and the results are shown in FIGS. 8 (a) and 8 (b), respectively. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 9
A microstructured film was formed on the surface of the SUS304 member in the same manner as in Example 1 except that the SUS304 member was used instead of the steel member.
In the same manner as in Example 2, SEM photographs of fine structures were taken, and the results are shown in FIGS. 9 (a) and 9 (b), respectively. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 10
The steel member in which rust is generated is coated in the same manner as in Example 1 except that 0.1% by mass of the sodium dihydrogen phosphate dihydrate is further blended in the film forming liquid of Example 1. Immerse in the forming solution. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, an SEM photograph of a fine structure was taken, and the result is shown in FIG. 10 (10,000 times). It can be seen that the obtained ultrafine structure has a concavo-convex shape of about 1 μm, and has a finer structure than Example 1.

Example 11
The steel member in which rust was generated was immersed in the film forming solution in the same manner as in Example 1 except that the film forming liquid of Example 1 was composed of two liquids. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
Specifically, a phosphoric acid aqueous solution in which half of the nonionic fluorosurfactant is blended in the phosphoric acid aqueous solution of Example 1 and a nonionic fluorosurfactant in half of the malic acid in Example 1 are blended. A malic acid solution containing the prepared phosphoric acid aqueous solution was separately prepared. A steel member similar to that used in Example 1 was first immersed in the phosphoric acid aqueous solution for 20 minutes and then immersed in malic acid for 1 minute to form a microstructured film on the surface of the steel member. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, an SEM photograph of a fine structure was taken, and the result is shown in FIG. 11 (10,000 times). It can be seen that the obtained ultrafine structure has an uneven shape of about 1 μm.

Example 12
Rust in the same manner as in Example 11 except that the sample was immersed in the phosphoric acid aqueous solution for 20 minutes and then immersed in the malic acid for 1 minute and then immersed in the phosphoric acid aqueous solution for 20 minutes instead of being immersed in malic acid for 1 minute. The steel member in which sag occurred was immersed in a film forming solution. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, a fine structure SEM photograph was taken, and the result is shown in FIG. 12 (10,000 times). It can be seen that the obtained fine structure has an uneven shape of about 1 μm, and has a finer structure than Example 11.

Example 13
The steel member in which rust is generated is immersed in the film forming solution in the same manner as in Example 1 except that the blending ratio of malic acid is 0.02% by mass instead of 0.1% by mass. did. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, a fine structure SEM photograph was taken, and the result is shown in FIG. 13 (10,000 times). It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 14
The steel member in which rust is generated is immersed in the film forming solution in the same manner as in Example 1 except that the mixing ratio of malic acid is 0.05% by mass, instead of 0.1% by mass. did. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, a fine structure SEM photograph was taken, and the result is shown in FIG. 14 (10,000 times). It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 15
The steel member in which rust was generated was immersed in the film forming solution in the same manner as in Example 1 except that the blending ratio of phosphoric acid was 5 mass% instead of 20 mass%. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, a fine structure SEM photograph was taken, and the result is shown in FIG. 15 (10,000 times). It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 16
The steel member in which rust was generated was immersed in the film-forming solution in the same manner as in Example 1 except that the mixing ratio of phosphoric acid was 10% by mass instead of 20% by mass. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 2, an SEM photograph of a fine structure was taken, and the result is shown in FIG. 16 (10,000 times). It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 17
The steel member in which rust was generated was immersed in the film forming solution in the same manner as in Example 1 except that the formic acid was used instead of the malic acid. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 1, SEM photographs (2000 times) of the fine structure were taken, and the results are shown in FIG. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Example 18
The steel member in which rust was generated was immersed in the film forming solution in the same manner as in Example 1 except that the methanesulfonic acid was used instead of the malic acid. The surface of the steel member was rusted, and a microstructured film was formed on the surface of the steel member.
In the same manner as in Example 1, SEM photographs (2000 times) of the fine structure were taken, and the results are shown in FIG. It can be seen that the obtained microstructure has an uneven shape of about 1 μm.

Comparative Example 1
A film was formed on the surface of the steel member in the same manner as in Example 1 except that the zinc phosphate solution was used as the film forming liquid and the steel member that was not rusted was used. The results are shown in FIGS. 19 (a) and 19 (b), respectively.
The thickness of the concavo-convex structure formed on the steel member surface is 2 to 8 μm, and it can be seen that the grain size of the structure is considerably large.
In addition, the zinc phosphate treatment solution contains a lot of zinc ions with a high environmental load, and zinc phosphate itself corresponds to an acute toxic substance, so using zinc phosphate is problematic from the viewpoint of environmental protection. .

Comparative Example 2
In the same manner as in Example 1, except that an anionic fluorosurfactant was used instead of the perfluoroalkylethylene oxide adduct (nonionic fluorosurfactant), the steel member in which rust was generated was used. It was immersed in the film forming solution. Rust on the surface of the steel member was removed. A film was formed on the surface of the steel member.
In the same manner as in Example 2, the surface was taken by SEM. The results are shown in FIGS. 20 (a) and 20 (b), respectively. It can be seen that a film having a fine structure such as an uneven structure or a crystal is not formed on the surface of the steel member.

Comparative Example 3
The steel member in which rust is generated is immersed in the film-forming solution in the same manner as in Example 1 except that the blending ratio of malic acid is set to 0.01% by mass instead of 0.1% by mass. did. Rust on the surface of the steel member was removed. A film was formed on the surface of the steel member.
SEM photographs were taken in the same manner as in Example 2, and the results are shown in FIG. 21 (10,000 times). It can be seen that the crystal structure formed on the surface of the steel member is unclear, the crystal is broken and formed, and a fine film structure cannot be obtained.

Comparative Example 4
The steel member in which rust was generated was immersed in the film-forming solution in the same manner as in Example 1 except that the mixing ratio of phosphoric acid was 3% by mass instead of 20% by mass. Rust on the surface of the steel member was removed. A film was formed on the surface of the steel member.
SEM photographs were taken in the same manner as in Example 2, and the results are shown in FIG. 22 (10,000 times). It can be seen that the crystal structure does not grow well on the surface of the steel member.

Test Example The performance of mechanical properties was evaluated using each of the film-forming metal members obtained by processing in Example 1 and Comparative Example 1 above. In addition, the film-forming metal members obtained in Examples 1 to 3 and Comparative Example 1 were used, respectively, to evaluate the performance against heat cycle and the conductive performance. Further, using each of the film forming solutions of Example 1 (malic acid), Example 4 (citric acid), Example 17 (formic acid), Example 18 (methanesulfonic acid) and Comparative Example 1, slow rust performance evaluated.
(Mechanical property evaluation test)
1) Cupping resistance (1)
The steel members obtained by the treatment in Example 1 and Comparative Example 1 were each coated with a polyester resin powder coating (product name Bileucia) made by Kansai Paint (powder coating). The test was conducted by the test method shown in Table 1. In each example, the number of samples of steel members was two. The results are shown in Table 1.

From Table 1 above, it can be seen that the film according to Example 1 is superior to Comparative Example 1 in terms of cupping resistance for evaluating adhesion due to deformation. Therefore, it is clear that Example 1 is superior to Comparative Example 1 in terms of resistance to deformation and adhesion (adhesion).

2) Cupping resistance (2), adhesion, impact resistance Polyester made by Kansai Paint was applied to the steel members obtained by processing in Examples 1, 4, 17, 17, and Comparative Example 1. Each of the resin powder coatings (product name Bileucia) was coated (powder coating), and the test was conducted with respect to cupping resistance, adhesion performance and impact resistance performance by the test methods shown in Table 2 below.
In Table 2, for each example, the number of samples of steel members was set to 5 each and expressed as an average value. The results are shown in Table 2.

From Table 2 above, the adhesion performance and the impact resistance performance were the same in both Examples and Comparative Examples.
The evaluation value of the anti-cupping performance is the amount of deformation indentation that appears as a crack on the surface of the coating film due to the separation between the coating film when the partial deformation is gradually increased. Therefore, the larger the value is, the more adherence is ensured following the deformation.
From the values in Table 2, it can be seen that those having the ultrafine coating structure of the example are superior in the above-mentioned cupping resistance performance to those of the comparative example.

(Resistance test against heat cycle)
In general, the base metal and the coating film have different coefficients of thermal expansion, which imposes a heavy load on the coating base film, and in a normal environment where the coated product is used, there is always a change in temperature. In order to evaluate the performance of the coating, it is important whether the film formed on the metal surface can maintain good adhesion to the coating film even when stress due to heat cycle is applied.
Accordingly, the steel members obtained in Examples 1 to 3 and Comparative Example 1 were each coated with a polyester resin powder coating (product name: Bileusia) manufactured by Kansai Paint, and the following test methods were used for heat cycle resistance performance. The test was conducted.

Test method (1) Step 1: Heat cycle load 80 ° C. −20 ° C. × 33 cycles 192 hours 30 minutes (Itabashi Rika Kogyo Co., Ltd., Program heat cycle test equipment)
350 minutes per cycle: The temperature was raised from -20 ° C to 80 ° C over 47 minutes. Subsequently, it hold | maintained at 80 degreeC for 165 minutes. Thereafter, the temperature was lowered from 80 ° C. to −20 ° C. in 13 minutes. Thereafter, it was kept at −20 ° C. for 125 minutes.
The above 1 cycle was repeated 33 times.
(2) Step 2: Cylindrical bending test The test was performed according to JIS K5600-5-1 (ISO 1519) bending resistance (cylindrical mandrel). The test results are shown in Table 3 below and FIGS.
However, the equipment used is a TQC mandrel bending tester, No. KT-SP1800 (ISO 1519 / JIS K5600-5-1 compliant product), the cylinder used is a φ20 mm cylindrical mandrel (FIGS. 23 to 26).
FIG. 27 shows a case where the cylinder used is a φ25 mm cylindrical mandrel.

It can be seen that the heat cycle resistance of the microstructure film of Example 1 is superior to that of Comparative Example 1.

(Conductivity test)
The conditions of the conductivity test of each film forming member in the solution are as follows.
Solution: 7% sodium sulfate solution Dimensions of film forming member: 70 × 150 mm
The solution is put in a glass container having a diameter of 150 mm and a depth of 80 mm to a depth of 50 mm. Next, a copper plate having a size of 100 × 200 mm and each film-forming member (treated plate) of Examples 1 to 3 and Comparative Example 1 were immersed vertically (in a standing state) in the liquid. At that time, the distance between the copper plate and the film forming member (treated plate) was 30 mm.
The resistance value between the copper plate and each treatment plate was measured, and the results are shown in Table 4.

Those having a fine crystal structure show a high conductivity value in the liquid, and from Table 4 above, the fine structure-forming film of the present invention has a higher conductivity in the liquid than that of the comparative example. It can be seen that

The microstructure film forming liquid of the present invention has an increased surface area due to such a microstructure, impurities are less likely to enter the crystal, and the film tends to follow the deformation of the metal substrate. It can be used as an excellent paint base film.

(Rust removal performance test)
Steel member plates in which rust is generated on the surface of the steel member (JIS C 1100: 100 × 70 × 0.8 mm) in each of the film forming liquids obtained in Example 1, Example 4, and Examples 17 to 18. Was immersed for 10 minutes. The slow rust performance was evaluated from the weight change (mg / cm ² / min) before and after immersion.
In addition, the rust degree of the said steel member board used for the said test used the SPCC rust board by which all are set to C in evaluation of the rust degree of JISZ0313.
Table 5 below shows the average of the test results performed five times.

As mentioned above, although the Example of this invention and its effect were demonstrated, the scope of the present invention is not limited to these. For example, in this example, it was assumed that all raw materials were blended in one liquid, but it is also possible to use phosphoric acid and organic acid separated into two or more liquids, such as separate liquids. It is.

The fine-structure film-forming liquid on the metal surface of the present invention has the above-described effects and is excellent in adhesion with the paint film, and therefore can be effectively applied as a paint base film-forming liquid.

Claims

Phosphoric acid, an organic acid, a nonionic fluorosurfactant, and water are essential components. The phosphoric acid is 2 to 60% by mass, the organic acid is 0.02 to 5% by mass, A fine film-forming liquid on a metal surface, characterized by containing 0.005 to 0.2% by mass of an ionic fluorosurfactant.
2. The microstructure coating film on a metal surface according to claim 1, further comprising 0.01 to 5% by mass of sodium dihydrogen phosphate dihydrate. Forming liquid.
The fine-structure film-forming liquid on the metal surface according to claim 1 or 2, wherein the nonionic fluorosurfactant is a perfluoroalkyl ethylene oxide adduct, a perfluoroalkyl sulfonic acid compound, and a perfluoroalkyl oxide adduct. A liquid for forming a microstructured film on a metal surface, characterized in that it is at least one compound selected from the group consisting of: