JP7161190B2 - Coating method of coating material, and metal material coated with coating material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a coating method of a coating material applied to the surface of a metal material to be coated, and a metal material coated with the coating material.

Conventionally, by coating the surface of metal materials such as steel and aluminum with a coating material, it is possible to prevent moisture from adhering to the surface of the metal material and prevent rust from occurring ( For example, see Patent Document 1).

JP-A-11-29724 (page 5)

However, in Patent Document 1, it is possible to form a coating layer by coating or immersing a coating material on the surface of a metal material to be coated, in a state in which water is attached due to dew condensation or the like. be. In such a case, on the back side of the coating film of the coating material that covers the metal material, that is, on the side where the coating material contacts the surface of the metal material, chemical reaction occurs between the moisture adhering to the metal surface and the metal, causing rust. There is a problem that the coating material may peel off from the back side due to the rust bumps that occur and grow over time.

In addition, since a large number of fine irregularities such as small scratches are usually formed on the metal surface during processing, even if you try to wipe off the moisture attached to the metal surface, Moisture could not be easily removed, and it was difficult to prevent rust from forming on the back side of the coating material.

Furthermore, gaps may occur between the coating material and the metal surface because the coating material is not sufficiently in contact with the metal surface, or the coating material after coating thermally expands and contracts. In such a case, there is a problem that water, which causes rusting, enters into this gap and a long-term rust prevention effect cannot be obtained.

The present invention has been made by paying attention to such problems, and a method of coating a coating material capable of obtaining a sufficient anticorrosive effect even on the back side of the coating material that coats the surface of the metal material, and a coating. An object of the present invention is to provide a metal material coated with a material.

In order to solve the above problems, the method of coating with a coating material of the present invention includes:
A method for coating a surface of a metal material to be coated with a coating material,
The raw material of the coating material is coated on the surface of the metal material to which moisture is attached, and the components contained in the raw material and moisture in the air are chemically reacted, and the components contained in the raw material and the surface of the metal material are coated. It is characterized by forming a thin film coating material containing SiO ₂ as a main component on the surface of the metal material by chemically reacting with adhering moisture.
According to this feature, the water that causes rust adhering to the surface of the metal material is used in a chemical reaction for the generation of a coating material mainly composed of SiO ₂ , so that the metal material is coated. In addition to being able to rapidly chemically react from both the surface side and the back layer side of the raw material coated, it can prevent rusting on the back layer side of the coating material coated on the metal material, and furthermore closely adheres to the surface of the metal material. It is possible to produce a coating material with high rust resistance that coats under conditions.

The surface layer surface of the coating material is characterized by being a smooth surface on which dimples composed of nano-level fine unevenness are formed.
According to this feature, by forming the surface layer surface of the coating material into a smooth surface with dimples formed of fine unevenness, it is difficult for moisture and foreign matter to adhere to the surface layer of the coating material, and in addition to high rust resistance, Water repellency and antifouling effect can be obtained.

The dimples are characterized in that they are formed by volatilizing a gas produced by a chemical reaction between moisture and components contained in the raw material.
According to this feature, dimples can be uniformly distributed on the surface of the coating material by utilizing volatilization of the gas generated by the chemical reaction between the components contained in the raw material and the moisture.

The coating material is characterized by having a film thickness of 10 nm to 1 μm.
According to this feature, since the coating material has an extremely thin film thickness, the thickness dimension of the metal material hardly changes compared to before coating, and the metal material can be applied to a wide range of uses.

It is characterized in that the surface of the metal material is roughened and then the raw material of the coating material is coated on the surface of the metal material.
According to this feature, by roughening the surface of the metal material in advance, the raw material of the coating material forms a film layer in a state in which it enters the irregularities formed by roughening the surface of the metal material. As a result, the anchor effect of the coating material adhering to the metal material is enhanced.

The method is characterized in that the surface of the metal material is coated with the raw material of the coating material after moisture is applied to the surface of the metal material.
According to this feature, the chemical reaction between the moisture attached to the surface of the metal material and the raw material of the coating material in contact with the surface of the metal material can be promoted.

The metal material coated with the coating material of the present invention is
A metal material whose surface is coated with a coating material,
The raw material of the coating material is coated on the surface of the metal material to which moisture is attached, and the components contained in the raw material and moisture in the air are chemically reacted, and the components contained in the raw material and the surface of the metal material are coated. It is characterized in that a thin film coating material containing SiO ₂ as a main component is formed on the surface of the metal material by causing a chemical reaction with the adhering moisture.
According to this feature, the water that causes rust adhering to the surface of the metal material is used in a chemical reaction for producing a coating material mainly composed of SiO2, so that the coating material is coated on the metal material. It is possible to provide a metal material coated with a high-quality coating material that not only prevents rusting on the back layer side of the metal, but also adheres to the surface.

The metal material is characterized by being made of a metal having a Mohs hardness lower than that of iron.
According to this feature, the coating material can be applied to a metal material having a relatively low Mohs hardness such as aluminum, zinc, lead, tin, gold, silver, copper, or brass. , the Mohs hardness of the coating object can be improved to a value higher than that of iron.

The metal material is characterized by being made of silver or copper.
According to this feature, discoloration and corrosion due to the generation of silver sulfide and copper sulfide can be prevented by coating the surface of the silver or copper metal material with the coating material.

The dimples are characterized by having irregularities with an arithmetic mean roughness Ra of 1 nm to 10 nm.
According to this feature, it is possible to obtain a dimple having a suitable nano-level concave-convex structure.

(a) to (c) are cross-sectional views showing, in chronological order, the mechanism by which a coating material is generated on a metal material in an example. It is the figure which imaged the surface of the metal material with which the coating material was coat|covered by the AFM measurement, (a) is the figure which the coating material covered with 1 layer, (b) is the figure which was covered with 3 layers of coating materials. FIG. 2 is an image of the surface of a metal material subjected to rust prevention, alkali resistance, and acid resistance tests, and (a) to (h) are diagrams showing test materials a to h, respectively. It is a diagram showing the results of testing the physical properties of the surface of aluminum foil by infrared spectroscopy, where (a) is an aluminum foil not coated with a coating material, (b) is an aluminum foil coated with a coating material, and (c). [FIG. 2] is a diagram showing an aluminum foil on which a curved surface portion is formed after being covered with a coating material; FIG. 2 is a diagram showing images of test materials after a first exposure test, (a) showing test materials (A) to (D), and (b) showing test materials (unmarked). It is the table|surface which evaluated the 1st exposure test result of a test material. It is a figure which imaged the test material after the 2nd exposure test, and is a figure which shows a test material (E) and a test material (unmarked). It is the table|surface which evaluated the 2nd exposure test result of the test material. FIG. 2 is an image of the surface of a silver test material subjected to a gas corrosion test, and (a) to (f) are diagrams showing a test material (Fa) to a test material (no mark a), respectively. FIG. 2 is an image of the surface of a copper test material on which a gas corrosion test was performed, and (a) to (f) are diagrams showing a test material (Fb) to a test material (unmarked b), respectively. It is the table|surface which measured the color difference of the silver test material which performed the gas corrosion test. It is the table|surface which measured the color difference of the copper test material which performed the gas corrosion test. It is a table|surface which shows the wear amount of the test material which performed the wear resistance test. It is the figure which imaged the test material which is performing an antifouling test. It is the figure which peeled off the sample from the test material, and imaged the condition which sprayed water. It is the figure which imaged the surface of the test material after peeling a sample. It is the figure which imaged the surface of the test material which performed the surface-roughness test. It is a table|surface which shows the arithmetic mean roughness of the test material which performed the surface-roughness test.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for coating a coating material according to the present invention and a mode for carrying out a metal material coated with a coating material will be described below with reference to FIGS. 1 to 18. FIG.

(Main component of coating material)
The coating material 15 is obtained by chemically reacting a stock solution 10 as a raw material obtained by diluting the main component described later with an organic solvent. A surface layer film having a thickness of several tens of nanometers to 1 μm is formed by performing coating processing such as dropping and spreading to form a single layer or a plurality of layers.

More specifically, the undiluted solution 10 of the coating material 15 is composed of at least a first component, a second component and an inert organic solvent as its main components. The first component is polyalkylsilazane, and includes at least one selected from hexamethyldisilazane, octamethylsilazane, cyclotetrasilazane, and tetramethylsilazane. The second component is perhydropolysilazane, which is an inorganic polymer composed only of —(SiH ₂ NH)— units, ie, silicon, nitrogen and hydrogen, and containing no organic components such as carbon. The coating material is produced by dissolving the first component and the second component in an inert organic solvent at a total concentration of 1 to 40% by mass in the state of the undiluted solution 10 before being applied to the surface of the metal material. . The organic solvent that dissolves the first and second components is preferably an organic solvent that is inert to the above components, such as an ether-based organic solvent.

(Metal material to be coated)
In this embodiment, the metal material 1 to be coated with the coating material 15 is a steel sheet whose surface is zinc-plated with iron (Fe) as the main component, but it is not limited to this as long as it is a metal that can rust even slightly. , for example, metals such as aluminum, zinc, nickel, tin, or copper, or alloys or castings containing any of these as main components, or the surfaces thereof may be subjected to plating such as hot-dip galvanization. The coating material 15 can be applied to various metal materials. Moreover, the metal material 1 is more preferably applied as a construction material or a temporary material used at a construction site or the like.

(Coating method of coating material)
Next, the coating method of the coating material 15 according to the present invention will be described.

First, when the metal material 1 is coated in the rolling process, which is a process prior to shape processing as a final product, a roll coater, for example, is used for the metal material sent in the longitudinal direction in a flat plate shape, although not shown. After coating with the undiluted solution of the coating material, bending and molding are performed by well-known machining.

Next, when coating the coating material 15 on the metal material that has been shape-processed as the final product, there are a method of coating using a jig such as a brush, a method of immersing the metal material in the coating material 15, and the like. As a coating method, a dipping method can be used to achieve uniform coating without unevenness, and good results can be obtained. In the case of coating, one-time coating causes less cracking and peeling of the coating film of the coating material 15 than the case of multiple coatings, and good results can be obtained.

(Mechanism of coating layer formation of coating material)
Next, the mechanism by which the coating layer of the coating material 15 according to the present invention is formed will be described. As shown in FIG. 1(a), in many cases, a plurality of water droplets 6, 6, . . . is doing. When the undiluted solution 10 of the coating material is coated on the surface 2 of the metal material 1 as a thin film by the method described above, the —(SiH ₂ NH) — unit component contained in the undiluted solution 10 is combined with moisture (H ₂ 0) in the air. The chemical reaction produces a coating layer of SiO ₂ with almost 100% purity on the surface 2 of the metal material 1 . Although a small amount of gas (NH ₃ , H ₂ ) is secondarily produced by the chemical reaction described above, these gases naturally volatilize into the atmosphere without remaining on the surface 2 of the metal material 1 .

That is, as shown in FIG. 1(b), the undiluted solution 10 chemically reacts with the moisture contained in the air on the surface layer 10a in contact with the air, resulting in hydrogen, ammonia, etc., which are by-products of the coating material. gas volatilizes from the surface layer, and a SiO ₂ layer 11, which is a coating layer, is formed on the surface layer side.

Further, the undiluted solution 10 of the coating material coated on the surface 2 of the metal material 1 chemically reacts with the moisture 6, 6, . . . As a result, gases such as hydrogen and ammonia rise in the coating layer and volatilize from the surface layer, and the SiO ₂ layer 12, which is the coating layer, is formed on the back layer side.

At the same time, the undiluted solution 10 coated on the surface 2 of the metal material 1 reacts with the hydroxyl groups —OH present terminating on the surface 2 of the metal material 1 and chemically As a result of the reaction, gases such as hydrogen and ammonia rise in the coating layer and volatilize from the surface layer, and the SiO ₂ layer 12, which is the coating layer, is generated on the back layer side.

In this manner, SiO ₂ layers 11 and 12 are first formed on the surface layer 10a and the back layer surface 10b of the undiluted solution 10 of the coating material, respectively. Next, the SiO ₂ layer 11 is spread from the surface layer side to the back layer side, and the SiO ₂ layer 12 is spread from the back layer side to the surface layer side, thereby sequentially forming an intermediate SiO ₂ layer. , and finally a SiO ₂ layer 15 of the coating material is produced over the surface and the rear surface.

As shown in FIG. 1(c), the surface 2 of the metal material 1 before being coated with the coating material 15 may be damaged by small scratches during the manufacturing process, etc., unless special surface treatment such as mirror finishing is performed. A large number of microscopic unevenness portions 3 are formed. The undiluted solution 10 of the coating material covers the surface 2 of the metal material 1 and enters the irregularities 3, and is cured as described above. Since it functions as the anchor portion 17 , the coating material 15 firmly adheres to the surface 2 of the metal material 1 .

In addition, when the surface 2 of the metal material 1 is a smooth surface having almost no irregularities 3 as described above, the surface 2 of the metal material 1 is roughened with a file or the like as a pretreatment for coating with the coating material 15. By doing so, the uneven portion 3 may be positively generated on the surface 2 of the metal material 1, and by doing so, the anchor effect of the coating material 15 can be obtained.

By performing this roughening treatment, it is preferable to form uneven portions 3 having an arithmetic average roughness in the range of about 1 to 500 μm on the surface 2 of the metal material 1. By doing so, the anchor effect of the coating material 15 can be improved. can be enhanced.

After the roughening treatment, the surface 2 of the metal material 1 is cleaned by blowing away metal powder generated by sanding or the like using an air jet means such as an air gun. Furthermore, after this cleaning treatment, by leaving a predetermined time, dew condensation or the like is generated on the surface 2 of the metal material 1, and naturally derived moisture is adhered.

In this case, after roughening and cleaning of the surface 2 of the metal material 1, moisture is applied to the surface 2 of the metal material 1, on which the uneven portions 3 are formed by roughening, by means of moisture imparting means such as spraying. may be actively adhered and then coated with the coating material 15. By doing so, the water adhering to the surface 2 of the metal material 1 and the coating material in contact with the surface 2 of the metal material 1 A chemical reaction with the stock solution 10 can be promoted. It should be noted that the surface 2 of the metal material 1 may be made to adhere to water by means of a water applying means without performing a roughening treatment.

(Shape of coating layer of coating material)
On the surface of the coating film of the coating material 15 that coats the surface 2 of the metal material 1, dimples 16 consisting of nano-level unevenness are formed on the traces of the volatilization of the by-product gas bubbles. More specifically, a large number of bubbles such as hydrogen and ammonia are generated by the chemical reaction described above, and when these bubbles are released into the air from the smooth surface of the coating material, the coating material in contact with the bubbles. It is assumed that nano-level unevenness is generated on the smooth surface due to the influence of the surface tension generated on the surface and the influence of the timing of the initial hardening of the surface accompanying the chemical reaction.

In addition, the dimples 16 formed on the surface of the coating film of the coating material 15 have smaller depth and height dimensions of the unevenness than the uneven portions 3 initially formed on the surface 2 of the metal material 1 before coating. Therefore, by coating the surface 2 of the metal material 1 with the coating material 15, the surface is generated smoother after the coating than before the coating.

Needless to say, the gas, which is a by-product, is uniformly generated on the surface of the coating film of the coating material 15. Therefore, the number of dimples 16 per unit area of the coating film is In this case, the depth of the concave portion and the height of the convex portion are uniformly formed without variation.

The coating material coated on the surface 2 of the metal material 1 includes the dimples 16 formed on the coating material 15 in the case of single-layer coating as shown in FIG. When the dimples 26 formed in the coating material 25 are compared with the dimples 26 formed in the coating material 25 in which the coating material 25 is coated in multiple layers, it is confirmed that the dimples 26 in which the coating material is coated in multiple layers have smaller depth and height dimensions of the unevenness. there is It is assumed that this is because the unevenness of the dimples 16 in the single-layer coating is smoothed out by coating the coating material multiple times, and smoother dimples 26 are formed.

(rust prevention, alkali resistance, acid resistance test)
Next, rust prevention tests i and ii, alkali resistance test and acid resistance test of the metal material coated with the coating material according to the present invention will be described. Of these, in the rust prevention tests i and ii, salt water of a predetermined concentration was continuously sprayed on the test material, and the state of rust formation was observed. First, the rust prevention test i will be explained. The test material a shown in FIG. , and sintered at 150° C. for 30 minutes, and the test material b shown in FIG.

As shown in FIG. 3( a ), the test material a was subjected to the salt spray for 4 hours, but no rust was observed. After 4 hours, spot-like rust was observed. In addition, no rust was observed in the test material a' after the salt water spray was continued for 8 hours, and after 8 hours, spot-like rust was observed. Furthermore, in the test material b, spot-like rust was confirmed several minutes after the start of the salt spray, and as shown in FIG. A pattern of rust was confirmed.

As a result of the above test, it was found that sintering at a predetermined temperature (approximately 150° C.) after coating accelerates the vitrification of the coating material, resulting in an early improvement in the antirust effect.

Next, the rust prevention test ii will be described. The test material c shown in FIG. It is an iron plate coated with a conventionally known coating material.

As shown in FIG. 3(c), when the test material c was sprayed with salt water for 24 hours, spots of rust were confirmed. On the other hand, as shown in FIG. 3(d), when the test material d was sprayed with salt water for 24 hours, many spots of rust were observed.

As a result of the above-described test, the coating material according to the present invention has a significant rust suppression effect as compared with conventionally known coating materials. This is because the coating material according to the present invention vitrifies the metal surface by utilizing moisture, and the coating material according to the present invention actively generates benign black rust on the metal surface to form a coating film on the metal surface. In order to protect , even if spot-like rust (red rust) occurs, it is considered that further growth of rust is suppressed.

Next, in the alkali resistance test, a test material made of aluminum was immersed in alkaline ionized water of a predetermined pH (pH 12.5 in this test), and then the state of the surface of the test material was observed. The test material e shown in FIG. 3(e) is an aluminum plate immersed in the coating material once, and the test material f shown in FIG. 3(f) is an aluminum plate not coated with the coating material for comparison. be.

As shown in FIG. 3(e), even when the test material e was immersed in the alkaline ionized water, no significant change was observed on the surface of the test material. On the other hand, as shown in FIG. 3(f), the surface of test material f changed into a mottled pattern as a result of being eroded by alkali.

As a result of the above tests, it was confirmed that the coating material according to the present invention has high alkali resistance.

Furthermore, in the acid resistance test, a sample made of galvanized steel was immersed in hydrochloric acid of a predetermined concentration (concentration of 9.5% in this test), and then the state of the surface of the sample was observed. The test material g shown in FIG. 3(g) is a galvanized steel sheet immersed in the coating material once, and the test material h shown in FIG. Steel plate.

As shown in Fig. 3(g), even when the sample g was immersed in hydrochloric acid, the galvanization of the sample g remained, and no significant change was observed on the surface. There was no change in appearance. On the other hand, as shown in FIG. 3(h), the zinc plating on the surface of test material h was eroded by hydrochloric acid, and as a result, the metal base with a slightly reddish color was exposed, and the surface was lustrous. also almost disappeared.

As a result of the above test, it was confirmed that the coating material according to the present invention has high acid resistance.

(Coating confirmation experiment)
As Experiment I for confirming the state of coating of the coating material, after coating the coating material 15 according to the present invention on a galvanized steel sheet by the above method, the steel sheet was press-molded at 90 degrees to form an angle portion, Hydrochloric acid having a concentration of about 10% was dripped onto the angle portion, and bubbling of hydrogen was confirmed. For comparison, the same angle portion was also formed on a steel plate not coated with the coating material 15, and the hydrochloric acid was dripped to compare the state of bubbling.

As a result of Experiment I, the amount of hydrogen bubbling was significantly reduced in the steel plate coated with the coating material 15 compared to the steel plate not coated with the coating material 15 . Since the amount of bubbling hydrogen is reduced in this way, it can be seen that the coating material 15 has an acid-resistant effect. Also, from this, it is assumed that the coating material is bent following the steel plate that is press-formed at 90 degrees, and that the coating condition can be maintained even at the angle portions of the steel plate.

Further, as Experiment II for confirming the state of coating, after coating a thin aluminum foil with the coating material 15 according to the present invention, a curved surface portion having a curvature radius R of about 5 mm to 10 mm was formed on the aluminum foil. The physical properties of the surface portion of were tested by a known infrared spectroscopic method. FIG. 4(c) shows the test results in which the curved surface portion was irradiated with infrared rays. For comparison, FIG. 4(a) shows the test results for the aluminum foil itself before being coated with the coating material 15, and FIG. It is a test result for a planar aluminum foil before irradiation. In FIG. 4, the horizontal axis indicates the wave number, and the vertical axis indicates the absorbance.

As shown in FIGS. 4(b) and 4(c), after coating with the coating material 15, peaks derived from Si—O bonds are similarly obtained regardless of whether the curved surface portion is formed or not. Therefore, it was confirmed that the coating material 15 coated on the aluminum foil was formed into a curved surface following the curved surface of the aluminum foil with a curvature radius R of about 5 mm to 10 mm. Therefore, the coating material 15 has a function of having flexibility to follow a curved surface having a radius of curvature R of 5 mm or more.

If the thickness of the coating material 15 that covers the surface 2 of the metal material 1 exceeds 1 μm, there is a possibility that the metal material 1 cannot follow the bending process after coating. Fear increases. Therefore, it is considered best to form the film thickness of the coating material 15 within the range of 500 nm to 1 μm.

(First exposure test)
Next, the first exposure test of the metal material coated with the coating material according to the present invention will be described. In this first exposure test, metal test materials (A) to (D) each coated with a plurality of types of coating materials described later, and a test material (unmarked) not coated with a coating material for comparison. are permanently placed for several months under the same environment exposed to flying foreign substances (in the present embodiment, near the coke oven in the steelworks, under a poor environment exposed to coke oven gas), and these It is a comparison of the conditions of rusting, staining, deposits, or discoloration occurring on the surfaces of test materials (A) to (D) (no mark).

As shown in FIGS. 5(a) and 5(b), a pipe 30 used as an erection material at a construction site or the like was used as a metal test material applied to this test. This pipe 30 is, for example, an iron or aluminum pipe used as a scaffolding material, and the entire surface thereof is subjected to a conventional antirust treatment by hot-dip galvanization.

The test material (A) is obtained by coating the surface of the construction material 30 with a silica glass coat. The silica glass coat is mainly applied to exhaust pipes, marine vessels, car painted surfaces, etc., and is used for reducing red rust to black rust and preventing corrosion. The test material (B) is obtained by coating the surface of the pipe 30 with the silica glass coat and the heat insulating glass coat described above. The thermal barrier glass coat is used for reducing dew condensation. The test material (C) was obtained by coating the surface of the pipe 30 with a polymer glass coat. The polymer glass coat is used for rust prevention. Furthermore, the test material (D) is obtained by coating the surface of the pipe 30 with a high transmission glass coat. The high transmission glass coat is used for anti-scratch applications. Lastly, in the test material (no mark), the surface of the pipe 30 was not coated and was only hot-dip galvanized.

Next, the conditions of rust and dirt generated on the metal surface of each test material by the first exposure test will be described in chronological order. Also, FIG. 6 shows a table of the results of evaluating the conditions of the test materials (A) to (D) (no mark).

・After 1 month, the test material (A) was in a dirty state with some particles such as gravel and mud adhering to it, but it could be removed by wiping. In the test material (B), particles such as gravel and mud were adhered, and some discoloration was observed. The test material (C) was in a dirty state with some particles such as gravel and mud adhering to it, but it could be removed by wiping. The test material (D) was in a dirty state with a small amount of particles such as gravel and mud adhering to it, but the adherence was the least among the test pieces and could be removed by wiping. In addition, many particles such as gravel and mud adhered to the test material (no mark), and they could not be easily removed by wiping.

・After 2 months, the test material (A) was in the same state of staining as after 1 month, and no discoloration was observed. In the test material (B), particles such as gravel, mud, etc. adhered to the test material (B), and some discoloration was observed, as was the case after one month. Test material (C) is in a dirty state with some particles such as sand and mud adhering, but the adhering matter can be removed by wiping, and it seems that it has been washed away by rainwater after one month. was taken. The test material (D) was in a dirty state with some particles such as gravel and mud adhering to it, but the adhering matter could be removed by wiping. Also, the test material (no mark) had particles such as sand, mud, etc., and adhered black lumps, and the adhered matter could not be removed by wiping. Furthermore, the generation of rust was also confirmed in the pockets of the struts.

・After 4 months The situation after 4 months of the first exposure test is shown in Figures 5 (a) and (b). The test material (A) did not show any significant discoloration, and the adhesion of particles could be removed by lightly wiping. The test material (B) had an increased degree of discoloration, and the adhering matter could not be removed even by rubbing. Sample material (C) was partially discolored, but the deposits could be removed by wiping. The test material (D) showed more discoloration than the previous time, but the deposits could be removed by wiping. In addition, the test material (no mark) had an increased number of particles and deposits such as black lumps, which could not be removed by wiping. Furthermore, generation of rust was also confirmed.

(Second exposure test)
Next, the second exposure test of the metal material coated with the coating material according to the present invention will be described. In this second exposure test, a metal test material (E) coated with a coating material of the type described later, and a test material (unmarked) not coated with a coating material for comparison, were subjected to indoor iron ore. It is permanently placed for several months in the same environment where iron powder etc. This is a comparison of discoloration.

As shown in FIG. 7, a pipe 40 used as an erection material at a construction site or the like was used as a metal test material applied to this test. This pipe 40 is the same type of pipe as the pipe 30 used in the first exposure test described above, and is, for example, an iron or aluminum pipe used as a scaffolding material. It has been subjected to anti-corrosion treatment.

A test material (E) is obtained by coating the surface of a pipe 40 with a silica glass coat. The silica glass coat is mainly applied to exhaust pipes, marine vessels, car painted surfaces, etc., and is used for reducing red rust to black rust and preventing corrosion. The test material (E) is a test material coated with the same silica glass coat as the test material (A) used in the first exposure test described above. In addition, the test material (no mark) is the one in which the surface of the pipe 40 is not coated and is only hot-dip galvanized.

Next, the conditions of rust and dirt generated on the metal surface of each test material in the second exposure test will be described. Further, FIG. 8 shows a table of the results of evaluating the conditions of each test material (E), (no mark).

・After 4 months Figure 7 shows the situation after 4 months of the second exposure test. The test material (E) had a slight amount of deposits that appeared to be iron powder, but no significant discoloration was observed. . On the other hand, with the test material (no mark), a large amount of deposits that seemed to be iron powder adhered to the surface of the test material, and they could not be removed by wiping dry or washing with water.

From these results, first of all, in the test material (no mark), the hot-dip galvanized surface of the iron test material (no mark) that is not coated with the coating material is compared with the iron powder (iron) with a Mohs hardness of 4. , the Mohs hardness is 2 to 3, which is softer, so it is presumed that the iron powder scattered near the test material (no mark) bites while damaging the surface of the test material (no mark).

On the other hand, in the test material (E), the surface of the test material (E) coated with a dense glass film has a Mohs hardness of 4.0, which is harder than the iron powder (iron) with a Mohs hardness of 4. Since it is 5 to 6.5, the iron powder scattered near the test material (E) is repelled without damaging the surface of the test material (E), and it is greatly suppressed from biting into the surface. It is speculated that

Therefore, according to the second exposure test, the metal material to be coated with the coating material according to the present invention is, for example, aluminum, zinc, lead, tin, gold, silver, copper or brass, which has a relatively low Mohs hardness. By coating the metal material with the coating material, the Mohs hardness of the coating target can be improved to 4.5 to 6.5, which is higher than that of iron. Therefore, for example, if the coating material according to the present invention is coated on the surface of an aluminum tire wheel of a vehicle, it is possible to reduce scratches caused by scattering iron powder on the tire wheel, and to greatly extend the service life. becomes possible.

(Gas corrosion test)
Next, the gas corrosion test of the metal material coated with the coating material according to the present invention will be described. In this gas corrosion test, silver and copper specimens coated with a coating material of the type described later, and silver and copper specimens coated with a different type of coating material from the present invention as comparison objects of the present invention. Place the test material and each silver and copper test material not coated with coating material in a test chamber (not shown) filled with an atmosphere of predetermined conditions containing gas that causes corrosion, and The test materials were exposed to the atmosphere for 24 hours under the same environment, and the discoloration, that is, the state of corrosion occurring on the surface of these test materials was compared.

More specifically, the predetermined conditions in the test chamber include sulfur dioxide (SO ₂ ) with a concentration of 10 ppm and hydrogen sulfide (H ₂ S) with a concentration of 3 ppm as a gas that causes corrosion, a temperature of 40 degrees, a humidity of 80%. Atmosphere. In addition, as the test materials described above, a silver metal plate and a copper metal plate were placed in the test chamber.

As shown in FIGS. 9(a) and 10(a), the test material (Fa) and the test material (Fb) reduce rust and prevent corrosion on the surfaces of silver and copper metal plates, respectively. It is coated with a silica glass coat. The silica glass coat is mainly applied to exhaust pipes, marine vessels, car painted surfaces, etc., and is used for reducing red rust to black rust and preventing corrosion.

Further, as shown in FIGS. 9(b) and 10(b), the test material (Ga) and the test material (Gb) are formed on the surfaces of the silver and copper metal plates, respectively. It was coated with the same silica glass coat as Fa) and test material (Fb) and then fired.

Further, as shown in FIGS. 9(c) and 10(c), the test material (Ha) and the test material (Hb) are applied to the surfaces of metal plates made of silver and copper, respectively. It is coated with three layers of silica glass coating suitable for the application.

Further, as shown in FIGS. 9(d) and 10(d), the test material (Ia) and the test material (Ib) are formed on the surfaces of the silver and copper metal plates, respectively. Ha) and five layers of the same silica glass coat as the test material (Hb) were coated.

Further, as shown in FIGS. 9(e) and 10(e), the test material (Ja) and the test material (Jb) were applied to the surfaces of silver and copper metal plates, respectively, with the present invention for comparison. are coated with different coating materials. The coating material differs from the coating material of the present invention in that it contains a large amount of organic components other than SiO ₂ .
Further, as shown in FIGS. 9(f) and 10(f), the test material (no mark a) and the test material (no mark b) were coated with any coating material on the surfaces of silver and copper metal plates, respectively. The metal substrate is exposed without any coating.

Next, the state of discoloration, ie, corrosion, that occurred on the metal surfaces of the silver and copper specimens in the gas corrosion test will be described. 11 and 12 are tables showing the surface colors of silver and copper specimens, respectively. The color was measured according to the spectrophotometric method and calculated according to the color difference in the Lab color space. The number of times of measurement was set to 3, and the average value is shown as the result.

・Silver test material Figures 9 (a) to (f) show the state of the metal surface of each silver test material before the gas corrosion test and after 24 hours have passed, and Figure 11 shows before the gas corrosion test. and the color difference of each silver test material after the test.

First, as shown in FIGS. 9(a) to (d) and FIG. 11, the test materials (Fa) to (Ia) coated with the coating material of the present invention are all confirmed to have discoloration etc. on the silver metal surface. No significant color difference was measured within a small margin of error. From this result, in the test materials (Fa) to (Ia), no chemical change such as corrosion occurred on the surface of each test material, and therefore the coating material according to the present invention is completely silver metal. It is considered that the material surface is coated.

On the other hand, as shown in FIGS. 9(e) and 11, in the test material (Ja) coated with a coating material different from the present invention for comparison, dark discoloration can be confirmed on the silver metal surface. A significant value of 15.7 was also measured for the color difference. From this result, it is considered that a small amount of silver sulfide (Ag ₂ S) is generated on the surface of the test material (Ja). It is considered that this is because a large amount of organic components other than SiO ₂ contained in the coating material to be compared is attacked by the acidic gas in the atmosphere, and as a result, the surface of the underlying silver metal material is exposed.

On the other hand, the coating material of the present invention has an extremely high purity of SiO ₂ and contains only trace amounts of organic components other than SiO ₂ . It is considered that corrosion does not occur because it is hardly attacked by acidic gases of

Also, as shown in FIGS. 9(f) and 11, in the test material (unmarked a) that is not coated with the coating material, the silver metal surface is discolored to black, and the color difference is a large value of 43.1. Measured. From this result, it is considered that silver sulfide (Ag ₂ S) is generated over the entire surface of the test material (no mark a).

・ Copper test material Figures 10 (a) to (f) show the state of the metal surface of each copper test material before the gas corrosion test and after 24 hours have passed, and Figure 12 shows before the gas corrosion test. and the color difference of each copper test material after the test.

First, as shown in FIGS. 10(a) to (d) and FIG. 12, the test materials (Fb) to (Ib) coated with the coating material of the present invention are all confirmed to have discoloration etc. on the copper metal surface. No significant color difference was measured within a small margin of error. From this result, in the test materials (Fb) to (Ib), no chemical change such as corrosion occurred on the surface of each test material, and therefore the coating material according to the present invention is completely made of copper metal. It is considered that the material surface is coated.

On the other hand, as shown in FIGS. 10(e) and 12, in the test material (Jb) coated with a coating material different from that of the present invention for comparison, dark discoloration was observed on the copper metal surface. A significant value of 49.8 was also measured for the color difference. From this result, it is considered that a small amount of copper (I) sulfide (Cu ₂ S) and copper (II) sulfide (CuS) are generated on the surface of the test material (Jb). It is considered that this is because a large amount of organic components other than SiO ₂ contained in the coating material to be compared is attacked by the acidic gas in the atmosphere, and as a result, the surface of the underlying copper metal material is exposed.

In contrast, the coating material of the present invention has an extremely high purity of SiO ₂ and contains only trace amounts of organic components other than SiO ₂ . It is considered that corrosion does not occur because it is hardly attacked by acidic gases of

Also, as shown in FIGS. 10(f) and 12, in the test material (unmarked b) that is not coated with the coating material, the copper metal surface is discolored black, and the color difference is a large value of 63.5. Measured. From this result, it is considered that copper (I) sulfide (Cu ₂ S) and copper (II) sulfide (CuS) are generated over the entire surface of the test material (no mark b).

(Abrasion resistance test)
Next, the wear resistance test of the metal material coated with the coating material according to the present invention will be described. In this wear resistance test, an aluminum test material coated with a coating material of the type described later, and an aluminum test material coated with a different type of coating material from the present invention as a comparison object of the present invention, And the aluminum test material not coated with the coating material is rotated a predetermined number of times (500 times in this example) while the wear wheel is pressed under a constant load (4.9 N in this example). This is a so-called Taber wear test in which the mass of the wear amount of each test material is measured.

As shown in FIG. 13, the test material (K) is an aluminum metal plate coated with a silica glass coat excellent in waterproof, scratch-proof, and antifouling properties. The silica glass coat is mainly applied to surface modification of smartphones, vehicles, etc. The test material (L) is an aluminum metal plate whose surface is coated with a silica glass coat that reduces rust and prevents corrosion. The silica glass coat is mainly applied to exhaust pipes, marine vessels, car painted surfaces, etc., and is used for reducing red rust to black rust and preventing corrosion. The test material (M) was obtained by coating the surface of a metal plate made of aluminum with the same silica glass coat as the above test material (L), followed by firing. Furthermore, the test material (N) is a metal plate made of aluminum coated with a coating material different from the present invention for comparison. The coating material differs from the coating material of the present invention in that it contains a large amount of organic components other than SiO ₂ . In addition, the test material (no mark) is an aluminum metal plate whose surface is not coated with any coating material, and the metal substrate is exposed. In order to confirm the reproducibility of the effect, the test material (K) and the test material (no mark) were tested three times in total.

Next, as shown in FIG. 13, the amount of wear generated in each test material in the wear resistance test will be described. In the first test, the wear amount of the test material (no mark) was 18 mg, the wear amount of the test material (K) was 14 mg, and the wear amount of the test material (L) was 15 mg. , and the wear amount of the test material (M) is 16 mg. was significantly smaller. The amount of wear of the test material (N), which is a comparative object, was 18 mg, which was the same as that of the test material (no mark).

In the second test, the wear amount of the test material (no mark) was 20 mg, while the wear amount of the test material (K) was 19 mg. The wear amount of K) was significantly smaller than that of the test material (no mark).

In the third test, the wear amount of the test material (no mark) was 132 mg, while the wear amount of the test material (K) was 116 mg. The wear amount of K) was significantly smaller than that of the test material (no mark).

According to the wear resistance test described above, the amount of wear of the metal material coated with the coating material according to the present invention was reduced by about 10 to 20% compared to the metal material not coated with any coating material. This is because by coating the coating material according to the present invention, the surface of the metal material has an extremely smooth surface structure with nano-level unevenness, that is, the coefficient of friction of the metal material coated with the coating material is reduced. It is considered that a high wear resistance effect is exhibited.

(Anti-fouling test)
Next, the antifouling test of the metal material coated with the coating material according to the present invention will be described. In this antifouling test, the surface of an aluminum test material coated with a coating material of the type described later and an aluminum test material not coated with a coating material as a comparison object of the present invention was tested. In this test, the antifouling performance was confirmed by trying to remove the sample with an adhesion tester after several days had passed with the sample applied to the object.

As shown in FIG. 14, the test material (P) is an aluminum scaffold plate coated with a silica glass coating excellent in waterproof, scratch-proof and stain-proof properties with a sponge or roller. The silica glass coat is mainly applied to exhaust pipes, marine vessels, car painted surfaces, etc., and is used for reducing red rust to black rust and preventing corrosion. In addition, the test material (no mark) is an aluminum metal plate whose surface is not coated with any coating material, and the metal substrate is exposed.

In addition, on the upper surface of each of the test material (P) and the test material (no mark), as a sample of the antifouling object, ricin, which is mainly used for spraying the outer wall, is applied and adhered (upper side in the figure ), and mortar, which is often used in construction work, was applied and adhered (lower side in the figure). After about 11 days had passed in a dry room after the coating, the stripping of the lysine and mortar was attempted.

As shown in FIGS. 15(a) and 15(b), the ricin and mortar adhering to each test material (P) and test material (unmarked) were peeled off with an adhesion tester (left side in the figure). Water was sprinkled on the surface of the peeled scaffold board (right side of the drawing). As shown on the right side of FIG. 15(a), the test material (P) exhibited a water-repellent effect in which a large number of fine droplets adhered. In addition, as shown on the right side of FIG. 15(b), the test material (no mark) exhibited a hydrophilic action of adhering in the form of stains on a wide surface. In addition, the adhesion tester for removing lysine and mortar adhering to each test material (P) and test material (no mark) was used to remove the mortar with a load of about 2 kg on the test material (P). On the other hand, in the test material (no mark), the mortar peeled off at a load of about 10 kg heavy scale.

According to the peeling test described above, the metal material coated with the coating material according to the present invention has a high peelability of the adhered antifouling object compared to the metal material not coated with any coating material. It was confirmed that

Also, as shown in FIG. 16, when the surface of each test material (P) and the test material (no mark) after peeling off the sample was visually observed, it was found that the surface of the test material (P) had On the other hand, on the surface of the test material (no mark), the delamination part was partially whitened. This is because even after the lysine and mortar adhering to the surface of the test material (P) were removed, the coating material according to the present invention remained without being peeled off, while it adhered to the test material (no mark). It is considered that the lysine and the mortar that have been cured become strongly alkaline during the curing process, corroding the surface of the test material (no mark) and whitening the aluminum.

According to the antifouling test described above, the metal material coated with the coating material according to the present invention has higher antifouling properties and corrosion resistance than the metal material not coated with any coating material. It was confirmed that

(Surface roughness test)
Next, the surface roughness test of the metal material coated with the coating material according to the present invention will be described. This surface roughness test was performed on the surface of a zinc steel specimen coated with a coating material of the type described below and a zinc steel specimen without a coating material as a comparison object of the present invention. This test confirms the smoothness of the test material by measuring the surface roughness of the test material with a surface roughness tester.

As shown in FIG. 17, the test material (Q) is a zinc steel metal plate used as a scaffolding material, the surface of which is coated with a silica glass coat that reduces rust and prevents corrosion. The silica glass coat is mainly applied to exhaust pipes, marine vessels, car painted surfaces, etc., and is used for reducing red rust to black rust and preventing corrosion. In addition, the test material (no mark) is a metal plate made of zinc steel, the surface of which is not coated with any coating material, and the metal substrate is exposed.

Three arbitrary points on the surface of each test material (Q) and test material (no mark) were selected, and the surface roughness of the points was measured by a surface roughness measuring machine (not shown). As shown in FIG. 18, in the test material (Q), the average value of the arithmetic mean roughness Ra at each point was 0.3322 μm, whereas in the test material (no mark), the arithmetic mean roughness at each point The average value of thickness Ra was 0.7762 μm.

According to the surface roughness test described above, it was confirmed that the coating of the zinc steel metal plate with the coating material resulted in a smoother surface than the metal substrate. Thus, it is considered that the coating of the coating material according to the present invention makes it difficult for dirt components, moisture, and chemical components to remain on the surface, and improves the antifouling effect and anticorrosion effect.

Among the test materials used in each test described above, the test material (A) for the first exposure test, the test material (E) for the second exposure test, the test material for the gas corrosion test ( Fa), test material (Fb), wear resistance test test material (L), antifouling test test material (P), and surface roughness test test material (Q) are the same coating It is mainly applied to exhaust pipes, marine vessels, car painted surfaces, etc., and is coated with a silica glass coat used for reducing red rust to black rust and preventing corrosion.

(Action and effect of the present invention)
As described above, according to the method of coating the coating material of the present invention, the surface 2 of the metal material 1 to which water is attached is coated with the undiluted solution 10 (raw material) of the coating material, and the components contained in the undiluted solution 10 and the air SiO ₂ as a main component on the surface 2 of the metal material 1 by chemically reacting the components contained in the undiluted solution 10 with the moisture 6 adhering to the surface 2 of the metal material 1. By producing a thin film coating material 15 that has been coated with water, the water 6 that causes rust adhering to the surface 2 of the metal material 1 is removed by a chemical reaction for producing the coating material 15 that has SiO ₂ as a main component. By using it, not only can the undiluted solution 10 coated on the metal material 1 be rapidly chemically reacted from both the surface layer surface 10a side and the back layer surface 10b side, but also the back side of the coating material 15 coated on the metal material 1 In addition, the coating material 15 having a high rust-preventive property that coats the surface 2 of the metal material 1 in close contact can be produced.

In addition, by forming the surface layer of the coating material 15 into a smooth surface on which the dimples 16 consisting of nano-level fine unevenness are formed, it is difficult for moisture and foreign matter to adhere to the surface layer of the coating material 15, and high rust resistance is achieved. In addition, water repellency and antifouling effects can be obtained.

In addition, by forming the dimples 16 by utilizing the volatilization of the gas generated by the chemical reaction between the components contained in the stock solution 10 and the moisture, the dimples 16 can be uniformly distributed on the surface of the coating material 15 .

In addition, since the coating material 15 has a film thickness of 10 nm to 1 μm, the coating material 15 has an extremely thin film thickness. , the metal material 1 can be applied to a wide range of uses.

Furthermore, after subjecting the surface 2 of the metal material 1 to roughening treatment, the surface 2 of the metal material 1 is coated with the undiluted solution 10 of the coating material, thereby roughening the surface 2 of the metal material 1 in advance. As a result, the undiluted solution 10 of the coating material forms a film layer in a state in which it enters the irregularities formed by roughening the surface 2 of the metal material 1, so the coating material 15 is an anchor that adheres to the metal material 1. more effective.

In addition, after the surface 2 of the metal material 1 is coated with moisture 10, the surface 2 of the metal material 1 is coated with the undiluted solution 10 of the coating material. A chemical reaction with the stock solution 10 of the coating material in contact with the surface 2 of the material 1 can be promoted.

Further, according to the metal material 1 coated with the coating material 15 of the present invention, the surface 2 of the metal material 1 to which water is attached is coated with the undiluted solution 10 of the coating material, and the components contained in the undiluted solution 10 and the moisture in the air and a chemical reaction between the components contained in the stock solution 10 and the water adhering to the surface 2 of the metal material 1, thereby forming a thin film mainly composed of SiO ₂ on the surface 2 of the metal material 1. Since the coating material 15 is produced, the water that causes rusting adhered to the surface 2 of the metal material 1 is used in a chemical reaction for producing the coating material 15 mainly composed of SiO2. In addition, it is possible to prevent rusting on the back side of the coating material 15 coated on the metal material 1, and to provide the metal material 1 coated with the high-quality coating material 15 that is in close contact with the surface.

In addition, as the metal material to be coated with the coating material, for example, aluminum, zinc, lead, tin, gold, silver, copper, or brass. A subject's Mohs hardness can be increased to a value higher than that of iron.

Furthermore, by coating the surface of a metal material made of silver or copper with a coating material, it is possible to prevent discoloration and corrosion due to generation of silver sulfide and copper sulfide.

Although the embodiments of the present invention have been described above with reference to the drawings, the specific configuration is not limited to these embodiments, and any changes or additions within the scope of the present invention are included in the present invention. be

For example, in the above-described embodiment, the coating material 15 contains approximately 100% SiO ₂ as the main component, but is not limited to this, and may contain other components as long as they are trace amounts or small amounts that do not affect SiO ₂ . may

Further, for example, in the above examples, the metal material is applied as the object to be coated with the coating material according to the present invention. By doing so, the surface hardness of the acrylic resin material is increased, and the service life of the abrasive that scatters inside the blasting machine is improved by about 10 times or more. You can get the effect of being able to

1 metal material 2 surface 3 uneven part 6 moisture 10 undiluted solution (raw material of coating material)
10a surface layer 10b rear surface 11, 12 SiO ₂ layer 15 coating material 16 dimple 17 anchor portion 25 coating material 26 dimple 30 pipe 40 pipe

Claims (6)

A method for coating a surface of a metal material to be coated with a coating material,
a step of making the surface of the metal material wet; Coating the raw material of the coating material on the surface of the metal material to which water is attachedand the process of
In the coating step, theIn addition to chemically reacting the ingredients contained in the raw material with the moisture in the air, the ingredients contained in the raw material and the surface of the metal material adheremade saidchemically react with waterBy releasing the gas generated from the surface of the metal material into the air, the surface of the metal material has a film thickness of 10 nm mainly composed of SiO2 having dimples consisting of nano-level fine unevenness on the surface layer surface. A coating material of 1 μm or less is produced by the aboveA method of covering a coating material, characterized by: 2. The coating method of the coating material according to claim 1 , wherein the surface of the metal material is roughened, and then the raw material of the coating material is coated on the surface of the metal material. 3. The coating method of the coating material according to claim 1, wherein the surface of the metal material is coated with the raw material of the coating material after moisture is applied to the surface of the metal material. A metal material whose surface is coated with a coating material,
On the surface of the metal material, a gas generated by a chemical reaction between the ingredients contained in the raw material of the coating material and the moisture adhering to the surface of the metal material is released into the air from the surface of the metal material. A coating material having dimples consisting of nano-level fine unevenness generated when the surface is coated with a coating material containing SiO2 as a main component and having a thickness of 10 nm or more and 1 μm or less on the surface layer surface. metal material. 5. The metal material coated with the coating material according to claim 4 , wherein the metal material is made of a metal having a Mohs hardness lower than that of iron. 6. The metal material coated with the coating material according to claim 4 , wherein the metal material is made of silver or copper.

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