JPH11166135A - Rust preventive coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a rust preventive film on a metal surface by an oxidation of a metal salt and simultaneously form a resin protective film on the surface thereof. SOLUTION: A molybdate or a tungstate is made to react on a metal surface and is reduced to an ion to produce an oxide film 2 and then an acetal resin of the polyvinylalcohol is deposited thereon to form a resin protective film 3 by precipitating a metal in an acetal resin solution of the polyvinylalcohol dissolving the molybdate or the tungstate or by subjecting thereof to an electrolytic treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[Industrial application] Prevents corrosion of concrete aggregates using steel bars, steel frames, etc., which causes cracks in concrete to reduce strength and weaken. This rust-preventive processing of automobile bodies and other steel moldings enhances the film strengthening of Parkaringni with a phosphoric acid film with synthetic resins and proteins, and also prevents the carcinogenicity of rust-proofing materials with nitroprusside. Titanium, zirconium and hafnium oxide are added to concrete to prevent concrete from cracking, increasing the bonding strength of concrete and adding sodium polyacrylate to prevent extreme drying and prevent dealkalization of concrete. Therefore, the durability of concrete moldings is extended. Also, when applying alkali molybdate, soluble resin and pigments to the surface treatment of aluminum or magnesium outer copper alloys or zinc alloys, in addition to concrete aggregates, a film that creates a glossy golden or iridescent color is created. Applied to decorative fittings, buttons, window frames, building materials, containers,
Increases resistance to corrosion. This molybdate
Tungstate, chromium salt, manganate, and peroxide have the effect of maintaining a higher level of natural metal color. The surface of the steel bridge made of caustic is also treated with iron tetroxide on the surface of the steel bridge. When post-treatment is performed, the effect is to increase the durability three times. Polyvinyl alcohol water or polyacrylic acid chromium water is mixed with this resin, and aldehyde, butyraldehyde, orylic aldehyde, ultrapine, etc. are added, and molybdate or tungstate aqueous liquid is mixed. Not only does the resulting film become insoluble in water, but also has a stronger contact property with concrete than other hydrophobic resins. Further, the bonding strength is stronger than that of an emulsified resin obtained by mixing polyvinyl acetate and polyethylene, and the hydrophobicity is inferior to the latter. In particular, in the glossy surface processing of aluminum alloys and aluminum metals, the formation of an oxide resin processed film after golden color processing by molybdate processing is 10 times higher in wear resistance and less discoloration. Since it is suitable for gold processing, its application range is wide for decoration and building material processing.

2. Description of the Related Art As a conventional technique, there is a parkerizing method as a steel surface treatment, which exerts a rust preventive action by a phosphoric acid film, and is used for rust preventive processing of automobile bodies and steel. . There is also a nitroprusside method, in which rust is prevented by the nitroprusside crystal volatilization method and a metallic luster is displayed forever, and a phosphoric acid is added to this nitroprusside to form a phosphoric acid film after rust prevention. ing. As a method for forming a surface oxide film on an aluminum plate or an aluminum alloy processed product, an electrolytic method is generally used. In many cases, however, decorative fogging or a glossy surface is lost, and tannic acid treatment is less beautiful.
In the case of false gold processing of aluminum products, a false gold surface was created by forming a surface film with a synthetic resin sol solution in which a yellow dye was dissolved.For example, the surface of a watch always contacts clothing. The resin film was thinly worn due to friction and could not keep the golden glossy surface for a long time.
When the surface of the aluminum surface that has been given a golden color by oxidation of the metal salt is further hardened by applying a hard resin of golden paint, the durability is improved more than 10 times, and the surface unique to false gold It is intended to develop a method for preventing a change in gloss.

SUMMARY OF THE INVENTION The present invention enhances the decorative value by forming a false gold process and an oxide film that shines a golden color on the surface of an aluminum alloy or an aluminum processed product, and increases the decorative value. Improving the low wear resistance of counterfeit gold processing, the golden color by abrasion resistance is improved more than 10 times by the two-step processing of the conventional resin film with abrasion resistance in the counterfeit metal method by oxide film formation. It was developed with the idea of preventing loss at least. Furthermore, it is intended to perform surface treatment of processed steel products, especially rust-preventive processing of concrete aggregates and steel materials. The combination of these two is intended to increase the processing amount and improve productivity. is there. In addition to improving the electrical loss due to the surface treatment of silica-coated steel sheets and electromagnets, the surface oxide film of silicon and germanium semiconductors is processed, and the heat resistance of the enamel wire is improved by forming the surface resistance film of the metal conductor. It is a measure.
Another object of the present invention is to develop a resin film capable of exhibiting an iridescent color by cinnamic aldehyde for performing iridescent processing on a glossy surface of stainless steel or chrome plating.

Means for Solving the Problems The oxide film processing on the surface of aluminum or aluminum alloy is not glossy due to the irregular surface film processing, and corrosion can be prevented for decorative processing, but the decorative appearance is good. In general, these metal surfaces are polished to create a shiny surface, but the color of the yellow pigment mixed with the synthetic resin often loses its luster due to aging or friction of the synthetic resin, and the value of false gold , It was necessary to prevent this from further decreasing. In order to maintain the golden color for a long time, it was necessary to form a metal oxide film directly on the aluminum metallic glossy surface, particularly a film close to the golden color. Therefore, molybdate or tungstate is used as an aqueous solution, and aluminum or an aluminum alloy is deposited on the solution or electrolytic treatment is performed, so that the molybdate reacts on the aluminum surface and dissolves in the molybdate solution. The acid ion is reduced, and the yellow color of Mo3 becomes
An O film is formed and adheres to the aluminum or aluminum alloy surface. The aluminum and the aluminum alloy which are washed with water and dried always have a golden color and have a film thickness of 0.1 to 10 μm on the surface. This golden color does not change even if exposed to sunlight for one year, and retains the golden color even when stored indoors for 20 years. To further protect the metal oxide film, a small amount of B.P. H. When T, a yellow dye and a curing agent are applied and cured, the composition is further strengthened with a protective film, the abrasion resistance is enhanced, the disappearance of the golden color on the surface is small, and the durability is 10%.
Strengthened for double maintenance. If a chitosan solution, a serine solution of silk amino acid, calcium alginate, or the like is added to the polyvinyl alcohol acetal solution, the hardness is further increased and the cost is reduced. In general, aluminum and aluminum alloy processing are not always in constant demand in terms of productivity.In parallel with this, when using the same liquid for surface treatment of building steel and other steel, the productivity is improved. Rationalization is performed. Also, when used for surface treatment of other copper alloys or tin alloys, a glossy oxide film can be formed. The surface treatment of motors and generators using electric wire coils and silicon steel sheets is surface oxidized with molybdate or tungstate water to form an electric resistance film, and the insulating properties of the silicon semiconductor germanium surface oxide film are enhanced. In addition, a stainless steel or chrome-plated surface is coated with a polyvinyl acetalized resin film of cinnamic aldehyde to give an aesthetic appearance.

[Function] Molybdate, tungstate, chromate, manganate, and peracid are dissolved in steel.
Separately, a steel product is added to a mixture of polyvinyl alcohol, polyacrylic acid chromium resin, chitin-chitosan solution, alkali alginate solution or protein solution dissolved in hot water and an aldehyde solution added with a metal chelate compound. When depositing, dissolve the thin iron ion oxide film adhering to the steel surface, then form a strengthened oxide film, and at the same time, form a synthetic resin, chitin-chitosan film, and alginate acid film, and oxidize the steel surface. Reinforcing bars and steel frames in concrete that prevent moisture from directly adhering prevent concrete cracks from destruction due to iron salt volume increase due to corrosion and dissolution of concrete pieces by iron ions, and demonstrate the rust-preventive hardening of reinforcing bars and steel frames After extending the durability of concrete, after processing the rust-preventive effect of steel bar processing such as Parker Rising It is reduced no more durable nitroprusside phosphate film to form an enhanced oxide film remarkably. In particular, when the concentration of the oxide film on the other metal surface of molybdate water increases, the corrosion resistance increases when a yellow film of molybdic acid is formed, but in a water solution of 20% or less from the viewpoint of cost and appearance. Since it forms a glossy surface which hardly replaces the metal surface, there is an advantage that the steel surface can be kept glossy, and tungstate exerts the second effect. When treated with chromic acid or permanganic acid solution, a black oxide film is formed on the steel surface and the metallic luster is lost, but a stable oxide film is formed. When treating an aluminum plate with this molybdate blue polyacetal resin,
Oxidation by molybdic acid and the formation of a thin molybdic acid deposited film give it a golden color, which is stable to light and does not change color after 20 years. This is the same with the case of tungstate, and when a thin film of Wo is formed on the surface, it takes on a golden color. The general Wo3 tungstic acid film is a yellow-white film which prevents corrosion of the steel or aluminum metal surface, but does not turn golden. Also in the case of molybdic acid, Mo3 has a yellow-white color, but the Mo film has a golden color and is used for decoration as false gold processing, and the processing of building materials is extremely beautiful. In addition, acetylacetone tungstic acid and acetylacetone molybdic acid are soluble in benzene and other organic solvents, and when mixed with polyvinyl alcohol acetalized resin or polyester resin and treated on the metal surface, an oxide resin film is formed. Mixing polyethylene, polypropylene powder, ethyl keiso, fluorinated resin, oils and fats, and parapine makes it hydrophobic, and a concrete molded product resistant to salt damage can be obtained. These molybdates and tungstates are more safe because their toxicity is lower than that of manganese, chromic or vanadate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the embodiments shown in the drawings.

FIG. 1 shows a front view of a reinforcing bar (1), and a reinforcing bar (1).
An oxide film (2) is formed on the surface of the substrate, and a corrosion-resistant film is formed by bonding a water-resistant resin film (3). (4) shows irregularities on the reinforcing bar surface.

FIG. 2 is a vertical cross-sectional view taken along line AB of a reinforcing bar.

FIG. 3 shows an oblique front view of a reinforced concrete column;
Vertical reinforcing bars (1b) (1'b) 1 "b) (1 '" b) and horizontal frame bars (2b) (2'b) (2 "b) (2'" b) (3b)
(3'b) (3 "b) (3 '" b) (4b) (4'b)
(4 "b) (4 '" b) is fitted and joined. this

FIG. 6 shows an oxide film and a resin film formed on the surface of a reinforcing bar according to the process chart shown in FIG.

FIG. 4 shows an oblique front view of an H-section steel, and shows an H-section steel (1a).
To

FIG. 6 is a process in which an oxide film (2a) is formed on the surface of the H-type (1a) by a dipping process based on the process diagram of FIG. 6 and a resin film is formed on the surface at the same time. It was processed at the same time.

FIG. 5 shows an oblique front view of a concrete column, in which a concrete column (5b) is placed.

FIG. 3 is a diagram showing a reinforcing bar housing obtained by hardening a bar.

FIG. 6 shows a process chart of oxide film processing. Is a steel material (1
c) into a hanging basket (2c),
The process proceeds in step c), and is deposited in the oxide film forming bath (4c) and reacted in the liquid. In order to perform the reaction promptly, the temperature is increased to 70 ° C. or higher.
In about 30 minutes, it is lifted up and down by lifts (5c) and (5'c), transferred to the dehydration tank (6c), separated into excess liquid, recovered in the dehydration tank, and dried ( The hanging basket (2c) transferred to the conveyor (3'c) in 7c) is a fan (8c).
(8'c) (8 "c) (8 '" c) to blow and dry. The hanging basket (2'c) after the drying is tilted with a lift to load the steel material (1c) on the trolley (9C), package it, and ship it.

The same applies to the case of the H-section steel of FIG. The same applies to the case where an aluminum plate, a magnesium plate, or an alloy plate is subjected to surface treatment. In addition, lightweight steel pipes, conduit tubes, and other rebars are similarly deposited. Similarly, the processing of automobile bodies and motorcycle frames by parker rising can be performed by oxidizing resin processing by deposition. The same processing is applied to the iridescent processing of the surface of the stainless steel plate, but iridescent processing is performed by repeating the deposition processing 2 to 5 times. In the gold processing of aluminum plates and aluminum molded products, a hardener is melted in an epoxy resin liquid and a golden paint is applied to the glossy aluminum surface and dried and solidified to give a golden color. There was a defect that the surface film peeled off and gradually changed to the original aluminum metal.However, in the processing of aluminum plates and aluminum molded products, when performing pretreatment by deposition with molybdate or tungstate resin solution A clear golden color is formed by surface oxidation. In particular, when molybdenum blue is formed, coloring becomes easy. After the surface is dried and the film is cured, the yellow color of the epoxy resin is applied and dried, and the golden color does not easily disappear due to abrasion with clothing like the former epoxy resin yellow color . in this case,
The outer case of the watch, which has been deposited in molybdenum blue liquor, has already made a golden color on the aluminum surface, but the surface coated with yellow epoxy resin has ten times more wear resistance. Therefore, the durability can be increased by using the same in the ring processing other than the watch, the plating of the button, the handbag and the buckle of the bag. In addition, in the case of lightning rods, roof decorations, handles, and other metalworking, it has a beautiful decorative value due to the fine aluminum glossy surface. or,
In the case of aluminum alloys used in building materials and in the processing of vehicle and airplane fuselage, silicon resin can be used instead of yellow bookkeeping resin in order to enhance light resistance. Even in this case, if the aluminum alloy surface is polished well and the surface is pre-treated with molybdate blue as a mirror surface, the discoloration is small, and the molybdate blue processed yellow retains the golden color even if it has been left indoors for 20 years, The weakness is due to the aging effect of the synthetic resin on light, which sometimes causes color blur. This golden color processing is in the oxide film of molybdate and tungstate, and the golden color of these molybdate and tungstate oxide films is impossible for manganese acid, chromic acid, and vanadate. It has a lustrous golden color. In addition, the iridescent processed product for the glossy stainless steel plate and the molded product thereof, when performing excessive dispersion of polyvinyl alcohol, cinnamic acid ester or cinnamic aldehyde by stirring with a stirrer, the iridescent film formation is improved. When a drop of heavy oil is added to this polyvinyl alcohol, the mixture is stirred and dispersed, and when acetalized, a deep rainbow color is exhibited. Acetalization of alcoholic water is performed. In addition, when a mixture of cyclohexanone, butyraldehyde, and octylaldehyde is added to polyvinyl alcohol water, it does not show iridescence, but when cinnamic aldehyde is added, it becomes iridescent. These stainless steel spoons that have been subjected to surface processing or iridescent processing of ornaments do not have to worry about discoloration for 3 to 5 years even if they are left, and have no dissolution property even in heated water. This is the result of acetalization progressing over time. A molded body in which steel frames and reinforcing bars are pre-processed by this method, dried and hardened by oxidizing resin processing, and buried in concrete, do not corrode the reinforcing bars or steel frames, but have zirconium oxide powder and hafnium oxide powder. 6% is preliminarily blended into cement for concrete conversion, and has an action to replace hydrogen bonding of water even when moisture in the concrete is lost. The bond is strengthened by the OH bond of zirconium, and concrete with high durability and earthquake resistance can be obtained. In addition, when sodium polyacrylate or chromium polyacrylate is previously mixed to prevent dehydration of concrete water, the water retention is improved and the change in strength is small. An example of the composition of the oxidized resin liquid used for the surface processing of the steel frame or the reinforcing bar is as follows.

[Example 1] (A) Polyvinyl alcohol powder 1500 weight degree 100 parts Water 1000 parts Benzaldehyde or cinnamic aldehyde 10 parts

[Example 1] (B) 20 parts of molybdate soda or sodium tungstate 200 parts of water

[Example 1] Solution A was dissolved by heating at 100 ° C, and then cooled to room temperature. An aldehyde solution was added and cooled to prevent acetalization.

[Example 1] The solution prepared from the solution B was mixed to obtain an oxidized resin solution.

[Example 2] (A) Polyvinyl alcohol 10% water 1000 parts White white carbon powder 3 parts or titanium white powder 10 parts

[Example 2] (B) Sodium molybdate 10% water or molybdenum blue 10 parts

[Example 2] Also in the same manner as the former, the steel material is deposited by processing and mixing, and the oxide resin film is processed on the steel surface.

[Example 3] Iron tube surface treatment (A) Polyvinyl alcohol 10% water 1000 parts Chitosan acetic acid 10% water 100 parts Molybdate blue 10% water 20 parts (B) Chitosan acetic acid 10% water 100 parts Paint 0.01 part

FIG. 6 shows a process according to the process chart.

[Example 4] Aluminum processed product Alkali molybdate or 20 parts Alkali tungstate water 80 parts

[Example 5] Aluminum alloy processing Molybdate blue or tungstate blue 20 parts Chitosan acetic acid aqueous solution 10% 80 parts Water 100 parts

[Example 6] Copper alloy tin alloy treatment Alkali molybdate or alkali tungstate 20 parts Water 80 parts Polyvinyl alcohol resin 20% water 100 parts Betaldehyde Cinnamic aldehyde 20 parts

[Example 7] Aluminum processed product for vehicle and airplane body (A) Molybdate blue or tungstate blue 20% water 100 parts (B) Polyether resin or glycol resin 100 parts Curing agent 1 part Dye 0.1 part

[Example 8] For aluminum foil (A) Chitosan 5% water 100 parts Molybdate blue or tungstate blue 50 parts Silk amino acid powder 1 part Sodium alginate 5% water 2 parts Dye 0.1 part (B) Epoxy resin 10 parts Hardener 0.1 part Dye 0.1 part Solvent 80 parts

[Example 9] Stainless steel processed product Chrome plated processed product Iridescent processing Polyvinyl alcohol 10% water 100 parts Cinnamic acid aldehyde 10 parts This oxide film formation by molybdate or tungstate is also used for surface processing of silicon semiconductor. The oxide film is a yellow oxide film of Mo3 or Wo3 or Mo, Mo2, W
Not only can o, Wo2, Wo5, etc. be formed, but also an S film glass film can be bonded. It is also used for changing the electric resistance value. Further, it is used not only for forming an insulating film on an aluminum plate or a silicon steel plate, but also for surface treatment of tin or a copper alloy. The silicon steel sheet whose surface is processed has high abrasion resistance, so that there is no change even at a temperature of 500 to 600 ° C., and there is no iron loss. Also, the formation of a surface oxide film on a copper coil wire increases heat resistance, withstands a temperature of 700 ° C., and is used for an electric coil.

FIG. 7 is a comparative property table showing abrasion resistance. The frictional felt moving left and right was brought into contact with the metal surface or the resin film surface, and the abrasion resistance was measured by the number of left and right movements. (A) is a conventional coating having a thickness of 10 microns, and (B) is the M of the present application.
(C) shows the formation of a Wo film, and (d) shows a high abrasion resistance, and decreases in the order of (C), (B) and (A). (A) shows an enameled wire, (B) shows a molybdate oxide film, (C) shows a tungstate oxide film, and (d) shows a tungstate oxide film + resin film. As a result, in the enameled wire coil, there is no abnormality at 300 ° C. or less, but at 500 ° C., carbonization causes insulation failure.
(B) and (C) do not change at 700 ° C., but (d)
Since the surface is resin-processed, carbonization occurs at 500 ° C. and the insulation deteriorates. However, unlike the enameled wire shown in FIG. The surface of a silicon steel sheet composite for a transformer or a motor magnet with a tungstate oxide film or a Mo3 film adhered thereto is effective in reducing iron loss due to eddy current. or,,

FIG. 5 is used as an aggregate of a concrete block.

FIG. 3

FIG. 4 shows that the structural super-steel material having a refined structure of iron crystal in which the steel has further increased strength holds twice the high tension of conventional steel, and therefore, when this steel material is used, corrosion proceeds. Since the strength is sharply reduced, it is particularly necessary to process the metal surface with an oxide resin. And to measure the concrete reinforcement, add zirconium and hafnium powder during cement mixing.
Hardening by adding 2% or more has the effect of enhancing the earthquake resistance of concrete. This is because when the water content in the concrete decreases, the hydrogen bonding force decreases and the aging due to the alkalinity is strengthened by the addition of zirconium and hafnium powder.

As is clear from the above description, the following effects can be obtained in the present invention. (1) In the surface oxidation of aluminum and aluminum alloys, conventional alumite processing is not glossy and unsuitable for decoration, but the formation of an oxide film of molybdic acid or tungstic acid in this method has a golden color. As a result, the added value is high when used for decorative articles, electric appliances and building materials. (2) In the conventional golden color processing, a dye obtained by dissolving a yellow dye in a synthetic resin sol is applied to a metallic glossy surface, so there is no light resistance, and the golden color is easily lost due to aging or wear of the resin. Mo or Wo on glossy surface of aluminum or aluminum metal
Since the metal oxide film is adhered, the change rate of light resistance is extremely small, and the golden color is maintained even after 20 years, and a synthetic resin film is further applied to the surface at the same time. The abrasion resistance is improved by 10 times or more than the conventional one. No discoloration occurs even when the temperature reaches 400 ° C.
Since the heat resistance temperature of the oxide film applied with resin withstands 700 ° C., the insulation temperature is increased by surface treatment of the semiconductor.
Also, in metal copper other than aluminum, copper alloy and tin alloy,
Since an oxide film can be formed, a high heat-resistant coil is made of copper enameled wire, which is useful as insulation for transformers and electromagnets. (3) It is also used for forming an oxide film of a silicon semiconductor or a germanium semiconductor, and is also used for a heat-resistant insulating film. Especially,
The oxide film of Mo or Wo has high resistance on the film surface, but has a low resistance value on the metal surface. (4) It is also used for surface insulation processing of aluminum wires, and a stable one can be obtained at a temperature, but the heat resistance temperature is 400 ° C. (5) The silicon oxide sheet having a surface oxide film formed thereon has a reduced iron loss and has a heat resistance of 700 ° C. Therefore, when used for an electromagnet of a transformer or an electric motor, heat resistance is higher than that of an enameled wire. (6) Oxidation of building materials, such as steel bars, steel frames, H-shaped steels, other lightweight steels, steel pipes, steel plates, etc., which are in high demand in order to improve productivity in the formation of surface oxidation of other alloys of aluminum. Rust prevention by film formation can be performed. (7) The formation of oxide film on reinforcing steel bars and mold steel used in concrete is not only resistant to salt damage and does not rapidly increase the amount of iron ions generated, but also uses salty sea sand that forms solidified concrete. Also zirconium, hafnium,
When polyacrylate is added, it is resistant to salt damage and hardly causes cracks in concrete. (8) Since the formation of the oxide film and the processing of the resin are performed simultaneously in the surface processing of the reinforcing bar and the steel frame, the process is simplified. (9) In the iridescent processing of the stainless chrome-plated surface, decorative iridescent processing can be performed by processing the acetalized resin paint of polyvinyl alcohol of cinnamic aldehyde. Also used for electrical appliances.

[Brief description of the drawings]

Fig. 1 Front view of a reinforcing bar

FIG. 2 is a vertical cross-sectional view of the reinforcing bar taken along AB line.

Fig. 3 Slant front view of concrete reinforced columns

FIG. 4 is an oblique front view of an H-section steel.

Fig. 5 Front view of concrete pillar

FIG. 6 is a process diagram of processing an oxide film.

FIG. 7 is a comparative property table showing abrasion resistance.

Claims (1)

[Claims] As described later, steel, steel processed products and aluminum processed products in which molybdate and tungsten blue are dissolved in polyvinyl alcohol acetalized resin solution are deposited, and an oxide resin film is formed on the metal surface. Which is dried and hardened, and is characterized by the fact that it is an oxide film-formed product for building materials, decorations, and electrical appliances.