JP2007077192A - Corrosion-resistant glittering pigment, method for producing the same and corrosion-resistant glittering coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a corrosion-resistant glittering pigment to form a red metallic coating film exhibiting a luxury color close to red metallic plating and having excellent corrosion resistance and chemical resistance. <P>SOLUTION: The pigment is a flaky metal containing ≥50 mass% copper, 32-43 mass% zinc and 3-7 mass% aluminum and having a brightness and chromaticity satisfying L*=35-90, a*=10-50 and b*=10-25 in the L*a*b* color specification system. Preferably, the surface reflectance of the flaky alloy is 25-65% to the light of 550 nm wavelength, the thickness of the alloy flake is 0.02-5 μm and the size of the alloy flake is 5-50 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a corrosion-resistant glitter pigment used when red metallic coating is applied to a substrate such as an automobile part or a household appliance part, a method for producing the same, and a corrosion-resistant glitter paint.

  As means for brightening the substrate, there are wet plating, vacuum deposition and metallic coating. In particular, metallic coating has a simple method and is widely used. In metallic coating, the base material is brightened by using a paint mixed with an aluminum pigment or an aluminum flake-like alloy piece. In order to protect the aluminum in the coating film, a clear coat is applied to the surface of the coating film.

  Aluminum flake-like alloy pieces are produced by mechanically crushing metal aluminum by stamp mill method, dry ball mill method, wet ball mill method, etc., or vacuum evaporation method in which metal aluminum is evaporated in vacuum to form an aluminum film It is common to make using

  Aluminum has the advantage of high surface reflectivity and low price. For this reason, it is used as a pigment which gives a glittering feeling as a flaky alloy piece (foil).

  When red metallic paint is applied to home appliances, mobile phone parts, body parts, etc., red pigments such as petals, cadmium red, cadmopon red, chrome red, molybdate orange and aluminum flake-like alloy pieces are mixed in the resin. Use paint.

  However, in a coating film painted with the paint (red metallic coating), red pigment red and aluminum white are conspicuous, and human eyes have a disadvantage that they appear pink as an intermediate color. In addition, since aluminum has a high surface reflectance of 80% or more in visible light, the red metallic paint mixed with aluminum becomes whitish, does not become red like red metallic plating, and lacks a high-class feeling. There is also.

  On the other hand, red metallic plating, which has a better finish than red metallic coating, has the following problems.

  When the red metallic plating is formed by a dry plating method such as a vacuum evaporation method, the color of the thin film is darkened due to the influence of gas such as oxygen, nitrogen, and argon during the film formation, and the color is not clean. This is because the surface reflectance of the electroplated thin film is about 60%, whereas the surface reflectance of the dry-plated thin film is as low as about 30 to 40%. Moreover, the dry plating thin film has low crack resistance.

  When the red metallic plating is formed by electroplating, the electroplating uses a harmful substance in the solution, so that the waste liquid treatment is costly. In addition, mixing of dissimilar metals makes it impossible to recycle plated products such as aluminum wheels.

  Since red metallic plating has such drawbacks, it is required to eliminate the disadvantages of red metallic coating.

  In order to deal with defects in the appearance of red metallic coating, a method of applying a blackish undercoat to the underlayer has been proposed (Patent Document 1 (Japanese Patent Laid-Open No. 62-13565), Patent Document 2 (Japanese Patent Laid-Open No. 9-126)). -290213).).

  On the other hand, metallic coating using aluminum flake-like alloy pieces has the following problems due to insufficient corrosion resistance of aluminum flake-like alloy pieces in addition to the above-mentioned appearance problems. It has been demanded.

  The aluminum flake-like alloy pieces are active, and when exposed to the atmosphere, an oxide film is formed on the surface and loses the glitter. In addition, as the oxide film grows, the adhesion between the substrate and the coating film (coating film adhesion) decreases.

  In an environment containing moisture, the aluminum flake-like alloy piece forms a hydroxide film on the surface instead of an oxide film. The formed hydroxide film easily becomes an oxide film by drying and heating of the coating film containing the hydroxide film. Since this coating film that has been dried and heated passes moisture, there is a possibility that aluminum and moisture react in the coating film (hydration reaction combined with water molecules), and the coating film may corrode and peel off. Specifically, when a thin film containing an aluminum flake-like alloy piece having a thickness of 0.05 to 1.0 μm is immersed in warm water at 40 to 60 ° C. without a top coat, a hydration reaction occurs, and 24 to 100 hours. Thus, the aluminum flake-like alloy pieces in the coating film are dissolved. Also, in the cast test (JIS 8502), which is a more severe corrosion condition than the salt spray test, even if the top coat is applied, the test solution penetrates through the top coat, and the aluminum flake-like alloy pieces in the paint film are removed in 60 hours or more. Dissolve.

  Thus, the aluminum flake-like alloy piece has a problem that it is vulnerable to corrosion. For this reason, it is necessary to make the top coat as a protective film thick and not to cause scratches.

  However, for example, the protective film tends to be thin at a deep part, and an acidic substance / alkaline substance may permeate and pass through the protective film, and the aluminum flake alloy piece may be dissolved. .

  In addition, if the top coat is damaged, for example, if the coating film on the vehicle body is damaged by a stepping stone while the car is running, or if the coating film is damaged during the cleaning of the vehicle body, When traveling in a zone where salt is sprayed to prevent freezing or in a hot and humid region, the aluminum flake-like alloy piece may come into contact with the external environment, and the coating may start corroding from the scratches.

  Once corrosion of the coating begins and proceeds, the aluminum flake alloy pieces dissolve and disappear, and the undercoat is exposed. Then, not only the original brilliant surface is damaged, but the adhesion between the undercoat and the topcoat is lost, and swelling occurs. Furthermore, there is a possibility of progressing to corrosion of the base material from that point.

  For this reason, various processing methods for improving the corrosion resistance and chemical resistance of aluminum flake alloy pieces have been proposed. However, since aluminum itself has low corrosion resistance and chemical resistance, a sufficient effect is not obtained.

  In the following (1) to (5), a proposed example using an aluminum flake-like alloy piece as a pigment and problems in the proposed example are described.

(1) Patent Document 3 (Japanese Patent Laid-Open No. 2000-354828)
The surface of the aluminum wheel is covered with a plating coat in which an aluminum flake-like alloy piece is mixed with an organic or inorganic coloring pigment. By mixing the reflection of the color pigment and the reflection of the aluminum flake-like alloy piece, a special color tone that meets the appearance design needs can be obtained. In order to obtain an appearance close to that of chrome plating, it is mixed with various pigments.

  However, the brightening material is aluminum, and this plated coating has low corrosion resistance and chemical resistance. For this reason, there is a high possibility that the flake-like alloy pieces will corrode at places where the protective film is difficult to be applied, such as corners and vertical surfaces of wheels. Moreover, since the aluminum flake-like alloy piece is used, only a whitish and high-quality appearance can be obtained. On the other hand, when the mixing ratio of the aluminum flake-like alloy pieces is reduced, the glitter feeling is lowered.

(2) Patent Document 4 (Japanese Patent Laid-Open No. 11-90318)
A composition containing an aluminum flake-like alloy piece and an organic solvent is coated on a phosphate group-containing resin. Special coating is performed to improve the coating film containing aluminum flake-like alloy pieces. However, this method has poor workability, is expensive, and cannot be applied when applied over a wide range.

(3) Patent Document 5 (Japanese Patent Laid-Open No. 9-122575)
In order to prevent the aluminum flake-like alloy piece from being discolored by the organic solvent, the aluminum flake-like alloy piece having a color difference of not less than color chart No. 4 on a gray scale for contamination is used after being immersed in the organic solvent. . However, since this coating film also includes aluminum flake-like alloy pieces, it has low corrosion resistance and chemical resistance.

(4) Patent Document 6 (Japanese Patent Laid-Open No. 7-150374)
In order to impart corrosion resistance, the aluminum flake-like alloy piece is treated with a corrosion inhibitor. Since the corrosion inhibitor contains expensive and rare metal water-soluble salts such as yttrium and rare earth metals, the cost increases. In addition, the process is complicated and the cost is high.

(5) Patent Document 7 (JP-A-7-133440), Patent Document 8 (JP-A-6-57171)
A molybdate film of 0.1 to 10% by mass in terms of Mo metal is formed on aluminum, and 0.05 to 5% by mass of phosphate ester in terms of P element is adsorbed on aluminum. Let However, this process is complicated and time consuming, and increases the cost.

Japanese Patent Laid-Open No. 62-13565 JP-A-9-290213 JP 2000-354828 A Japanese Patent Application Laid-Open No. 11-90318 Japanese Patent Laid-Open No. 9-122575 JP-A-7-150374 JP-A-7-133440 JP-A-6-57171

  The present invention has been made in view of such problems, and a red metallic coating having excellent corrosion resistance and chemical resistance as well as a high-grade color close to that of a red metallic plating coating film. An object of the present invention is to provide a corrosion-resistant glitter pigment and a corrosion-resistant glitter paint using the same.

  The corrosion-resistant bright pigment according to the present invention contains 50% by mass or more of copper, 32 to 43% by mass of zinc, and 3 to 7% by mass of aluminum, and has a lightness L * = 35 in the L * a * b * color system. It is characterized by comprising a flake-like alloy piece having ˜90 and chromaticity of a * = 10-50 and b * = 10-25. Here, the L * a * b * color system is a color system adopted in JISZ8729, and is a color system that expresses lightness as L * and chromaticity indicating hue and saturation as a * and b *. It is a system.

  The surface reflectance of the flaky alloy piece is preferably 25 to 65% with respect to light having a wavelength of 550 nm, and the thickness of the flaky alloy piece is preferably 0.02 to 5 μm, The size of the flaky alloy piece is preferably 5 to 50 μm. Here, the size of the flake-shaped alloy piece means the constant direction diameter of the alloy piece (the length of the longer side of the vertical and horizontal sides of the rectangle circumscribing the alloy piece).

  The corrosion-resistant glitter paint according to the present invention is characterized by containing the corrosion-resistant glitter pigment and the resin, or the corrosion-resistant glitter pigment, the resin, and the red pigment.

  The resin is preferably an acrylic urethane resin or a resin in which an acrylic urethane resin and a melamine resin are mixed, and the red pigment is composed of a petal, cadmium red, cadmopon red, chrome red, vermilion, molybdate orange. One or more inorganic pigments selected from the group are preferred.

  A first aspect of the method for producing a corrosion-resistant bright pigment according to the present invention is a sputtering method or a vapor deposition method for forming a thin film containing 50% by mass or more of copper, 32 to 43% by mass of zinc, and 3 to 7% by mass of aluminum. It is characterized by comprising Step 1 for forming and Step 2 for pulverizing the thin film obtained in Step 1 to obtain a flake-like alloy piece to obtain the corrosion-resistant bright pigment according to the present invention.

  The second aspect of the method for producing a corrosion-resistant bright pigment according to the present invention is a method in which a metal raw material is dissolved in a vacuum and contains 50 mass% or more of copper, 32 to 43 mass% of zinc, and 3 to 7 mass% of aluminum. Step 1 for obtaining an alloy, and Step 2 for obtaining the corrosion-resistant bright pigment according to the present invention by pulverizing the alloy obtained in Step 1 with a grinder and then stamping to obtain a flake-like alloy piece. It is characterized by.

  Since the corrosion-resistant bright pigment according to the present invention has lightness and chromaticity of L * = 35 to 90, a * = 10 to 50, b * = 10 to 25 in the L * a * b * color system, The coating film obtained from the corrosion-resistant glitter paint using the pigment according to the present invention has a high-grade appearance close to that of red metallic plating. Moreover, the corrosion-resistant glitter pigment according to the present invention has excellent corrosion resistance and chemical resistance.

  For this reason, the corrosion-resistant bright pigment according to the present invention can be suitably used for coating home appliances, mobile phone parts, car body parts and the like.

  In addition, when the thickness of the flake-like alloy piece constituting the corrosion-resistant glitter pigment according to the present invention is 0.02 to 5 μm, the color and glitter of the painted surface become better and the coating film is less likely to crack. Become. In this case, since the thickness of the flaky alloy piece is very thin, even if it is melted together with the base metal, the ratio of mixing into the base metal is very small and can be reused, so it is excellent in recyclability. It becomes.

  Furthermore, the corrosion-resistant bright pigment according to the present invention does not use a material harmful to the human body and does not require wastewater treatment during production, and is therefore environmentally friendly and safe.

  In addition, forming a coating film with a paint using the corrosion-resistant bright pigment according to the present invention can be carried out by a simple coating method, so that it is excellent in workability, and the paint is applied to a product that requires design properties. Also suitable for.

  Hereinafter, the best mode for carrying out the present invention will be described.

1) Content of copper, aluminum and zinc The anticorrosive bright pigment according to the present invention contains 50 mass% or more of copper, 32 to 43 mass% of zinc, 3 to 7 mass% of aluminum, and L * a * b *. In the color system, the lightness and chromaticity are L * = 35 to 90, a * = 10 to 50, and b * = 10 to 25.

  The reason why the corrosion-resistant glitter pigment according to the present invention is composed of a flake-shaped alloy piece is because the flake-shaped alloy piece has a high proportion of flat surfaces in the surface, surface reflection easily occurs, and is excellent in glitter. Surface reflection is one of the important performances of anticorrosive glitter pigments.

  The brightness in the L * a * b * color system of the flake-shaped alloy piece constituting the corrosion-resistant bright pigment according to the present invention is L * = 35 to 90, the chromaticity is a * = 10 to 50, and b * = 10. The reason defined as 25 is to obtain a high-grade red color close to red metallic plating in the coated film.

  When L * is less than 35, the brightness and gloss of the appearance are reduced, and the metallic feeling of the coating film is impaired, which is not preferable. If L * exceeds 90, the color of the coating film is too bright and it is difficult to recognize the red color tone, which is not preferable.

  If a * is less than 10, the red color tone is lowered, and the vividness of the coating film is impaired. When a * exceeds 50, redness is too strong, and the color of the coating film is not preferable because it deviates from the copper color. Here, the copper color is a color generated by selectively absorbing wavelengths near 250 nm and 470 nm, particularly by selectively absorbing light having a wavelength near 470 nm (blue green).

  If b * is less than 10, the color of the coating becomes dull and coppery, which is not preferable. If b * exceeds 25, the color of the coating film becomes yellowish and deviates from the copper color.

  In addition, the color of the coating film after coating becomes a high-grade red color similar to that of red metallic plating because the brightness of the coating film is L * = 35 to 90, the chromaticity is a * = 10 to 50, and b *. = 10 to 25, it is more preferable that the lightness of the coating film is L * = 40 to 80, and the chromaticity is a * = 15 to 50 and b * = 10 to 20.

  The reason why it is necessary to contain 50% by mass or more of copper, 32 to 43% by mass of zinc, and 3 to 7% by mass of aluminum is that lightness and chromaticity are L * = 35 to 90, a * = 10 to 50, This is because a flaky alloy piece having b * = 10 to 25 is obtained.

  In the present invention, copper has a function of providing a red base color that appears in the flaky alloy pieces. By adding other metals to copper, corrosion resistance and workability can be improved, and the hue can also be changed.

  When the copper content is less than 50% by mass, the color of the flake-like alloy piece is dark brown with a hue of blackish brown. For this reason, the lightness and chromaticity of the flake-shaped alloy pieces are L * a * b * color system, L * = 33 to 51 for L *, a * = 3 to 40 for a *, and b *. Is b * = 3 to 20, which does not fall within the scope of the present invention, and the desired red color cannot be obtained.

  In the present invention, zinc functions to shift the wavelength absorption band to the short wavelength side.

  When the zinc content is less than 32% by mass, the flake-like alloy piece has a strong copper color and is not reddish. For this reason, the brightness and chromaticity of the flake-shaped alloy pieces are L * a * b * color system, L * = 45 to 56 for L *, a * = 12 to 14 for a *, and b *. B * = 7 to 9, which is not within the scope of the present invention, and the desired red color cannot be obtained. On the other hand, when the zinc content exceeds 43% by mass, the color of the flaky alloy piece is brown. For this reason, the brightness and chromaticity of the flake-shaped alloy pieces are in the L * a * b * color system, L * = 36 to 38 for L *, a * = 15 to 18 for a *, and b *. B * = 6-8, which is not within the scope of the present invention, and the desired red color cannot be obtained.

  In the present invention, aluminum functions to shift the wavelength absorption band of the alloy to the short wavelength side with a small addition amount.

  When the aluminum content is less than 3% by mass, the flake-like alloy piece has a strong copper color and is not reddish. For this reason, the brightness and chromaticity of the flake-shaped alloy pieces are L * a * b * color system, L * = 41 to 51 for L *, a * = 2 to 3 for a *, and b *. Is b * = 25 to 31, which is not within the scope of the present invention, and the desired red color cannot be obtained.

  On the other hand, when the aluminum content exceeds 7% by mass, it becomes gray and whitish. Therefore, in the L * a * b * color system, L * = 48 to 58 for L *, a * = 6 to 8 for a *, and b * = 20 to 25 for b *. The desired red color cannot be obtained.

  Here, the reason why copper exhibits a specific colored gloss is because copper selectively absorbs light in a specific wavelength range. Copper has a characteristic of selectively absorbing light in the wavelength range near 250 nm (ultraviolet light) and light in the wavelength range near 470 nm (blue-green visible light). The absorption of light that affects the color of copper is the absorption of light in the wavelength region near 470 nm, which is the visible light region. In the reflected light of visible light with respect to copper, blue-green, which is the color of light in the wavelength region near 470 nm, decreases. For this reason, the visible copper color is a blue-green aftercolor, that is, copper red.

  Absorption near a wavelength of 250 nm occurs because conduction electrons absorb incident photons and excite them to a higher level vacant band. Absorption near a wavelength of 470 nm occurs because photoelectrons corresponding to the wavelength band excite d-band electrons to a vacant level higher than the Fermi level of the conductor.

  On the other hand, many metals such as aluminum almost completely reflect visible light and infrared rays and have a metallic luster.

  The reason why the color changes depending on the alloy composition as described above relates to the following matters. That is, when copper is alloyed with zinc, conduction electrons increase and the Fermi level increases, so the absorption band shifts to the short wavelength side, and the hue shifts to brass.

  When 50% or more of zinc is added, the alloy exhibits total reflection and the hue becomes silver white. On the other hand, when copper is alloyed with aluminum, the number of conduction electrons per atom of the copper alloy is larger than when zinc is alloyed with the Fermi level.

  For this reason, when aluminum is added to copper, the absorption band shifts to the short wavelength side with a smaller addition amount than when zinc is added.

  Next, the corrosion resistance of the corrosion-resistant bright pigment according to the present invention will be described.

  Copper is a metal with high corrosion resistance. Stainless steel and titanium maintain their corrosion resistance by passivating their surfaces, whereas copper and copper alloys, which are noble metals, themselves maintain invariant states in a wide potential range and pH range.

  However, copper is weak against strong alkalis and corrodes.

  In this respect, the flake-shaped alloy piece constituting the corrosion-resistant bright pigment according to the present invention is hardly corroded even by strong alkali because the predetermined amounts of zinc and aluminum are added to copper.

  Zinc has a function of forming a dense oxide film. For this reason, when zinc is added to copper, it contributes to the improvement of corrosion resistance. If the zinc content is less than 32% by mass, this function is not sufficiently exhibited. On the other hand, when the zinc content exceeds 43% by mass, the hardness of the material decreases and the color becomes silver white.

  Aluminum has a function of forming a strong and thick oxide film. For this reason, when aluminum is added to copper, it contributes to the improvement of corrosion resistance. If the aluminum content is less than 3% by mass, this function is not sufficiently exhibited. On the other hand, if the aluminum content exceeds 7% by mass, the hardness of the material decreases and the color becomes silver white.

2) Thickness and size of flake-shaped alloy pieces The inventors of the present invention have a surface reflectance of 25 to 65% with respect to light having a wavelength of 550 nm, which constitutes the corrosion-resistant bright pigment according to the present invention. It was found that the hue of the coating film after painting was red with a high-class feeling close to that of red metallic plating.

  Since the surface reflectance is related to the thickness of the flaky alloy piece and the length of one side, it is preferable to appropriately adjust the thickness and size, and the thickness is 0.02 to 5 μm, and the size is 5 to 50 μm. It is preferable that

  If the thickness of the flake-shaped alloy piece is less than 0.02 μm, the base (resin coating film) can be seen through, and the lightness and chromaticity of the painted surface is the target range (L * a * b * color) In the system, L * = 35 to 90, a * = 10 to 50, and b * = 10 to 25) are easily removed. In addition, the surface reflectance is lowered and the glitter is lost, which is not preferable.

  When the thickness of the flaky alloy piece exceeds 5 μm, the internal stress of the flaky alloy piece becomes high, and the flaky alloy piece is easily cracked. For this reason, there is a high possibility that cracks will enter the coated film after being dried. Note that even if the thickness of the flake-shaped alloy piece exceeds 5 μm, the surface reflectance does not change, the film formation time is increased, the time required for production is increased, and the cost is merely increased.

  If the size of the flaky alloy piece is less than 5 μm, the reflecting surface becomes small and the glitter feeling is impaired, which is not preferable.

  When the size of the flake-shaped alloy piece exceeds 50 μm, the reflecting surface spreads and the surface reflectance increases, but when the painted surface is viewed from above, there is a portion where the flake-shaped alloy pieces do not overlap each other and the base is visible It is possible and not preferred.

3) Method for producing flake-like alloy piece The flake-like alloy piece constituting the corrosion-resistant bright pigment according to the present invention can be produced by a sputtering method or a vapor deposition method. Specifically, a thin film containing 50% by mass or more of copper, 32 to 43% by mass of zinc, and 3 to 7% by mass of aluminum can be formed, and the thin film can be pulverized.

  The sputtering method used to form a thin film as a raw material for the flake-shaped alloy piece is such that argon ions are struck against the target in a vacuum to give energy, and the atoms constituting the target are ejected, and the target (substrate) is ejected. It is the method of making it adhere.

  Since the sputtering method is not a method of vaporizing with heat and flying atoms, there is no component deviation due to vapor pressure unlike the vacuum deposition method. Therefore, if only a target having one composition is used, a film having almost the same composition as the target composition can be obtained.

  Moreover, it is also possible to obtain a copper-zinc-aluminum alloy thin film by disposing a copper target, a zinc target, and an aluminum target and forming films simultaneously. In this case, the alloy ratio can be adjusted by adjusting the input current of each target.

  The sputtering method may be either a DC magnetron or an RF magnetron. The target can be produced by a melting method or a sintering method.

  The thin film formed on the substrate is scraped or peeled off and collected, then pulverized with a ball mill, etc., or placed in a solution and then pulverized by applying ultrasonic waves to form a flaky alloy piece. Can do. Alternatively, the whole substrate can be put in a solution, and the thin film formed on the substrate can be pulverized while being chemically peeled to form a flaky alloy piece.

  Further, the flake-like alloy piece constituting the corrosion-resistant bright pigment according to the present invention is obtained by dissolving a metal raw material in a vacuum, 50 mass% or more of copper, 32 to 43 mass% of zinc, and 3 to 7 mass% of aluminum. It can also be produced by a method in which an alloy containing is prepared, the alloy is pulverized with a pulverizer, and then stamped to obtain a flaky alloy piece.

  The surface of the flake-like alloy piece constituting the corrosion-resistant glitter pigment according to the present invention is coated with an inorganic material such as silica or an organic material, so that further elution prevention and corrosion resistance can be improved.

4) Corrosion-resistant glitter paint The color-resistant glitter paint according to the present invention is prepared by blending the corrosion-resistant glitter pigment according to the present invention and the resin in an appropriate ratio and stirring well using a stirrer such as a stirrer. Can do.

  As the resin to be used, an acrylic urethane resin or a mixture of an acrylic urethane resin and a melamine resin can be suitably used, but is not limited thereto.

  In addition, a red pigment may be added and added in order to adjust the glitter and chromaticity so as to obtain a high-grade color close to red metallic plating. As the red pigment, a petal (ferric oxide) or an inorganic pigment such as cadmium red, cadmopon red, chrome red, vermilion, molybdate orange, and the like can be preferably used. But the same effect can be obtained.

  The corrosion-resistant bright paint thus produced is sprayed onto a coated object with a spray gun or the like, and is then heated and dried under predetermined conditions.

  The method of heat drying is appropriately selected according to the shape of the coated object. At that time, if the temperature distribution is large, drying unevenness occurs, and therefore, it is preferable to carry out with a hot air drier, a convection oven or the like that is unlikely to generate uneven drying.

[Example 1]
Cu: Zn: Al was weighed so as to have a mass ratio of 60: 35: 5, placed in a vacuum apparatus (AIH-w36200SBT ion plating apparatus manufactured by Shinko Seisakusho Co., Ltd.), and vacuum melted by an electron beam. An alloy was made.

  When the brightness and chromaticity of the alloy were measured with a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.), L * = 47, a * = 48, and b * = 23.

  The alloy was pulverized into fine particles of 1 to 3 μm by a jet mill pulverizer and stamped to obtain flake-like alloy pieces having a thickness of 1 μm and a size of 40 μm. The flake-shaped alloy piece was reddish to the naked eye. Further, the reflectance of the obtained flaky alloy piece was measured with light having a wavelength of 550 nm using the spectrophotometer, and found to be 55%.

10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin and stirred well using a stirrer to prepare a corrosion-resistant glitter paint. The paint was put in a spray gun and applied to a black plastic plate (50 mm × 100 mm × thickness 1 mm) at a pressure of ² kg / cm ² .

  After coating, it was dried at 80 ° C. for 30 minutes using a hot air dryer (manufactured by Kato Corporation, JMB23DP, heating capacity 9 kw). The painted surface after drying had a bronze color with the naked eye.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured with a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.), L * = 45, a * = 45, and b * = 22. The reflectance of the coated surface of the plastic plate was 53% when measured with light having a wavelength of 550 nm using the spectrophotometer.

  Next, 10 g of the dial as a red pigment and 20 g of the flake-like alloy piece were placed in 50 g of the acrylic resin and 50 g of the melamine resin, and stirred well using a stirrer to prepare a corrosion-resistant bright paint. The paint was applied to an iron plate (50 mm × 100 mm × thickness 0.5 mm), and after the coating, it was dried at 150 ° C. for 20 minutes using a hot air dryer in the same manner as described above. The painted surface after drying was a red metallic color with a brilliant feeling to the naked eye.

  The brightness and chromaticity of the coated surface of the iron plate were measured with a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.), and L * = 44, a * = 48, and b * = 20. The reflectance of the coated surface of the iron plate was measured with light having a wavelength of 550 nm using the spectrophotometer and found to be 50%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Example 2]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 65: 32: 3.

  When the brightness and chromaticity of the alloy were measured in the same manner as in Example 1, they were L * = 52, a * = 45, and b * = 15.

  The alloy was made into a flaky alloy piece having a thickness of 2 μm and a size of 35 μm in the same manner as in Example 1. The flake-shaped alloy piece was reddish to the naked eye. Further, the reflectance of the obtained flaky alloy piece was measured in the same manner as in Example 1. As a result, it was 58%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a corrosion-resistant glitter paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After painting, it was dried at 80 ° C. for 30 minutes. The painted surface after drying had a bronze color with the naked eye.

  The lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1. The results were L * = 50, a * = 43, and b * = 13. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 56%.

  Next, 50 g of acrylic resin and 50 g of melamine resin were charged with 10 g of a petal as a red pigment and 20 g of the flake-like alloy piece. A color-resistant glittering paint was prepared in the same manner as in Example 1 and applied to an iron plate. . After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was a red metallic color with a brilliant feeling to the naked eye.

  When the brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1, they were L * = 54, a * = 45, and b * = 18. Moreover, when the reflectance of the coating surface of this iron plate was measured similarly to Example 1, it was 53%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Example 3]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 50: 43: 7.

  The brightness and chromaticity of the alloy were measured in the same manner as in Example 1. The results were L * = 40, a * = 42, and b * = 24.

  The alloy was made into a flaky alloy piece having a thickness of 4 μm and a size of 6 μm in the same manner as in Example 1. The flaky alloy pieces were copper red with the naked eye. The reflectance of the flaky alloy piece was measured in the same manner as in Example 1 and found to be 48%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a corrosion-resistant glitter paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After coating, it was dried at 80 ° C. for 30 minutes. The painted surface after drying had a bronze color with the naked eye.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1, L * = 37, a * = 38, and b * = 18. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 45%.

  Next, 50 g of acrylic resin and 50 g of melamine resin were charged with 10 g of a petal as a red pigment and 20 g of the flake-like alloy piece. A corrosion-resistant glitter paint was prepared in the same manner as in Example 1 and applied to an iron plate. After coating, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was a red metallic color with a brilliant feeling to the naked eye.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 40, a * = 43, and b * = 20. The reflectance of the painted surface of the iron was measured in the same manner as in Example 1 and found to be 42%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Example 4]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 56: 38: 6.

  The brightness and chromaticity of the alloy were measured in the same manner as in Example 1. The results were L * = 54, a * = 38, and b * = 12.

  The alloy was made into a flaky alloy piece having a thickness of 0.03 μm and a size of 45 μm in the same manner as in Example 1. The flake-shaped alloy piece was reddish to the naked eye. Further, the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, and found to be 50%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a corrosion-resistant glitter paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After painting, it was dried at 80 ° C. for 30 minutes. The painted surface after drying was reddish to the naked eye.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1, L * = 52, a * = 34, and b * = 10. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 47%.

  Next, 50 g of acrylic resin and 50 g of melamine resin were charged with 10 g of a petal as a red pigment and 20 g of the flake-like alloy piece. A corrosion-resistant glitter paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was a red metallic color with a brilliant feeling to the naked eye.

  The brightness and chromaticity of the coated surface of the iron plate were measured in the same manner as in Example 1. The results were L * = 56, a * = 42, and b * = 16. Moreover, when the reflectance of the coating surface of this iron plate was measured similarly to Example 1, it was 45%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Example 5]
An alloy was prepared in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 60: 35: 5, and a target having a diameter of 100 mmφ and a thickness of 3 mm was prepared using the alloy. Produced.

  When the brightness and chromaticity of the target were measured by the same method as in Example 1, they were L * = 47, a * = 48, and b * = 23.

  Next, the target is set in a vacuum apparatus (SH-S100, DC magnetron method manufactured by Nippon Vacuum Technology Co., Ltd.), and a polypropylene film (a lacquer is applied on the surface to form a lacquer layer by 1 μm using an electron beam). The film was vacuum-deposited to form a thin film. The film thickness was 0.04 μm. The thin film was immersed in MEK (methyl ethyl ketone), only polypropylene was dissolved, and only the thin film was taken out.

  The thin film was made 14 μm in size with an ultrasonic pulverizer (manufactured by Ipros) to obtain a flake-like alloy piece. The flake-shaped alloy piece was reddish to the naked eye. Moreover, when the reflectance of the obtained flaky alloy piece was measured in the same manner as in Example 1, it was 60%.

  The flaky alloy piece was put into MEK to prepare a dispersion so that the mass ratio was 10%, and 90 g of a transparent acrylic urethane resin was added to 10 g of the dispersion. And it stirred well using the stirrer and produced the corrosion-proof glittering coating material.

  The paint was applied to a black plastic plate in the same manner as in Example 1. After painting, it was dried at 80 ° C. for 30 minutes. The painted surface of the plastic plate after drying had a bronze color with the naked eye.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1, L * = 45, a * = 45, and b * = 17. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 58%.

  Next, 50 g of acrylic resin and 50 g of melamine resin were charged with 10 g of a petal as a red pigment and 20 g of the flake-like alloy piece. A corrosion-resistant glitter paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was a red metallic color with a brilliant feeling to the naked eye.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 44, a * = 48, and b * = 20. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 56%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Example 6]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 60: 35: 5.

  The brightness and chromaticity of the alloy were measured in the same manner as in Example 1. The results were L * = 47, a * = 48, and b * = 23.

  The alloy was made into a flaky alloy piece having a thickness of 1 μm and a size of 40 μm in the same manner as in Example 1. The flake-shaped alloy piece was reddish to the naked eye. Further, the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, and found to be 55%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a corrosion-resistant glitter paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After painting, it was dried at 80 ° C. for 30 minutes. The painted surface after drying had a bronze color with the naked eye.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1, L * = 45, a * = 45, and b * = 17. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 53%.

  Next, 10 g of chrome red as a red pigment and 20 g of the flake-like alloy piece were placed in 50 g of acrylic resin and 50 g of melamine resin, and a corrosion-resistant bright paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was a red metallic color with a brilliant feeling to the naked eye.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 44, a * = 48, and b * = 20. Moreover, when the reflectance of the coating surface of this iron plate was measured similarly to Example 1, it was 52%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Comparative Example 1]
The Cu ingot was put into a fine powder of 1 to 3 μm using a jet mill grinder. The fine powder was stamped into flaky metal pieces having a thickness of 1 μm and a size of 40 μm. The flaky alloy piece was copper-colored with the naked eye. When the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, it was 65%.

  When the brightness and chromaticity of the Cu ingot were measured by the same method as in Example 1, they were L * = 83, a * = 16, and b * = 16.

10 g of the flaky metal piece was added to 90 g of a transparent acrylic urethane resin and stirred well using a stirrer to prepare a paint. The paint was put in a spray gun and applied to a black plastic plate at a pressure of ² kg / cm ² . After coating, it was dried at 80 ° C. for 30 minutes. The painted surface after drying had a bronze color with the naked eye.

  The lightness and chromaticity of the coated surface of the plastic plate were measured in the same manner as in Example 1. The results were L * = 80, a * = 16, and b * = 14. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 63%.

  Next, 10 g of a petite as a red pigment and 20 g of the flake-like alloy piece were placed in 50 g of an acrylic resin and 50 g of a melamine resin, and a paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was a red metallic color with a brilliant feeling to the naked eye.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 78, a * = 30, and b * = 18. When the reflectance of the iron plate was measured in the same manner as in Example 1, it was 60%.

  Next, when the iron plate was immersed in a 5% NaOH solution for 24 hours, the color of copper was changed and 50% of the area was changed to green.

[Comparative Example 2]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 49: 46: 5.

  The brightness and chromaticity of the alloy were measured in the same manner as in Example 1. The results were L * = 33, a * = 40, and b * = 20.

  The alloy was made into a flaky alloy piece having a thickness of 6 μm and a size of 52 μm in the same manner as in Example 1. The flake-like alloy pieces looked brownish to the naked eye. When the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, it was 42%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After painting, it was dried at 80 ° C. for 30 minutes. The painted surface after drying looked brownish.

  The lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1. The results were L * = 30, a * = 37, and b * = 17. When the reflectance of the plastic plate was measured in the same manner as in Example 1, it was 39%.

  Next, 10 g of a petite as a red pigment and 20 g of the flake-like alloy piece were placed in 50 g of an acrylic resin and 50 g of a melamine resin, and a paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying looked brownish.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 28, a * = 41, and b * = 50. When the reflectance of the iron plate was measured in the same manner as in Example 1, it was 35%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Comparative Example 3]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 43: 55: 2.

  The brightness and chromaticity of the alloy were measured in the same manner as in Example 1. The results were L * = 51, a * = 3, and b * = 29.

  The alloy was formed into a flake-shaped alloy piece having a thickness of 0.01 μm and a size of 4 μm in the same manner as in Example 1. The flake-like alloy piece had a red color tone and a yellowish color with the naked eye. When the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, it was 25%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After painting, it was dried at 80 ° C. for 30 minutes. The painted surface after drying had a reddish appearance with a naked eye and a yellowish appearance.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1, L * = 48, a * = 1, and b * = 27. Further, the reflectance of the plastic plate was measured in the same manner as in Example 1, and found to be 24%.

  Next, 10 g of a petite as a red pigment and 20 g of the flake-like alloy piece were placed in 50 g of an acrylic resin and 50 g of a melamine resin, and a paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying had a reddish appearance with a naked eye and a yellowish appearance.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 50, a * = 5, and b * = 30. Further, the reflectance of the plastic plate was measured in the same manner as in Example 1, and found to be 23%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Comparative Example 4]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 42: 55: 3.

  The brightness and chromaticity of the alloy were measured in the same manner as in Example 1. The results were L * = 48, a * = 3, and b * = 31.

  The alloy was formed into a flaky alloy piece having a thickness of 2 μm and a size of 60 μm in the same manner as in Example 1. The flaky alloy piece was reddish yellowish to the naked eye. When the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, it was 44%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After painting, it was dried at 80 ° C. for 30 minutes. The painted surface after drying was yellowish red with the naked eye, the ground was visible, and the overlapping of pigment steps was conspicuous.

  The lightness and chromaticity of the coated surface of the plastic plate were measured in the same manner as in Example 1. The results were L * = 46, a * = 1, and b * = 28. Further, the reflectance of the plastic plate was measured in the same manner as in Example 1, and found to be 42%.

  Next, 10 g of the dial as a red pigment and 20 g of the flake-shaped alloy piece were placed in 50 g of acrylic resin and 50 g of melamine resin, and a paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was red with a yellowish tinge, the base was visible, and the overlap of pigment steps was conspicuous.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 44, a * = 5, and b * = 25. Moreover, when the reflectance of this iron plate was measured similarly to Example 1, it was 41%.

  Next, the iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Comparative Example 5]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 66: 28: 6.

  When the brightness and chromaticity of the alloy were measured in the same manner as in Example 1, they were L * = 54, a * = 3, and b * = 45.

  The alloy was made into a flaky alloy piece having a thickness of 1 μm and a size of 55 μm in the same manner as in Example 1. The flaky alloy piece was reddish yellowish to the naked eye.

  When the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, it was 54%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After coating, it was dried at 80 ° C. for 30 minutes. The painted surface after drying was yellowish to the naked eye.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1, L * = 52, a * = 1, and b * = 43. Further, the reflectance of the plastic plate was measured in the same manner as in Example 1, and found to be 52%.

  Next, 10 g of a petite as a red pigment and 20 g of the flake-like alloy piece were placed in 50 g of an acrylic resin and 50 g of a melamine resin, and a paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was yellowish red with the naked eye. In addition, the appearance was grainy and there was no denseness.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 50, a * = 4, and b * = 40. When the reflectance of the iron plate was measured in the same manner as in Example 1, it was 50%.

  The iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

[Comparative Example 6]
An alloy was produced in the same manner as in Example 1 except that the mass ratio of Cu: Zn: Al was 43: 55: 2.

  The brightness and chromaticity of the alloy were measured in the same manner as in Example 1. The results were L * = 51, a * = 3, and b * = 29.

  The alloy was formed into a flake-shaped alloy piece having a thickness of 0.01 μm and a size of 4 μm in the same manner as in Example 1. The flaky alloy piece was reddish yellowish to the naked eye. Further, the reflectance of the flaky alloy piece was measured in the same manner as in Example 1, and found to be 25%.

  10 g of the flaky alloy piece was added to 90 g of a transparent acrylic urethane resin, and a paint was prepared in the same manner as in Example 1 and applied to a black plastic plate. After coating, it was dried at 80 ° C. for 30 minutes. The painted surface after drying had a reddish appearance with a naked eye and a yellowish appearance.

  When the lightness and chromaticity of the coated surface of the plastic plate were measured by the same method as in Example 1, L * = 48, a * = 1, and b * = 27. Further, the reflectance of the coated surface of the plastic plate was measured in the same manner as in Example 1, and found to be 24%.

  Next, 10 g of cadmium red as a red pigment and 20 g of the flake-like alloy piece were placed in 50 g of acrylic resin and 50 g of melamine resin, and a paint was prepared in the same manner as in Example 1 and applied to an iron plate. After painting, it was dried at 150 ° C. for 20 minutes. The painted surface after drying was reddish and yellowish to the naked eye.

  The brightness and chromaticity of the coated surface of the iron plate were measured by the same method as in Example 1. The results were L * = 50, a * = 5, and b * = 30. Moreover, when the reflectance of the coating surface of this iron plate was measured similarly to Example 1, it was 23%.

  The iron plate was immersed in a 5% NaOH solution for 24 hours, but the metal was not dissolved and the appearance was not changed.

  In Examples 1 to 6 in which the composition of the flaky alloy pieces is within the scope of the present invention, the brightness and chromaticity of the alloy are also within the scope of the present invention (L * = 35 to 90 in the L * a * b * color system). A * = 10-50, b * = 10-25). For this reason, the lightness and chromaticity of the painted surfaces of the plastic plate and the iron plate coated with the paint produced using the flake-like alloy piece made of the alloy are also L * = 35 in the L * a * b * color system. ˜90, a * = 10 to 50, b * = 10 to 25, and a high-grade appearance close to that of red metallic plating was obtained. Moreover, the corrosion resistance of the coating film was also good.

  On the other hand, Comparative Examples 2 to 6 in which the composition of the flaky alloy pieces does not fall within the scope of the present invention, the brightness and chromaticity of the alloy are also within the scope of the present invention (in the L * a * b * color system). L * = 35 to 90, a * = 10 to 50, b * = 10 to 25). For this reason, the lightness and chromaticity of the painted surfaces of the plastic plate and the iron plate coated with the paint produced using the flake-like alloy piece made of the alloy are also L * = 35 in the L * a * b * color system. It was not in the range of -90, a * = 10-50, b * = 10-25, and it did not become a high-grade appearance close to red metallic plating. Further, in Comparative Example 1 in which the composition of the flake-shaped alloy piece is composed only of Cu, the brightness and chromaticity of the alloy and the brightness and chromaticity of the painted surface are L * = 35 to 90 in the L * a * b * color system. It was in the range of a * = 10-50, b * = 10-25, and the painted surface had a high-grade appearance close to red metallic plating. However, the corrosion resistance of the coating film was not good.

Claims (11)

  Contains 50 mass% or more of copper, 32 to 43 mass% of zinc, and 3 to 7 mass% of aluminum. In the L * a * b * color system, the lightness is L * = 35 to 90, and the chromaticity is a * = 10. A corrosion-resistant glitter pigment characterized by comprising a flake-like alloy piece having ˜50 and b * = 10 to 25.   The corrosion-resistant glitter pigment according to claim 1, wherein the surface reflectance of the flaky alloy piece is 25 to 65% with respect to light having a wavelength of 550 nm.   The corrosion-resistant bright pigment according to claim 1 or 2, wherein the flake-shaped alloy piece has a thickness of 0.02 to 5 µm.   The corrosion-resistant bright pigment according to claim 1, wherein the flake-shaped alloy piece has a size of 5 to 50 μm.   5. A corrosion-resistant glitter paint comprising the corrosion-resistant glitter pigment according to claim 1 and a resin.   The corrosion-resistant glitter paint according to claim 5, wherein the resin is an acrylic urethane resin or a resin obtained by mixing an acrylic urethane resin and a melamine resin.   5. A corrosion-resistant glitter paint comprising the corrosion-resistant glitter pigment according to any one of claims 1 to 4, a resin, and a red pigment.   8. The corrosion-resistant glitter paint according to claim 7, wherein the resin is an acrylic urethane resin or a resin obtained by mixing an acrylic urethane resin and a melamine resin.   The red pigment is one or more inorganic pigments selected from the group consisting of petals, cadmium red, cadmopon red, chrome red, vermilion, and molybdate orange. Corrosion-resistant glitter paint.   Step 1 of forming a thin film containing 50% by mass or more of copper, 32 to 43% by mass of zinc, and 3 to 7% by mass of aluminum by sputtering or vapor deposition, and crushing the thin film obtained in Step 1 to form flakes And obtaining a corrosion-resistant glitter pigment according to any one of claims 1 to 4, and obtaining a corrosion-resistant glitter pigment.   Step 1 to obtain an alloy containing 50% by mass or more of copper, 32 to 43% by mass of zinc and 3 to 7% by mass of aluminum by melting a metal raw material in a vacuum, and the alloy obtained in step 1 with a pulverizer After pulverizing, stamping to obtain a flake-like alloy piece, and obtaining the corrosion-resistant bright pigment according to any one of claims 1 to 4, comprising a step 2 for producing a corrosion-resistant bright pigment.