JP2006028426A - Corrosion-resistant brilliant pigment, and coating composition for corrosion-resistant brilliant coating film obtained using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a corrosion-resistant brilliant pigment which has external appearances close to those obtained by chrome electroplating, can cope with needs for novel pigments requiring the adjustment of brightness and color tones and gives a coating film exhibiting excellent corrosion resistance and chemical resistance instead of a brilliant pigment obtained using an aluminum flake. <P>SOLUTION: The corrosion-resistant brilliant pigment comprises a first flaky metal piece (M1) and a second flaky metal piece (M2) having a different color tone from that of the first flaky metal piece (M1), and the second flaky metal piece (M2) is of one color or of two or more colors. Otherwise, the second flaky metal piece (M2) is different in the surface reflectance properties from the first flaky metal piece (M1). Preferably, the first flaky metal piece (M1) and the second flaky metal piece (M2) have a size of 10-100 μm and a thickness of 0.01-0.1 μm, respectively. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a corrosion-resistant bright pigment suitable for brightening substrates such as automobile parts and household appliance parts.

  As means for brightening substrates such as automobile parts and home appliance parts, there are wet plating, vacuum deposition and metallic coating. In particular, metallic coating has a simple method and is widely used. That is, it is a coating method in which an aluminum pigment or flake is mixed in a paint in order to brighten the substrate, and a clear coat is applied thereon to protect the aluminum.

  In general, aluminum flake is a vacuum deposition method in which metallic aluminum is mechanically pulverized by a stamp mill method, dry ball mill method or wet ball mill method, or an aluminum film is formed by evaporating metal aluminum in a vacuum. Or the like.

  By the way, since aluminum is advantageous in that it is inexpensive and has a high surface reflectance, aluminum foil and aluminum thin film are widely used as pigments.

  However, aluminum has the disadvantages that the surface reflectance is as high as 80% or more in visible light, the appearance is whitish, and lacks a high-class feeling like chrome plating.

  On the other hand, the use of chrome plating as a means for brightening has problems for the following reasons. That is, when a chromium thin film is formed by a dry plating method, the color of the thin film becomes dark due to the influence of a gas such as oxygen, nitrogen or argon during the film formation. The surface reflectance of the chromium thin film by the dry plating method is about 30 to 40%, which is lower than that of the surface reflectance of the chromium thin film by the electroplating method. Further, chrome plating has low crack resistance, and also has a disadvantage that it cannot be recycled because of dissimilar metals when it is used for an aluminum wheel or the like in consideration of the environment.

  In the case of using aluminum flakes, a method of applying a blackish undercoat to the underlayer has been adopted in order to compensate for the appearance defects (see Japanese Patent Application Laid-Open No. 62-13565).

  In addition, aluminum foils and thin films are active, and when exposed to the air, an oxide film is formed and the glitter is lost. 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, a hydroxide film is formed instead of an oxide film. A hydroxide film formed on an aluminum foil or thin film easily becomes an oxide film by drying and heating the coating film containing it, but the dried and heated film has water permeability. Therefore, the hydration reaction that water and aluminum that have passed through the coating film react in the coating film (bonds with water molecules) may lead to corrosion and peeling of the coating film. Specifically, an aluminum thin film having a film thickness of 0.05 μm to 1.0 μm dissolves in 24 to 100 hours by a hydration reaction when immersed in warm water of 40 ° C. to 60 ° C. without a top coat. Moreover, a mixed solution of 4% salt water and 0.027% cupric chloride (dihydrate) was sprayed on a test tank (JIS H 8502; a test tank set at 50 ° C.) In the case of evaluating the corrosiveness and corrosion resistance of the test piece), even when the topcoat is applied, the test solution penetrates through the topcoat and the aluminum thin film dissolves in 60 hours or more.

  Even when an aluminum foil or thin film having such a property is used as aluminum flakes, if the top coat as a protective film is thick or does not cause scratches, no serious problem will occur. However, even in this case, for example, when the substrate has irregularities, the protective film is thinned in the recessed part, and chemicals such as acid or alkali penetrate the protective film, and the aluminum foil or thin film is removed. Dissolve. Also, if the top coat is damaged when used in rough roads, coastal areas, areas where salt is sprayed to prevent freezing, or hot and humid areas, for example, the actual vehicle may be damaged by stepping stones while driving, If a vehicle gets scratched during cleaning, the aluminum foil or film touches the external environment, and the coating begins to corrode from the scratch. Once the coating corrosion begins and proceeds, the aluminum foil and film dissolve and disappear, exposing the undercoat. In this case, not only the original brilliant surface is impaired, but also the undercoat and the topcoat are not closely adhered, and swelling occurs. Furthermore, there is a possibility of progressing to corrosion of the base material from that point.

  Conventionally, various processing methods for improving the corrosion resistance and chemical resistance of aluminum foils and thin films have been proposed. However, since the corrosion resistance and chemical resistance of aluminum itself are low, the actual situation is that a great effect is not obtained. These proposed examples and their drawbacks are shown in the following (1) to (7).

(1) JP 2000-354828 A The surface of an aluminum wheel is covered with a plating-like coat in which aluminum flakes are mixed in an organic or inorganic color pigment. By mixing the reflection of the color pigment and the reflection of the aluminum flakes, 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.

(2) JP, 7-292294, A Scale-like colored metal pigment (Am) and one or more scale-like colored metal pigments (An) having a color tone different from that of the scale-like colored metal pigment (Am) It is a color flip-flop metallic paint. Specifically, a combination of various colored pigments attached to the surface of scaly aluminum flakes is combined.

  However, the pigments described in Japanese Patent Application Laid-Open Nos. 2000-354828 and 7-292294 are made of aluminum as a brightening material, and these plated coatings have low corrosion resistance and chemical resistance. Therefore, there is a high possibility that aluminum flakes are dissolved at places where the protective film is difficult to be applied, such as corners and vertical surfaces of wheels. In addition, since aluminum flakes are used, it is impossible to overcome the appearance that is whitish and has no sense of quality. Further, depending on the method for adjusting the mixing ratio of the aluminum flakes, the glitter feeling is lowered.

(3) JP-A-9-311561 Aluminum flakes are coated on a phosphate group-containing resin. Special coating is applied to improve the aluminum flake coating. However, this method has poor workability, is expensive, and cannot be applied in a wide range.

(4) Japanese Unexamined Patent Publication No. 9-122575 In order to prevent aluminum flakes from being discolored by an organic solvent, the color change after immersion in an organic solvent is a gray scale for contamination and has a color difference of color chart 4 or more. Use flakes. However, since this coating film also contains aluminum flakes, the chemical resistance is low.

(5) JP-A-7-133440 In order to impart corrosion resistance, aluminum flakes are treated with a corrosion inhibitor. Corrosion inhibitors include water soluble salts such as yttrium and rare earth metals. However, it is necessary to process the aluminum flakes through a complicated process using such a precious metal, and the aluminum flakes are expensive.

(6) JP-A-6-57171 A molybdic acid coating film of 0.1 to 10% by mass in terms of Mo metal is formed on aluminum, and on that, 0.005 in terms of P element relative to aluminum. 0.5 to 5% by mass of phosphate ester is adsorbed. However, this process is complicated and time consuming, and increases the cost.

  As another problem, the brightness and color tone of the aluminum foil and thin film alone are the same, so that the need for a new pigment that needs to be adjusted for brightness and color tone cannot be answered.

  Moreover, since the metal thin film itself formed by the vapor deposition method has poor color tone, a colored metal pigment was obtained by putting a metal foil film into the colored pigment and covering the surface, but it was not sufficient.

(7) Japanese Patent Application Laid-Open No. 2003-292823 By using a flake-like alloy piece containing 15 to 50% by mass of titanium and the balance being aluminum and inevitable impurities, an appearance close to electrochrome plating and excellent corrosion resistance and chemical resistance Corrosion-resistant glitter pigments can be obtained, which can provide a coating film having a flaky structure, but in the production method, a flake-like alloy is produced by sputtering using an Al-Ti alloy as a target, and only the color of the composition of the target used can be produced. First, in order to meet the customer's demand for color tone, it was necessary to prepare a number of targets to make a flake-like alloy, and select the color tone from among them, which required time and cost for development. .

Japanese Patent Laid-Open No. 62-13565

JP 2000-354828 A

JP 7-292294 A

JP-A-9-311561

Japanese Patent Laid-Open No. 9-122575

JP-A-7-133440

JP-A-6-57171

JP 2003-292823 A

  The object of the present invention is to solve the above problems, meet the needs of new pigments that have an appearance close to electrochrome plating, and need to adjust brightness and color tone, and have excellent corrosion resistance and chemical resistance. An object of the present invention is to provide a corrosion-resistant bright pigment capable of obtaining a coating film having the same, instead of the bright pigment using aluminum flakes.

  One aspect of the corrosion-resistant bright pigment of the present invention is a first flaky metal piece (M1) and a second flaky metal piece having a color tone different from the color tone of the first flaky metal piece (M1) ( M2) and the second flaky metal piece (M2) has one color or two or more colors.

  A different aspect of the corrosion-resistant bright pigment of the present invention has a surface reflectance characteristic different from the surface reflectance characteristics of the first flaky metal piece (M1) and the first flaky metal piece (M1), In addition, the second flaky metal piece (M2) has one color or two or more colors.

  Furthermore, the first flaky metal piece (M1) and the second flaky metal piece (M2) preferably have a size of 10 μm to 100 μm.

  The first flaky metal piece (M1) and the second flaky metal piece (M2) preferably have a thickness of 0.01 μm to 0.1 μm.

  Further, the first flaky metal piece (M1) is 20 to 95% by mass of Al flake, and the remaining second flaky metal piece (M2) is Ti flake, Ni flake, Ti alloy. It is preferable that it is 1 or more types chosen from flakes and Ni alloy flakes.

  The first flaky metal piece (M1) and the second flaky metal piece (M2) are preferably obtained by pulverizing a thin film formed by a sputtering method or a vapor deposition method.

  The coating composition for a corrosion-resistant glitter coating film of the present invention contains any one of the above-mentioned corrosion-resistant glitter pigments and a vehicle.

  The corrosion-resistant bright pigment according to the present invention has an appearance close to that of electrochrome plating, can respond to new needs that require adjustment of brightness and color tone in a short period of time, has excellent design properties, and excellent corrosion resistance And has chemical resistance. In addition, since the anticorrosive glitter pigment of the present invention is environmentally friendly and safe, it is excellent in recyclability and can be surface-treated by a simple coating method, so that it is excellent in workability.

  By using the obtained anticorrosive luster pigment, pigments of various colors can be produced, and can be used for various designs by the mixing method, and excellent pigments can be provided.

  One aspect of the corrosion-resistant bright pigment of the present invention is a first flaky metal piece (M1) and a second flaky metal piece having a color tone different from the color tone of the first flaky metal piece (M1) ( M2) and the second flaky metal piece (M2) has one color or two or more colors.

  Moreover, the different aspect of the corrosion-resistant bright pigment of the present invention has the first flaky metal piece (M1) and surface reflectance characteristics different from the surface reflectance characteristics of the first flaky metal piece (M1). The second flaky metal piece (M2) is contained, and the second flaky metal piece (M2) has one color or two or more colors.

  The first flaky metal piece (M1) is 20 to 95% by mass of Al flakes. The remaining second flaky metal piece (M2) is at least one selected from Ti flakes, Ni flakes, Ti alloy flakes and Ni alloy flakes.

  Here, Ti-Al and Ti-Al-V are preferable as the Ti alloy flakes, and Inconel and Hastelloy are preferable as the Ni alloy flakes.

  When flaky metal pieces having different surface reflectances are present in the same area, there is an illusion that a human eye will see a color tone intermediate between the respective color tones of the flaky metal piece. By utilizing this, by mixing Al flakes with a light color tone and one or more flake-like metal pieces selected from Ti flakes, Ni flakes, Ti alloy flakes and Ni alloy flakes with a black color tone, The tone becomes dark and calm, and the color tone can be changed with each content.

  In Patent Document 8, one color tone is obtained with a flake-like alloy having a single composition of Ti: 15 to 40% and Al: the balance, but the present invention mixes two or more types of flakes having different color tones, and For this reason, there is a feature that you can easily and freely change the color tone by changing the mixing ratio. In addition, regarding corrosion resistance and chemical resistance, an oxide film is formed on each of the obtained mixed flakes, but the oxide film of Ti or Ni is dense and strong, and becomes a pseudo alloy by mixing. The oxide film is also considered to be stronger than conventional Al flakes.

  Since chrome plating used in the past uses harmful chemicals, it may not be approved as a surface treatment method in the future, and similar luster is mixed with two or more kinds of flakes of different colors. This is also useful for environmental measures.

  If the Al flakes are less than 20% by mass, the color becomes brownish, and the surface reflectance is lowered. If the Al flakes exceed 95% by mass, the appearance of Al is close and the corrosion resistance is not improved.

  In the corrosion-resistant glitter pigment of the present invention, Ti and Ni lower the surface reflectance, and Al increases the surface reflectance. Therefore, the anticorrosion bright pigment of the present invention is brighter than Ti or Ni, and the color tone is gray. Therefore, a coating film having a surface reflectance and appearance close to those of electrochrome plating can be obtained by the corrosion-resistant bright pigment of the present invention. A coating film having a color tone from light gray to dark brown can also be obtained by appropriately selecting the composition.

  Furthermore, Ti, Ni, Ti alloys and Ni alloys significantly improve corrosion resistance and chemical resistance, and Al significantly improves crack resistance. Even if the content of Ti, Ni, Ti alloy and Ni alloy is less than 5% by mass or more than 80% by mass, the surface reflectance and the appearance are far from the electrochrome plating.

  As described above, the corrosion-resistant glitter pigment (flake material) of the present invention is composed of a plurality of flake-like metal pieces. In the anticorrosive bright pigment, surface reflection is one of the important performances, and the flake-like metal piece is suitable because the ratio of the plane to the surface is high.

  Furthermore, the first flaky metal piece (M1) and the second flaky metal piece (M2) preferably have a size of 10 μm to 100 μm.

  Here, the size of the flake-shaped metal piece refers to the fixed direction diameter of the flake-shaped metal piece (longitudinal length of the rectangle circumscribing the metal piece, the length of the horizontal side). When the size of the flaky metal piece is less than 10 μm, the reflection surface becomes small, and the glitter feeling is impaired. On the other hand, when the size of the flaky metal piece exceeds 100 μm, the reflection surface spreads and the surface reflectance increases, but the gap between adjacent flaky metal pieces becomes large, and the substrate may be visible.

  The first flaky metal piece (M1) and the second flaky metal piece (M2) preferably have a thickness of 0.01 μm to 0.1 μm.

  If the thickness of the flaky metal piece is less than 0.01 μm, the underlayer can be seen through, giving a whitish appearance, and the surface reflectance is too low. On the other hand, if the thickness of the flaky metal piece exceeds 0.1 μm, the stress of the flaky metal piece increases, and the possibility of cracking in the flaky metal piece increases. Even if the thickness of the flaky metal piece exceeds 0.1 μm, it takes a long time to form a thin film as a raw material for the flaky metal piece, and the surface reflectance does not change, and the cost increases.

  In order to obtain a coating film having surface reflectance and appearance close to those of electrochrome plating, the surface reflectance of the flaky metal piece is preferably 25 to 65% with light having a wavelength of 550 nm. For that purpose, the mixing ratio of each flaky metal piece may be appropriately adjusted according to the thickness and size of the flaky metal piece to be used. By mixing vapor deposition flakes having a high surface reflectivity and a low metal appearance with flake-like metal pieces of colored metal, a corrosion-resistant bright pigment having a new color tone can be obtained.

  The sputtering method used when forming a thin film as a raw material for the flaky metal piece gives energy by causing argon ions to collide with the target in a vacuum, causing atoms constituting the target to jump out, and an object (substrate) It is the method of making it adhere to. This sputtering method is not a method of vaporizing and flying with heat, so there is no component deviation due to vapor pressure. Therefore, if only a target having one composition is used, a film having almost the same composition as that of the target can be obtained. Moreover, the thin film used as the raw material of the flaky metal piece can also be formed by a vapor deposition method or an ion plating method.

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

  The thin film formed on the substrate is collected by scraping or peeling off, and then pulverized by a conventional method such as a ball mill or by applying ultrasonic waves after being placed in a solution. Alternatively, the thin film formed on the substrate can be pulverized while being chemically peeled after being placed in the solution together with the substrate.

  The coating composition for a corrosion-resistant glitter coating film of the present invention contains any one of the above-mentioned corrosion-resistant glitter pigments and a vehicle.

  The dry film thickness of the corrosion-resistant glittering coating film obtained by the present invention is preferably 20 μm to 100 μm, and if it falls outside this range, the coating film appearance may be lowered. More preferably, it is 30 micrometers-50 micrometers. The preferable content of the anticorrosive luster pigment of the present invention is 5 to 25 parts by mass with respect to 100 parts by mass of vehicle solids in the coating film. If the amount is less than 5 parts by mass, the concealing property of the anticorrosive glittering pigment may be deteriorated, and there is a possibility that a coating film expressing vivid whiteness may not be obtained. There is. More preferably, it is 5-15 mass parts.

  In the present invention, the vehicle used for forming the corrosion-resistant glitter coating film, and contained in the coating composition for corrosion-resistant glitter coating film, disperses the corrosion-resistant glitter pigment, and comprises a coating film-forming resin and If necessary, it is composed of a crosslinking agent.

  Examples of the resin for forming a coating film include (a) acrylic resin, (b) polyester resin, (c) alkyd resin, (d) fluororesin, (e) epoxy resin, (f) polyurethane resin, (g) A polyether resin etc. are mentioned, These can be used individually or in combination of 2 or more types. In particular, (a) an acrylic resin and (b) a polyester resin are preferable.

(A) Acrylic resin Examples of the acrylic resin include a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Acrylic monomers include acrylic acid or methacrylic acid methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, etc. Esterified products, ring-opening adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate, acrylic acid or glycidyl methacrylate, acrylamide, methacrylamide and N-methylolacrylamide, (meth) acrylic esters of polyhydric alcohols Etc. Examples of the ethylenically unsaturated monomer include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.

(B) Polyester resin Examples of the polyester resin include saturated polyester resins and unsaturated polyester resins, and examples include condensates obtained by heat condensation of polybasic acids and polyhydric alcohols. Examples of the polybasic acid include saturated polybasic acid and unsaturated polybasic acid. Examples of the saturated polybasic acid include phthalic anhydride, terephthalic acid, succinic acid, and the like. Examples thereof include maleic acid, maleic anhydride, and fumaric acid. Examples of the polyhydric alcohol include dihydric alcohol and trihydric alcohol. Examples of the dihydric alcohol include ethylene glycol and diethylene glycol. Examples of the trihydric alcohol include glycerin and trimethylolpropane. Etc.

(C) Alkyd resin As the alkyd resin, in addition to the polybasic acid and the polyhydric alcohol, oil and fat fatty acid (soybean oil, linseed oil, coconut oil, stearic acid, etc.), natural resin (rosin, amber, etc.), etc. An alkyd resin obtained by reacting a modifying agent can be used.

(D) Fluororesin As the fluororesin, any one of vinylidene fluoride resin, tetrafluoroethylene resin or a mixture thereof, a polymerizable compound containing a fluoroolefin and a hydroxy group, and other copolymerizable vinyl compounds are used. Examples thereof include resins made of various fluorine-based copolymers obtained by copolymerizing the following monomers.

(E) Epoxy resin Examples of the epoxy resin include resins obtained by the reaction of bisphenol and epichlorohydrin. Examples of bisphenol include bisphenol A and F. Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001, Epicoat 1004, Epicoat 1007, and Epicoat 1009.

(F) Polyurethane resin Examples of the polyurethane resin include resins having a urethane bond obtained from various polyol components such as acrylic, polyester, polyether, and polycarbonate and a polyisocyanate compound. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and mixtures thereof (TDI), diphenylmethane-4,4 ′. -Diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), and mixtures thereof (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3 '-Dimethyl-4,4'-biphenylene diisocyanate, xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (HXDI) Etc. It can be.

(G) Polyether resin The polyether resin is a polymer or copolymer having an ether bond, such as a polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether, or bisphenol A. Or the polyether resin which has at least 2 hydroxyl group per molecule, such as polyether derived from aromatic polyhydroxy compounds, such as bisphenol F, can be mentioned. In addition, the polyether resin reacts with polyvalent carboxylic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, or reactive derivatives such as these acid anhydrides. And a carboxyl group-containing polyether resin obtained by the above process.

  In addition, the coating film forming resin includes a curable type and a lacquer type. Usually, a curable type is used. In the case of a curable type, it is used by mixing with a crosslinking agent such as an amino resin, a (block) polyisocyanate compound, an amine, a polyamide, or a polyvalent carboxylic acid, and the curing reaction proceeds with heating or at room temperature. be able to. It is also possible to use a lacquer type coating film-forming resin having no curability and a curable type coating film-forming resin in combination.

  When the vehicle contains a cross-linking agent, the ratio of the resin for forming a coating film and the cross-linking agent is 90 to 50% by mass of the resin for forming a film and 10 to 50% by mass of the cross-linking agent in terms of solid content. The film-forming resin is preferably 85 to 60% by mass and the crosslinking agent is 15 to 40% by mass. When the crosslinking agent is less than 10% by mass (when the coating film forming resin exceeds 90% by mass), crosslinking in the coating film is not sufficient. On the other hand, when the crosslinking agent exceeds 50% by mass (when the coating film forming resin is less than 50% by mass), the storage stability of the coating composition is lowered and the curing rate is increased, so that the coating film appearance is deteriorated. .

  Specific examples of the crosslinking agent include isocyanates and amine-based crosslinking agents.

Example 1
Using a 10 cm square, 1 mm thick polypropylene plate substrate, immersing it in an acrylic lacquer paint (manufactured by Nippon Paint) solution and forming an acrylic coating film having a thickness of about 0.1 μm on the substrate surface. Using an aluminum target having a diameter of 250 mm and a thickness of 5 mm produced by a melting method, an aluminum thin film was formed by a direct current magnetron sputtering method as follows.

First, the substrate after film formation was set in a direct current magnetron sputtering apparatus (manufactured by Nippon Vacuum), first evacuated to 7 × 10 ⁻³ Pa, and then introduced argon gas until 2 × 10 ⁻¹ Pa. Other film formation conditions were as follows: distance between target and substrate: 107 mm, substrate rotation speed: 9 rpm, target current: 3 A (voltage: 650 V), film formation time: 2 minutes.

  Next, the substrate on which the aluminum thin film was formed was immersed in an acetone solution, the acrylic coating film was eluted, and the aluminum thin film was peeled from the substrate. Then, it grind | pulverized for 60 second with the ultrasonic wave (90W, 43kW) in the solvent, and obtained Al flakes.

  Furthermore, Ti flakes were similarly obtained using a Ti target instead of the Al target.

  The obtained Al flakes had a thickness of 0.07 μm and a size of about 50 μm. The obtained Ti flakes had a thickness of 0.06 μm and a size of about 46 μm.

  Furthermore, the surface reflectance was measured with light having a wavelength of 550 nm using a spectrophotometer (manufactured by Hitachi, Ltd., U-2810). The surface reflectance of Al flakes was 75%, and the surface reflectance of Ti flakes was 20%.

  The obtained Al flakes and Ti flakes were mixed at a mass ratio of Al flakes: Ti flakes of 20%: 80%, 10 g was weighed and prepared into 90 g of solvent (MEK), 100 mg was weighed, and 200 mg of acetone was added. To obtain a first paint. Furthermore, the second paint was obtained by setting the mass ratio of Al flakes: Ti flakes to 40%: 60%, and the third paint was obtained by setting the mass ratio of Al flakes: Ti flakes to 80%: 20%.

  The surface reflectance of the first paint was measured with light having a wavelength of 550 nm using a spectrophotometer (manufactured by Hitachi, U-2810). The surface reflectance of the first paint was 24%.

  The surface reflectance of the second paint was 42%, and the surface reflectance of the third paint was 65%.

  A coating film was actually formed and the following evaluation was performed.

Aluminum alloy casting AC4C (Al-Si-Mg based) plate material (thickness 3 mm), was formed to 80g / m ² ~150g / m ² of chromium amount conversion coating with chromate treatment. Next, in order to smooth the surface, 100 μm of acrylic powder coating was applied and dried at 150 ° C. for 1 hour. Further, a clear polyester / melamine resin as an undercoat was formed to 30 μm with an air spray gun and dried at 140 ° C. for 30 minutes to obtain a substrate.

  Then, the above-mentioned 1st coating material was apply | coated 1 micrometer-2 micrometers by the air spray on the said base material. On top of that, three types of top coats of acrylic / melamine resin with a thickness of 5 μm, 10 μm and 25 μm were formed with an air spray gun and dried at 140 ° C. for 30 minutes.

  The external appearance of the three kinds of surface treatment materials having different color tones obtained as described above was free from cracks and cracks, and had a high brightness and a color tone close to that of chrome plating compared to conventional metallic coating materials. The surface reflectance of the coating film obtained from the first paint was 34%.

  In addition, these surface treatment materials were evaluated for test items shown in Table 1 and mainly based on electroplating standards. As a result, all the test items were passed. Table 1 shows the surface reflectance of the coating film, test items, test method, and test results obtained.

  Similarly, using the second paint and the third paint, three types of surface treatment materials having different color tones were obtained, and the same test was performed. The surface reflectance of the coating film obtained with the second coating material was 48%, and the surface reflectance of the coating film obtained with the third coating material was 62%. The test results obtained are shown in Table 1.

(Example 2)
Ni flakes and Al flakes were obtained in the same manner as in Example 1 except that a Ni target was used instead of the Ti target.

  The obtained Ni flakes had a thickness of 0.07 μm and a size of about 55 μm. Moreover, the surface reflectance of the Ni flakes measured in the same manner as in Example 1 was 25%.

  Furthermore, as in Example 1, when the first paint, the second paint, and the third paint were obtained and the surface reflectance was measured, the surface reflectance of the first paint was 35%. The surface reflectance of the second paint was 52%, and the surface reflectance of the third paint was 72%.

  Moreover, it carried out similarly to Example 1, and formed the coating film actually and evaluated. The surface reflectance of the coating film obtained with the first paint was 38%, and the surface reflectance of the coating film obtained with the second paint was 51%, which was obtained with the third paint. The surface reflectance of the coating film was 65%. Table 2 shows the results.

  Moreover, the appearance of the obtained surface treatment material was free from cracks and cracks, and had a high brightness and a color tone close to that of chrome plating compared to conventional metallic coating materials.

Example 3
Ti-Al-V flakes and Al flakes were obtained in the same manner as in Example 1 except that a Ti-Al-V target was used instead of the Ti target.

  The obtained Ti—Al—V flakes had a thickness of 0.06 μm and a size of about 53 μm. Moreover, the surface reflectance of the Ti—Al—V flakes measured in the same manner as in Example 1 was 35%.

  Furthermore, as in Example 1, when the first paint, the second paint, and the third paint were obtained and the surface reflectance was measured, the surface reflectance of the first paint was 41%. The surface reflectance of the second paint was 53%, and the surface reflectance of the third paint was 68%.

  Moreover, it carried out similarly to Example 1, and formed the coating film actually and evaluated. The surface reflectance of the coating film obtained with the first paint was 42%, and the surface reflectance of the coating film obtained with the second paint was 52%, which was obtained with the third paint. The surface reflectance of the coating film was 65%. Table 3 shows the results. As in Examples 1 and 2, the appearance of the obtained surface treatment material was free from cracks and cracks, and had a high brightness and color tone close to that of chrome plating compared to conventional metallic coating materials.

Example 4
Hastelloy flakes and Al flakes were obtained in the same manner as in Example 1 except that a Hastelloy C alloy target was used instead of the Ti target.

  The obtained Hastelloy flakes had a thickness of 0.07 μm and a size of about 52 μm. Further, the surface reflectance of Hastelloy flakes measured in the same manner as in Example 1 was 45%.

  Furthermore, as in Example 1, when the first paint, the second paint, and the third paint were obtained and the surface reflectance was measured, the surface reflectance of the first paint was 48%. The surface reflectance of the second paint was 54%, and the surface reflectance of the third paint was 68%.

  Moreover, it carried out similarly to Example 1, and formed the coating film actually and evaluated. The surface reflectance of the coating film obtained with the first paint was 47%, and the surface reflectance of the coating film obtained with the second paint was 53%, which was obtained with the third paint. The surface reflectance of the coating film was 65%. Table 4 shows the results. As in Examples 1 and 2, the appearance of the obtained surface treatment material was free from cracks and cracks, and had a high brightness and color tone close to that of chrome plating compared to conventional metallic coating materials.

(Comparative Example 1)
10 g of Al flakes obtained in Example 1 were weighed and prepared in 20 g of the solvent butyl acetate, and applied to the substrate obtained in Example 1 by an air spray gun in an amount of 1.0 μm to 1.5 μm. Two types of acrylic and melamine resin top coats having a thickness of 5 μm and 10 μm were formed with an air spray gun and dried at 140 ° C. for 30 minutes.

The two tones of different surface treatment material obtained as described above, 1 cm ³ hanging 5 wt% sulfuric acid, for 4 hours, was allowed to stand, the thickness of the top coat in the surface treatment material 5 [mu] m, and titrated A portion of the aluminum flake material was 100% dissolved. Further, in the surface treatment material having a top coat film thickness of 10 μm, 50% of the aluminum flake material in the titrated portion was dissolved.

  Further, a cross-cut was put into two types of surface treatment materials produced in the same manner, and a cast test was performed. As a result, after 12 hours, dissolution of the aluminum flake material occurred at a width of 5 mm from the crosscut portion.

  Moreover, the crosscut was put into 2 types of surface treatment materials produced similarly, and the 60 degreeC warm water test was implemented. As a result, after 36 hours, dissolution of the aluminum flake material occurred from the cross cut portion.

Claims (7)

  Containing a first flake-shaped metal piece (M1) and a second flake-shaped metal piece (M2) having a color tone different from the color tone of the first flake-shaped metal piece (M1), and the second The flake-like metal piece (M2) has one or more colors, and is a corrosion-resistant bright pigment.   A first flaky metal piece (M1) and a second flaky metal piece (M2) having a surface reflectance characteristic different from the surface reflectance characteristic of the first flaky metal piece (M1). And the second flake-like metal piece (M2) has one color or two or more colors.   The corrosion-resistant bright pigment according to claim 1 or 2, wherein the first flaky metal piece (M1) and the second flaky metal piece (M2) have a size of 10 µm to 100 µm.   The corrosion-resistant glitter according to claim 1 or 2, wherein the first flaky metal piece (M1) and the second flaky metal piece (M2) have a thickness of 0.01 µm to 0.1 µm. Pigments.   The first flake-like metal piece (M1) is 20 to 95% by mass of Al flake, and the remaining second flake-like metal piece (M2) is Ti flakes, Ni flakes, Ti alloy flakes and The corrosion-resistant glitter pigment according to any one of claims 1 to 4, wherein the pigment is one or more selected from Ni alloy flakes.   The first flaky metal piece (M1) and the second flaky metal piece (M2) are obtained by pulverizing a thin film formed by sputtering or vapor deposition. A corrosion-resistant bright pigment according to claim 1.   A coating composition for a corrosion-resistant glitter coating film, comprising the corrosion-resistant glitter pigment according to any one of claims 1 to 6 and a vehicle.