JP2006257241A - Glitter pigment and coating material composition for glitter coating film and method for producing glitter pigment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide glitter pigment and coating material composition for glitter coating film inexpensively having an appearance resembling the electric chromium plating, coping with new need of pigment for adjusting the lightness and the color tone, further obtain the coating film having excellent resistance to corrosion and chemicals resistance. <P>SOLUTION: The pigment is constituted with thin film flakes composed of at least one kind of metal selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy and gold alloy and the surface reflection coefficient of the thin film flake metal piece is adjusted to 10 to 70% to the light having a wavelength of 550 nm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a luster pigment, a coating composition for luster coating film, and a method for producing the luster pigment, and can be suitably used for brightening substrates such as automobile parts and household appliance parts.

  Means for brightening substrates such as automobile parts and home appliance parts include wet plating, vacuum deposition and metallic coating. In particular, metallic coating has a simple method and is widely used. In the metallic coating, in order to brighten the base material, after coating using a paint mixed with an aluminum pigment or flakes, a clear coat for protecting aluminum is further applied on the coating.

  Aluminum flakes used in metallic coating are generally produced by mechanically crushing metallic aluminum using a stamp mill, dry ball mill, or wet ball mill, or obtained by vacuum deposition. That is, the aluminum thin film obtained by evaporating metallic aluminum in a vacuum is made into a thin piece.

  Aluminum is advantageous in that it is a metal that is inexpensive and has a high surface reflectance. Therefore, a flaky aluminum foil or film is used as a pigment in metallic coating. However, the surface reflectance of aluminum with respect to visible light is as high as 80% or more. For this reason, the metallic coating using aluminum has a defect in appearance such that the appearance is whitish and lacks a high-class feeling like chrome plating.

  On the other hand, when chromium plating is used as a means for brightening, if the chromium thin film is formed by a dry plating method, the color of the thin film becomes dark due to the influence of gases such as oxygen, nitrogen, and argon during the film formation. There is a problem. That is, the surface reflectance of the chromium thin film obtained by the electroplating method is about 60%, whereas the surface reflectance of the chromium thin film obtained by the dry plating method is as low as about 30 to 40%. Chrome plating also has the problem of low crack resistance. Further, when chrome plating is used for an aluminum wheel or the like, since different metals are mixed, it becomes difficult to perform recycling, which is also a problem from the viewpoint of environmental considerations.

  In the case of using aluminum as a bright pigment, a method of applying a blackish undercoat as a base has been proposed in order to compensate for the above-mentioned defects in appearance (for example, Patent Document 1 (Japanese Patent Laid-Open No. 62-13565)). .

  However, since aluminum foil and thin film are active, an oxide film is formed when exposed to the atmosphere, and not only the glittering feeling is lost, but also the adhesion between the substrate and the coating film as the oxide film grows. There exists a problem that property (coating-film adhesiveness) falls. Further, in an environment containing moisture, a hydroxide film is formed instead of an oxide film. However, a hydroxide film formed on an aluminum foil or thin film can be easily dried or heated to form an oxide film. It becomes. Thus, since the oxide film produced from the hydroxide film by drying and heating has water permeability, a hydration reaction between the water that has passed through the oxide film and aluminum occurs in the coating film. Corrosion and delamination can occur.

  Specifically, when an aluminum thin film having a film thickness of 0.05 to 1.0 μm is immersed in warm water at 40 to 60 ° C. without a top coat (a protective coating layer formed on the aluminum thin film), the hydration reaction causes Dissolves in 24-100 hours. Moreover, a mixed solution of 4% salt water and 0.027% cupric chloride (dihydrate) was sprayed on a test tank (JIS H 8502; set at 50 ° C.), In the case where the corrosion resistance and corrosion resistance of the test piece are evaluated), even if a top coat is applied on the aluminum thin film, the test solution penetrates through the top coat, and the aluminum thin film dissolves in 60 hours or more.

  Aluminum foil and thin film have the above-mentioned properties. However, when the top coat as a protective film is thick and the top coat is not damaged, no major problem occurs.

  However, for example, when the substrate is uneven, the protective film on the aluminum foil or thin film formed on the substrate may be thin at the recessed part. Or chemicals such as alkali penetrate and dissolve aluminum foil and thin film. Also, it is used in bad road areas, coastal areas, areas where salt is sprayed to prevent freezing, hot and humid areas, etc. When the top coat is damaged, for example, the actual vehicle is running and scratched by stepping stones. If the vehicle gets scratched during cleaning, the aluminum foil or thin 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 layer. In this case, not only the original brilliant surface is damaged, but also 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 these problems, various treatment 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) Patent Document 2 (Japanese Patent Laid-Open No. 2000-354828) describes that the surface of an aluminum wheel is coated 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, it is possible to obtain a special color tone that meets the appearance design needs. By mixing with various pigments, an appearance close to that of chrome plating can be obtained.

(2) Patent Document 3 (Japanese Patent Laid-Open No. 7-292294) includes a scaly colored metal pigment (Am) and one or more scaly colored metal pigments (An) having different colors. A color flip-flop metallic paint is described. Specifically, it is a combination of scaly aluminum flakes with various colored pigments attached thereto.

  However, in the pigments described in Patent Documents 2 and 3, the material to be brightened is aluminum, and the plating coat using the pigment has low corrosion resistance and chemical resistance. Therefore, there is a high possibility that the flakes are dissolved at places where it is difficult to apply the protective film, 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) Patent Document 4 (Japanese Patent Laid-Open No. 11-90318) describes coating aluminum flakes on a phosphate group-containing resin. In order to improve the aluminum flake coating film, special coating is performed. However, this method is inferior in workability, increases in cost, and cannot be applied when applied over a wide range.

(4) In Patent Document 5 (Japanese Patent Application Laid-Open No. 9-122575), in order to prevent the aluminum flakes from being discolored by the organic solvent, the color change after being immersed in the organic solvent is colored with a gray scale for contamination. It is described that aluminum flakes having a color difference of No. 4 or more are used. However, since this coating film also contains aluminum flakes, the chemical resistance is low.

(5) Patent Document 6 (Japanese Patent Laid-Open No. 7-150374) describes that aluminum flakes are treated with a corrosion inhibitor in order to impart corrosion resistance. Water-soluble salts such as rare earth metals are included. In addition to the use of such precious metals, aluminum flakes are processed through a complicated process, so that the aluminum flakes are expensive.

(6) In Patent Document 7 (Japanese Patent Laid-Open No. 7-133440), a molybdate film of 0.1% by mass to 10% by mass in terms of Mo metal is formed on aluminum, and aluminum is formed thereon. It is described that 0.05 mass% to 5 mass% of phosphate ester is adsorbed in terms of P element. However, this process is complicated and time consuming, and increases the cost.

(7) Patent Document 8 (Japanese Patent Application Laid-Open No. 2003-292823) describes that flake powder is produced with an Al—Ti film using a sputtering method, but the sputtering method has a slow film formation rate, Low productivity increases the cost of flakes.

  In addition, since the brightness and the color tone are the same only with the aluminum flake-like foil or thin film, there is a problem that the need for a new pigment that needs to adjust the brightness and the color tone cannot be answered.

Japanese Patent Laid-Open No. 62-13565

JP 2000-354828 A

JP 7-292294 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 2003-292823 A

  The present invention has been made in view of such a problem, has an appearance that is cheap and has an appearance close to that of electrochrome plating, can meet the needs of new pigments that need to be adjusted in brightness and color tone, and It is an object of the present invention to provide a glitter pigment and a paint composition for glitter coating, which can obtain a coating having excellent corrosion resistance and chemical resistance.

  The first aspect of the glitter pigment according to the present invention is a glitter pigment made of a thin-film flaky metal piece, and the thin-film flaky metal piece is copper, silver, tin, nickel, gold, a copper alloy, a silver alloy, It is made of at least one metal selected from the group consisting of a tin alloy, a nickel alloy, and a gold alloy, and the thin film flaky metal piece has a surface reflectance of 10 to 70% with respect to light having a wavelength of 550 nm. It is characterized by that.

  The second aspect of the glitter pigment according to the present invention is a glitter pigment composed of a thin film flaky metal piece having a two-layer structure, and the first layer of the thin film flaky metal piece is made of copper, silver, tin, nickel, It consists of a thin film of at least one metal selected from the group consisting of gold, copper alloy, silver alloy, tin alloy, nickel alloy and gold alloy. The second layer is chromium, titanium, nickel, chromium alloy, titanium alloy, nickel. It consists of a thin film of at least one metal selected from the group consisting of alloys.

  It is preferable that the surface reflectance of the first layer and the surface reflectance of the second layer of the thin film flaky metal piece having the two-layer structure are 10 to 70% with respect to light having a wavelength of 550 nm.

  The thin film flaky metal piece preferably has a film thickness of 10 to 200 nm and a size of 5 to 40 μm in a constant direction diameter. Here, the fixed direction diameter is the length of the longer side of the lengths of the vertical and horizontal sides of the rectangle circumscribing the metal piece.

  The coating composition for a glittering coating film according to the present invention is characterized by containing the glittering pigment and a vehicle.

  The glitter coating film according to the present invention is formed using the coating composition for glitter coating film.

  A first aspect of the method for producing a glitter pigment according to the present invention is characterized in that a thin-film flaky metal piece is produced using an electroless plating method.

  In the second aspect of the method for producing the glitter pigment according to the present invention, a metal thin film is formed on a substrate by vapor deposition or sputtering, and then a metal thin film is further formed on the metal thin film using an electroplating method. Thus, a thin-film flaky metal piece is produced.

  The third aspect of the method for producing the glitter pigment according to the present invention is as follows: (a) a metal thin film is formed on the substrate by electroless plating, or (b) metal is deposited on the substrate by vapor deposition or sputtering. After forming the thin film, a step 1 of forming a metal thin film on the metal thin film using an electroplating method, and the metal thin film formed in the step 1 is peeled off from the substrate and pulverized to form a thin film flake-shaped metal piece Step 2 to obtain the above. The thickness of the metal thin film formed in the step 1 is preferably 10 to 200 nm.

  The fourth aspect of the method for producing the glitter pigment according to the present invention is as follows: (a) a metal thin film is formed on the substrate by electroless plating, or (b) metal is deposited on the substrate by vapor deposition or sputtering. After forming the thin film, a step 1 of forming a metal thin film on the metal thin film by using an electroplating method, and an electroless plating method or an electroplating method on the metal thin film formed in the step 1 Forming a thin film made of the same or different metal as the metal thin film formed in step 1 to obtain a metal thin film having a two-layer structure; peeling off the metal thin film having the two-layer structure formed in step 2 from the substrate; And a step 3 of obtaining a thin-film flaky metal piece by pulverization. The film thickness of the two-layered metal thin film formed in the step 2 is preferably 10 to 200 nm.

  The fifth aspect of the method for producing the glitter pigment according to the present invention is as follows. (A) By using the electroless plating method, copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin on the substrate. Forming a thin film made of at least one metal selected from the group consisting of an alloy, a nickel alloy, and a gold alloy, or (b) forming a metal thin film on a substrate by vapor deposition or sputtering; A thin film made of at least one metal selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy is formed on the thin film by electroplating. It has the process 1 which forms, and the process 2 which peels the metal thin film formed at the said process 1 from a board | substrate, and obtains a thin film flake-like metal piece by grinding | pulverizing. The thickness of the metal thin film formed in the step 1 is preferably 10 to 200 nm.

  The sixth aspect of the method for producing the glitter pigment according to the present invention is as follows. (A) By using the electroless plating method, copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin on the substrate Forming a thin film made of at least one metal selected from the group consisting of an alloy, a nickel alloy, and a gold alloy, or (b) forming a metal thin film on a substrate by vapor deposition or sputtering; A thin film made of at least one metal selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy is formed on the thin film by electroplating. Step 1 of forming and at least one selected from the group consisting of chromium, titanium, nickel, chromium alloy, titanium alloy, nickel alloy by electroless plating or electroplating on the metal thin film formed in step 1 Seed metal Step 2 for obtaining a thin metal film having a two-layer structure by forming a thin film comprising the steps, and Step 3 for obtaining a thin-film flake-shaped metal piece by peeling and crushing the metal thin film having the two-layer structure formed in Step 2 from the substrate It is characterized by having. The film thickness of the two-layered metal thin film formed in the step 2 is preferably 10 to 200 nm.

  The metal thin film formed on the substrate by the vapor deposition method or the sputtering method is at least one selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy. It is preferable to consist of these metals.

  According to the glittering pigment and the coating composition for glittering coating film according to the present invention, there is a need for a new pigment (reflectance is low) that has an appearance that is cheap and has an appearance close to that of electrochrome plating, and that needs to adjust brightness and color tone. From a small blackish appearance to a bright metallic glossy appearance with a high reflectivity, it is possible to obtain a coating film with excellent design and a coating film with excellent corrosion resistance and chemical resistance Can do.

  Further, according to the coating composition for glittering coating film according to the present invention, since a thin film having the above characteristics can be formed by a coating method, it is easier to construct than the case of forming a glittering thin film using electroplating. In the case of large parts, it is extremely advantageous particularly in terms of workability.

  Furthermore, since the method for producing a glittering pigment according to the present invention is based on a wet method, there is an advantage that the productivity is high and the cost of the pigment is reduced.

  The present inventor peels off a metal thin film (including those obtained by laminating the same or different metal thin films) from a substrate by using an electroless plating method or after performing electroless plating. By using the thin-film flaky metal piece produced by pulverization as a bright pigment, it has a good characteristic, that is, an appearance that is inexpensive and close to electrochrome plating, and it is necessary to adjust brightness and color tone The present inventors have found that a coating film that can meet the needs of pigments and that has excellent corrosion resistance and chemical resistance can be obtained.

  In addition, the present inventor uses a method of forming a metal thin film by the electroless plating method. After forming a metal thin film on a substrate by a vapor deposition method or a sputtering method, the metal thin film is formed on the metal thin film by using an electroplating method. It has been found that the method of forming a thin film may be replaced.

1. Bright pigment The bright pigment according to the present invention is made of at least one metal selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy. It consists of a thin film flake-like metal piece, and the surface reflectance of this thin film flake-like metal piece is 10 to 70% with respect to light having a wavelength of 550 nm.

  The reason why the glitter pigment according to the present invention is composed of a thin film flake-shaped metal piece is that the surface reflectance is one of the important performances in the glitter pigment. This is because the surface reflectance increases because the ratio of the plane is high.

  This is because, by using these thin-film flaky metal pieces as a glitter pigment, a coating film having a strong glitter feeling is formed, and the color tone can be easily adjusted.

  In addition, it is preferable from the viewpoint of corrosion resistance to form at least one metal thin film selected from chromium, titanium, nickel and alloys thereof by electroplating on the thin film flaky metal piece.

  The thin-film flaky metal piece includes a metal thin film (on which the same or different metal thin films are laminated) formed on a substrate by using an electroless plating method or after electroless plating is performed by using an electroplating method. ) Is peeled from the substrate and pulverized.

  The method of forming a metal thin film by the electroless plating method is a method of forming a metal thin film on the metal thin film by using an electroplating method after forming the metal thin film on the substrate by vapor deposition or sputtering. It may be replaced with. The metal thin film formed on the substrate by vapor deposition or sputtering is for the purpose of obtaining electrical conductivity, and is made of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy. A metal thin film made of at least one metal selected from the group is preferably used.

  It is preferable to use a plastic or metal plate as the substrate when the metal thin film is produced by the electroless plating method. Acrylic, polyester, rubber-based, phenolic is used on the substrate so that the plating film can be peeled off after the film formation. Apply thin resin. Then, the substrate can be immersed in an electroless plating solution to obtain an electroless plating film made of an arbitrary component. It is desirable to control by the plating time at the time of metal thin film preparation so that the film thickness of a metal piece may become a film thickness according to a use.

  The surface reflectance of the thin-film flaky metal piece obtained by the method described above is preferably 10 to 70% with respect to light having a wavelength of 550 nm. By setting the surface reflectance in such a range, the obtained corrosion-resistant bright coating film can be a coating film having a surface reflectance and appearance close to those of electrochrome plating. If it is out of the above range, a coating film having surface reflectance and appearance close to that of electrochrome plating cannot be obtained.

  In order to obtain the above-described surface reflectance, the thickness and size of the thin-film flake-shaped metal piece to be used are 10 to 200 nm in film thickness, the size is a fixed direction diameter (rectangular vertical and horizontal circumscribing the metal piece) The length of the longer side among the lengths of the sides is preferably 5 to 40 μm. Thereby, the surface reflectance of each metal film of a flaky metal piece can be suitably adjusted within the range of said surface reflectance.

  When the film thickness of the thin-film flaky metal piece is less than 10 nm, the glitter feeling becomes poor and light is transmitted. When the thickness is greater than 200 nm, when the thin film flake-shaped metal pieces are overlapped to form a coating film, a step is formed and irregular reflection occurs, resulting in a whitish color and a loss of brightness. Further, even if the thickness exceeds 200 nm, the surface reflectance does not change, and it takes time to produce a thin film, resulting in high costs.

  As for the size of the thin-film flaky metal piece, when the constant direction diameter is smaller than 5 μm, the reflection area is small and the glitter feeling is poor. On the other hand, if it exceeds 40 μm, the coating film loses its denseness. In addition, there is a possibility that it will not be possible to pass through the dust collecting filter of the painting line.

  The thickness of the metal thin film produced by the electroless plating method or the electroplating method is preferably 10 to 200 nm. If the thickness is less than 10 nm, the underlayer can be seen through, giving a whitish appearance, and the surface reflectance is too low. On the other hand, when the thickness exceeds 200 nm, the stress generated in the flaky metal piece in the coating film increases, and the possibility of cracking in the flaky metal piece increases. Further, even if the thickness exceeds 200 nm, the surface reflectance does not change, and it takes only a long time to form a film, which increases the cost.

  A thin film formed on a resin substrate by a wet plating method (electroless plating method or electroplating method) is immersed in a solvent together with the substrate, and a thin resin layer applied before the thin film is formed on the substrate is melted on the substrate. A thin film flake-shaped metal piece having an arbitrary size can be obtained by pulverizing the obtained thin film. As the solvent, for example, a ketone solvent can be used. As a method for pulverizing the obtained thin film, a conventional method such as a ball mill or a method in which ultrasonic waves are applied after being placed in a solution can be used. Alternatively, the thin film formed on the substrate can be pulverized while being peeled chemically from the substrate after being placed in the solution together with the substrate.

  In order to obtain a light-colored metal piece, the thin film flake-like metal piece constituting the glitter pigment according to the present invention is nickel, tin, copper, silver, gold, nickel alloy, tin alloy, copper alloy, silver alloy, It is desirable to be made of a gold alloy.

  In order to improve the corrosion resistance, it is desirable to deposit a metal thin film by plating chromium, titanium, or nickel on the thin film flake-like metal piece. In addition, a thin flaky metal piece obtained by electroplating a thin film of chrome, titanium or nickel on a metal thin film obtained by electroless plating is used as a pigment, thereby providing a coating with a strong glitter feeling. A film can be formed. The deposited second layer metal (chromium, titanium, nickel) has high reflectivity, contributes to the improvement of the reflectivity of the thin-film flaky metal piece, and easily becomes an oxide film, which is passivated, Contributes to improved corrosion resistance.

  In thin film flake metal pieces obtained by plating chromium, titanium and nickel, plating with chromium, titanium and nickel is mainly formed to improve corrosion resistance, but at the same time, the surface reflectance of the thin film flake metal pieces Can be high. The surface reflectance of each element of chromium, titanium, and nickel is approximately 60%, 56%, and 58% with respect to light having a wavelength of 550 nm, respectively.

  By forming an electroplating thin film on the thin film obtained by the electroless plating method or electroplating method, and changing the color tone of each thin film, a thin film flake-like metal piece having two colors can be produced. , It can be excellent in design.

  For example, if a copper thin film is formed by electroless plating, and then a chromium thin film is formed by electroplating, the surface on one side of the obtained thin film flake-like metal piece becomes a dark thin film with low reflectivity. The opposite surface is in a bright metallic luster with high reflectivity. Further, when a conductive metal film (for example, aluminum, copper, tin, nickel) is formed by vapor deposition or sputtering, and a chromium thin film is formed thereon by electroplating, the resulting thin film flake-shaped metal piece The surface on one side is dark and has a low reflectance, and the surface on the other side is bright and has a high reflectance of metallic luster. For this reason, the pigment of a new color tone can be obtained by selecting each surface reflectance.

  As described above, the pigment according to the present invention appropriately adjusts the surface reflectance and color tone by adjusting the film thickness and size (constant direction diameter) of the thin-film flaky metal piece or by forming a two-layer structure. Since it can be selected, by using the pigment according to the present invention, it is possible to form a coating film having a low reflectance and a blackish appearance to a coating film having a high reflectance and a bright metallic luster.

2. Glossy Coating Film Composition The glittering coating composition according to the present invention can be obtained by mixing any of the above-described glittering pigments and a vehicle.

  The preferable content of the glitter pigment in the paint composition for a glittering coating film of the present invention is 5 to 30 parts by mass with respect to 100 parts by mass of vehicle solids in the coating composition. When the amount is less than 5 parts by mass, the concealing property of the glitter pigment is lowered, and there is a possibility that a coating film expressing clear whiteness may not be obtained. When the amount exceeds 30 parts by mass, the appearance of the coating film may be deteriorated. is there. From the viewpoint of the appearance of the coating film, 5 to 15 parts by mass is more preferable.

  The vehicle used in the present invention disperses the glitter pigment, and is composed of a coating film forming resin and, if necessary, a crosslinking agent.

  Examples of the resin for forming a coating film constituting the vehicle include (a) acrylic resin, (b) polyester resin, (c) alkyd resin, (d) fluororesin, (e) epoxy resin, (f) polyurethane resin, (G) A polyether resin etc. can be mentioned, These can be used individually or in combination of 2 or more types. In particular, acrylic resins and polyester resins are preferred from the viewpoint of weather resistance and adhesion.

(A) As an acrylic resin, the copolymer of an acryl-type monomer and another ethylenically unsaturated monomer can be mentioned. Acrylic monomers that can be used in the copolymer include acrylic acid or methacrylic acid methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-hydroxy. Esterified compounds such as ethyl and 2-hydroxypropyl, ring-opening adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate, acrylic acid or glycidyl methacrylate, acrylamide, methacrylamide and N-methylolacrylamide, polyhydric alcohol (Meth) acrylic acid ester and the like. Examples of the ethylenically unsaturated monomer include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.

(B) As a polyester resin, a saturated polyester resin and an unsaturated polyester resin can be mentioned, Specifically, the condensate obtained by heat-condensing a polybasic acid and a polyhydric alcohol can be mentioned, for example. . Examples of polybasic acids include saturated polybasic acids and unsaturated polybasic acids. Examples of saturated polybasic acids include phthalic anhydride, terephthalic acid, succinic acid, and the like. Examples of the basic acid include maleic acid, maleic anhydride, fumaric acid and the like. 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.

(C) Examples of alkyd resins include the polybasic acids and polyhydric alcohols, and other modifiers such as fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.) and natural resins (rosin, succinic acid, etc.). An alkyd resin obtained by reacting can be used.

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

(E) As an epoxy resin, the resin etc. which are obtained by reaction of bisphenol and epichlorohydrin can be mentioned. 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) As a polyurethane resin, resin which has a urethane bond obtained by various polyol components, such as an acryl, polyester, polyether, a polycarbonate, and a polyisocyanate compound can be mentioned. 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. Rukoto can.

(G) The polyether resin is a polymer or copolymer having an ether bond, such as a polyoxyethylene-based polyether, a polyoxypropylene-based polyether, or a polyoxybutylene-based polyether, or bisphenol A or bisphenol F. And polyether resins having at least two hydroxyl groups per molecule, such as polyethers derived from aromatic polyhydroxy compounds such as 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.

  The coating film-forming resins described above include a curable type and a lacquer type. Usually, a curable type film-forming resin is used. In the case of a curable type film-forming resin, 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 heating. Or the curing reaction can proceed at room temperature. 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 used in the present invention contains a cross-linking agent, the ratio of the film-forming resin to the cross-linking agent is 90 to 50% by mass of the film-forming resin in terms of solid content and 10 to 50% of the cross-linking agent. It is mass%, Preferably the resin for film formation is 85-60 mass%, and a crosslinking agent is 15-40 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, if the crosslinking agent exceeds 50% by mass (if the coating film forming resin is less than 50% by mass), the storage stability of the coating composition decreases and the curing rate increases, resulting in poor coating appearance. In addition, as a crosslinking agent, an isocyanate type, an amine type crosslinking agent, etc. can be mentioned.

  A glittering coating film is obtained by coating the resulting coating composition for glittering coating film using a coating spray or the like.

  In order to make the obtained glittering coating film a surface reflectance and appearance close to those of electrochrome plating, the surface reflectance of the flaky metal piece is 10 to 70% with respect to light having a wavelength of 550 nm. Is desirable. Then, the thickness and size of the flaky metal piece to be used are adjusted so as to fall within the predetermined range as described above, and the surface reflectance of each metal film of the flaky metal piece is appropriately adjusted within the above range. It is preferable to do. As for the dry film thickness of the coating film obtained, 5-50 micrometers is preferable and when it remove | deviates from this range, there exists a possibility that a coating-film external appearance may fall. More preferably, it is 10-30 micrometers.

  The glitter coating film according to the present invention is obtained by coating the obtained coating composition for glitter coating film on a substrate to form a glitter coating film as a base coat layer, and then topping the glitter coating film on the substrate. The coating layer can be obtained by forming at least one clear coating film.

  In the case where the base material is a base coat that has been undercoated with an undercoat or an intermediate coat, the present invention is applied to the base coat by a wet-on-wet (W / W) method or a wet-on-dry (W / D) method. The glittering paint composition according to the present invention can be applied. A method for coating the glittering paint composition according to the present invention on the substrate is not particularly limited, but a spray method, a roll coater method and the like are preferable.

  It is preferable to form at least one clear coating film as a topcoat layer on the formed glittering coating film. When a lot of glitter pigment is contained in the base coat layer, the glitter of the surface can be improved by applying two or more clear paints.

  As the clear coating used as the top coat layer, a coating generally used for top coating can be used. For example, a mixture of at least one thermosetting resin selected from an acrylic resin, a polyester resin, a fluororesin, an epoxy resin, a polyurethane resin, a polyether resin, and a modified resin thereof and the above-described crosslinking agent is used. be able to. In addition, these clear paints may contain additives such as coloring pigments, extender pigments, modifiers, UV absorbers, leveling agents, dispersants, antifoaming agents, etc., as long as they do not impair the transparency. It is possible to mix.

  Thus, the topcoat layer formed using the clear paint is baked at 120 to 160 ° C. for a predetermined time together with the glittering coating film and, if necessary, the base coating film, thereby completing the coating film. The dry thickness of the top coat layer is preferably 10 to 80 μm per coat layer, and more preferably 20 to 50 μm.

  As described above, by using the coating composition for glittering coating film according to the present invention, a glittering coating film can be obtained by coating, and therefore, when a glittering thin film is formed using electroplating treatment Compared to this, it has excellent workability and is extremely advantageous especially in the case of large parts.

Example 1
A polypropylene plate having a width of 30 cm, a length of 100 cm, and a thickness of 0.5 mm was used as a substrate. After immersing the substrate in an acrylic lacquer paint (manufactured by Nippon Paint) solution, the substrate was suspended vertically and the excess paint was Dropped. The substrate was dried in the atmosphere for 60 minutes to form a smooth coating film of acrylic lacquer paint having a thickness of about 0.1 μm on the substrate.

  Thereafter, the substrate after the coating film was formed was immersed in an electroless copper plating solution (manufactured by Uemura Kogyo Co., Ltd., product name: Sulcup (trademark)) for 1 minute at a liquid temperature of 50 °, and a copper thin film having a film thickness of 30 nm was applied to the substrate. Formed on the membrane.

  Next, when the polypropylene plate after forming the thin film was immersed in methyl ethyl ketone (MEK) together with the substrate, the acrylic lacquer was eluted and the thin film was peeled off. The exfoliated thin film is immersed in acetone, and while being immersed in acetone, it is pulverized with ultrasonic waves (output: 90 W, frequency: 43 kHz) for 5 minutes, and the thin film is flaked and then dried. A flaky metal piece was obtained. The size (constant direction diameter) of the obtained flaky metal piece was about 35 μm.

  Furthermore, the surface reflectance of the obtained thin film flaky metal piece was measured with a light having a wavelength of 550 nm using a spectrophotometer (manufactured by Hitachi, Ltd.). The surface reflectance was 53%.

  10 g of the obtained thin film flaky metal piece was prepared in 20 g of a solvent (ethyl acetate), and the metal piece was dispersed evenly with ultrasonic waves, and then dispersed in an acrylic resin. A coating composition for a film was obtained.

  Next, the obtained coating composition was actually applied to a substrate, and a coating film was formed for evaluation.

As the substrate, the following was used. On the aluminum alloy casting AC4C (Al-Si-Mg-based) plate (thickness 3 mm), a chemical conversion film is formed to a chromium content of 80 to 150 g / m ² by chromate treatment. In order to smooth the surface, 100 μm of acrylic powder paint was applied and dried at 150 ° C. for 1 hour. Further, as an undercoat, a clear paint polyester / melamine resin was formed to 30 μm with an air spray gun and dried at 140 ° C. for 30 minutes to obtain a base material.

  Then, the coating composition for glittering coating film of a present Example was apply | coated by 1-2 micrometers by the air spray on the said base material. A top coat of acrylic / melamine resin having a thickness of 5 μm, 10 μm and 25 μm was formed with an air spray gun and dried at 140 ° C. for 30 minutes.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling compared to the conventional red metallic coating material.

  Further, based on the test items mainly based on the electroplating standard, the corrosion resistance of the coating films of the three types of surface treatment materials having different topcoat thicknesses was evaluated. Specifically, 1% sodium hydroxide and 2% sulfuric acid were dropped onto the surface of the coating film of the obtained surface treatment material to evaluate the corrosion resistance of the coating film, and a salt spray test was performed. The standing time after dropping 1% sodium hydroxide and 2% sulfuric acid on the surface of the coating film of the surface treatment material was 5 minutes, 2.5 hours, 3.5 hours, and 5.0 hours. The test conditions for the salt spray test were in accordance with JIS H8502. As a result, all the test items were passed regardless of the thickness of the top coat. Table 1 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

  When 1% sodium hydroxide is dropped on the surface of the coating film of the obtained surface treatment material and left for 5.0 hours, and when 2% sulfuric acid is dropped and left for 5.0 hours, partial discoloration occurs. Although it was observed, dissolution was not observed in other cases.

(Example 2)
After electroless copper plating in the same manner as in Example 1, electroplating was performed by immersing in a chromium plating solution (product name: Asahi Chrome (registered trademark)) for 1 minute to form a 50 nm-thick chromium thin film. Formed. Then, in the same manner as in Example 1, the thin film was peeled off, pulverized, and then dried to obtain a flaky metal piece.

  When the surface reflectance of the obtained thin film flaky metal piece was measured in the same manner as in Example 1 from the chromium thin film side, the surface reflectance was 65%.

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high brightness compared to the conventional metallic coating material, and had a chrome-plated appearance and a red color on the back.

  Further, based on the test items mainly based on the electroplating standard, the corrosion resistance of the coating films of the three types of surface treatment materials having different topcoat thicknesses was evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 1 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

(Example 3)
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, an electroless nickel solution (manufactured by Uemura Kogyo Co., Ltd., product name: Nimden (registered trademark)) was used at a liquid temperature of 50 ° C. for 1 minute. Immersion plating was performed to obtain a nickel thin film with a thickness of 30 nm. In the same manner as in Example 1, the thin film was peeled off, pulverized, and then dried to obtain a flaky metal piece. The size (constant direction diameter) of the obtained thin-film flaky metal piece was about 38 μm.

  When the surface reflectance of the obtained thin-film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 55%.

  Except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate), a coating composition for glittering coating film of this example was obtained in the same manner as in Example 1 and carried out. A coating film was obtained in the same manner as in Example 1, and surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling and a color tone close to chrome plating as compared with conventional metallic coating materials.

  Further, based on the test items mainly based on the electroplating standard, the corrosion resistance of the coating films of the three types of surface treatment materials having different topcoat thicknesses was evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 1 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

Example 4
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, an electroless silver plating solution (manufactured by Uemura Kogyo Co., Ltd., product name: Presa (registered trademark)) was used, and the temperature was 30 ° C. Plating was performed by dipping for a minute to obtain a silver thin film having a thickness of 45 nm. In the same manner as in Example 1, the thin film was peeled off, pulverized, and then dried to obtain a flaky metal piece. The size (constant direction diameter) of the obtained thin-film flaky metal piece was about 40 μm.

  When the surface reflectance of the obtained thin film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 57%.

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling and a color tone close to chrome plating as compared with conventional metallic coating materials.

  Further, based on the test items mainly based on the electroplating standard, the corrosion resistance of the coating films of the three types of surface treatment materials having different topcoat thicknesses was evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 1 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

(Example 5)
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, an electroless gold plating solution (product name: Goblite (registered trademark)) was used for 1 minute at a liquid temperature of 30 ° C. Immersion plating was performed to obtain a gold thin film with a thickness of 25 nm. In the same manner as in Example 1, the thin film was peeled off, pulverized, and then dried to obtain a flaky metal piece. The size (constant direction diameter) of the obtained thin-film flaky metal piece was about 30 μm.

  When the surface reflectance of the obtained thin-film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 68%.

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high radiance compared to conventional metallic coating materials.

  In addition, based on test items mainly based on electroplating standards, coating films of three types of surface treatment materials having different topcoat thicknesses were evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 2 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

(Example 6)
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, an electroless gold plating solution (product name: Goblite (registered trademark)) was used for 1 minute at a liquid temperature of 30 ° C. Immersion plating was performed to obtain a gold thin film with a thickness of 25 nm. Furthermore, it was immersed in a nickel plating solution (Kamimura Kogyo, product name: Asahilite (registered trademark)) for 0.5 minutes, and electroplated to form a nickel thin film having a thickness of 50 nm.

  The reflectance of the nickel thin film after film formation was 55%. Further, in the same manner as in Example 1, the thin film was peeled off, pulverized, and then dried to obtain a flaky metal piece. The size (constant direction diameter) of the obtained thin-film flaky metal piece was about 40 μm.

  When the surface reflectance of the obtained thin-film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 55% when measured from the nickel side and 68% when measured from the gold side on the back surface. .

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling and a color tone close to chrome plating as compared with conventional metallic coating materials.

  In addition, based on test items mainly based on electroplating standards, coating films of three types of surface treatment materials having different topcoat thicknesses were evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 2 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

(Example 7)
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, an electroless nickel plating solution (manufactured by Uemura Kogyo Co., Ltd., product name: Nimden (registered trademark)) was used. Plating was performed by dipping for 5 minutes to form a nickel thin film having a thickness of 50 nm. Furthermore, it was immersed in a nickel plating solution (manufactured by Uemura Kogyo, product name: Asahilite (registered trademark)) for 2 minutes, and electroplated to form a nickel thin film having a thickness of 50 nm. In the same manner as in Example 1, the thin film was peeled off, pulverized, and then dried to obtain a flaky metal piece. The size (constant direction diameter) of the obtained thin-film flaky metal piece was about 40 μm.

  When the surface reflectance of the obtained thin-film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 62%.

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling and a color tone close to chrome plating as compared with conventional metallic coating materials.

  In addition, based on test items mainly based on electroplating standards, coating films of three types of surface treatment materials having different topcoat thicknesses were evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 2 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

(Example 8)
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, an electroless nickel plating solution (manufactured by Uemura Kogyo Co., Ltd., product name: Nimden (registered trademark)) was used, and the liquid temperature was adjusted to 30 ° C. Plating was performed by immersing for 50 minutes to form a 50 nm nickel film. Further, it was immersed in a chromium plating solution (product name: Asahi Chrome (registered trademark)) for 0.5 minutes for electroplating to form a chromium thin film having a thickness of 30 nm.

  In the same manner as in Example 1, the thin film was peeled off, pulverized, and then dried to obtain a flaky metal piece. The size (constant direction diameter) of the obtained thin-film flaky metal piece was about 35 μm.

  When the surface reflectance of the obtained thin film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 65%.

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling and a color tone close to chrome plating as compared with conventional metallic coating materials.

  In addition, based on test items mainly based on electroplating standards, coating films of three types of surface treatment materials having different topcoat thicknesses were evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 2 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

Example 9
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, a nickel film having a thickness of 20 nm was formed using an ion plating apparatus. Thereafter, electroplating was performed by immersing in a chromium plating solution (product name: Asahi Chrome (registered trademark)) for 0.5 minutes to form a chromium thin film having a thickness of 30 nm on the nickel film. Other processes and conditions were the same as those in Example 1.

  When the surface reflectance of the obtained thin-film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 62%.

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling and a color tone close to chrome plating as compared with conventional metallic coating materials.

  In addition, based on test items mainly based on electroplating standards, coating films of three types of surface treatment materials having different topcoat thicknesses were evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 2 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

(Example 10)
After a smooth coating film of acrylic lacquer paint was formed on the substrate in the same manner as in Example 1, a 40 nm copper film was formed on the acrylic lacquer using an ion plating apparatus. Thereafter, electroplating was performed by immersing in a chromium plating solution (product name: Asahi Chrome (registered trademark)) for 0.5 minutes to form a chromium thin film having a thickness of 30 nm on the copper film. Other processes and conditions were the same as those in Example 1.

  When the surface reflectance of the obtained thin-film flaky metal piece was measured in the same manner as in Example 1, the surface reflectance was 62%.

  A coating composition for a glittering coating film of this example was obtained in the same manner as in Example 1 except that 0.01 g of the obtained thin film flaky metal piece was prepared in 90 g of a solvent (ethyl acetate). And the coating film was obtained like Example 1 and the surface treatment was performed.

  The external appearance of the surface treatment material obtained as described above was free from cracks and cracks, and had a high glitter feeling and a color tone close to chrome plating as compared with conventional metallic coating materials.

  In addition, based on test items mainly based on electroplating standards, coating films of three types of surface treatment materials having different topcoat thicknesses were evaluated. A specific evaluation method is the same as that in the first embodiment. As a result, all the test items were passed regardless of the thickness of the top coat. Table 2 shows test items, test methods, and test results obtained. Similar evaluation results were obtained for the three types of surface treatment materials having different topcoat thicknesses.

(Comparative Example 1)
A 10 cm square, 1 mm thick polypropylene plate substrate was used and dipped in an acrylic lacquer paint (manufactured by Nippon Paint) solution to form an acrylic lacquer paint film having a thickness of about 0.1 μm on the substrate surface.

  Thereafter, an ion plating apparatus (manufactured by Shinko Seisakusho Co., Ltd.) having an electron gun and having three crucibles for evaporating metal was used as the vapor deposition apparatus, and the evaporation source was only Al and each was placed in the crucible.

  After the substrate on which the acrylic lacquer coating film was formed was placed in a vapor deposition apparatus, the evaporation source was evaporated, and a thin film having a thickness of 20 nm was formed on the substrate by vapor deposition. Here, the film formation current of the electron gun was set to 230 mA, and film formation was performed for 5 minutes. The reflectance of the obtained thin film was 80%.

  Next, when the polypropylene plate was immersed in acetone together with the substrate, the acrylic lacquer was eluted and the thin film was peeled off. The peeled thin film was immersed in acetone and pulverized with ultrasonic waves (output: 90 W, frequency: 43 kHz) for 5 minutes and dried to obtain a flaky metal piece. The size of the obtained flaky metal piece was about 44 μm.

  Furthermore, when the surface reflectance of the obtained Al flakes was measured in the same manner as in Example 1, the surface reflectance was 70%.

  1 g of the obtained Al flakes was prepared in 99 g of a solvent (methyl ethyl ketone (MEK)), and the metal pieces were uniformly dispersed by ultrasonic waves, and then dispersed in an acrylic resin to obtain a coating composition of this comparative example. Obtained. And the coating film was obtained like Example 1 and the surface treatment was performed.

  The appearance of the surface treatment material obtained as described above was free from cracks and cracks.

  In addition, based on test items mainly based on electroplating standards, coating films of three types of surface treatment materials having different topcoat thicknesses were evaluated. A specific evaluation method is the same as that in the first embodiment.

  When 1% sodium hydroxide was added dropwise, Al flakes in the coating film were dissolved in a test time of 2.5 hours. When 2% sulfuric acid was added dropwise, Al flakes in the coating film were dissolved in 5.0 hours. The test results are shown in Table 3.

Claims (17)

  A bright pigment comprising a thin-film flaky metal piece, wherein the thin-film flaky metal piece is selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy and gold alloy A glittering pigment comprising the thin film flake-like metal piece having a surface reflectance of 10 to 70% with respect to light having a wavelength of 550 nm.   A glittering pigment comprising a thin-film flaky metal piece having a two-layer structure, wherein the first layer of the thin-film flaky metal piece is copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy And at least one metal selected from the group consisting of chromium, titanium, nickel, a chromium alloy, a titanium alloy, and a nickel alloy, the second layer comprising a thin film of at least one metal selected from the group consisting of gold alloys A luster pigment characterized by comprising a thin film of   The surface reflectance of the first layer and the surface reflectance of the second layer of the thin-film flaky metal piece having the two-layer structure are both 10 to 70% with respect to light having a wavelength of 550 nm. Item 3. The bright pigment according to Item 2.   The glitter pigment according to any one of claims 1 to 3, having a thickness of 10 to 200 nm and a size of 5 to 40 µm in a constant direction diameter.   A paint composition for a glittering coating film, comprising the glittering pigment according to any one of claims 1 to 4 and a vehicle.   A glittering coating film formed using the coating composition for the glittering coating film according to claim 5.   A method for producing a luster pigment, comprising producing a thin-film flaky metal piece using an electroless plating method.   A thin film flaky metal piece is formed by forming a metal thin film on a substrate by vapor deposition or sputtering, and then forming a metal thin film on the metal thin film by using an electroplating method. Method for producing a pigment.   (A) A metal thin film is formed on the substrate by electroless plating, or (b) a metal thin film is formed on the substrate by vapor deposition or sputtering, and then an electroplating method is used on the metal thin film. A step 1 for forming a metal thin film, and a step 2 for obtaining a thin film flake-like metal piece by peeling the metal thin film formed in the step 1 from the substrate and crushing the metal thin film. Production method.   The method for producing a glittering pigment according to claim 9, wherein the thickness of the metal thin film formed in the step 1 is 10 to 200 nm.   (A) A metal thin film is formed on the substrate by electroless plating, or (b) a metal thin film is formed on the substrate by vapor deposition or sputtering, and then an electroplating method is used on the metal thin film. Step 1 for forming a metal thin film, and a thin film made of the same or different metal as the metal thin film formed in Step 1 on the metal thin film formed in Step 1 by electroless plating or electroplating. Step 2 to obtain a two-layer metal thin film and Step 3 to obtain a thin-film flaky metal piece by peeling and crushing the two-layer metal thin film formed in Step 2 from the substrate. A method for producing a luster pigment, comprising:   The method for producing a glittering pigment according to claim 11, wherein the thickness of the metal thin film having a two-layer structure formed in the step 2 is 10 to 200 nm.   (A) At least one selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy on the substrate by using an electroless plating method (B) After forming a metal thin film on the substrate by vapor deposition or sputtering, copper, silver, tin, nickel using an electroplating method on the metal thin film Step 1 of forming a thin film made of at least one metal selected from the group consisting of gold, copper alloy, silver alloy, tin alloy, nickel alloy and gold alloy, and the metal thin film formed in Step 1 as a substrate And a step 2 of obtaining a thin-film flaky metal piece by pulverizing and pulverizing.   The method for producing a glitter pigment according to claim 13, wherein the thickness of the thin film formed in the step 1 is 10 to 200 nm.   (A) At least one selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy on the substrate by using an electroless plating method (B) After forming a metal thin film on the substrate by vapor deposition or sputtering, copper, silver, tin, nickel using an electroplating method on the metal thin film Step 1 of forming a thin film made of at least one metal selected from the group consisting of gold, copper alloy, silver alloy, tin alloy, nickel alloy and gold alloy, and on the metal thin film formed in Step 1 above, A two-layer metal thin film is formed by forming a thin film made of at least one metal selected from the group consisting of chromium, titanium, nickel, chromium alloy, titanium alloy, and nickel alloy by electroless plating or electroplating. Craft 2, the process and peeling the metal thin film having a two-layer structure formed from the substrate 2, the manufacturing method of the bright pigment characterized by having a step 3 of obtaining a thin flake-shaped metal piece by grinding.   The method for producing a glittering pigment according to claim 15, wherein the thickness of the metal thin film having a two-layer structure formed in the step 2 is set to 10 to 200 nm.   The metal thin film formed on the substrate by vapor deposition or sputtering is at least one selected from the group consisting of copper, silver, tin, nickel, gold, copper alloy, silver alloy, tin alloy, nickel alloy, and gold alloy It consists of metals, The manufacturing method of the luster pigment in any one of Claims 8-16 characterized by the above-mentioned.