JP2005161275A - High color saturation layered coating film and method of forming coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a layered coating film having high color saturation and excellent substrate shielding ability and exhibiting interference action to give fertile designability and a method of forming the coating film. <P>SOLUTION: The coating film is a layered coating film at least having a substrate layers 20 and 21 formed on the surface of a material 10 to be coated, a base coating film layer 30 formed on the substrate layer, a luster material-containing coating film layer 70 formed on the surface of the base coating film layer and a colored coating film layer 40 formed on the surface of the luster material-containing coating film layer 70. The lightness of the base coating film layer 30 is higher than that of the colored coating film layer 40 and the colored coating film layer 40 contains an atomized coloring material having 30-300 nm average particle diameter. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminated coating film and a method for forming a coating film that have high chroma and excellent base concealing properties.

  Among the indices that represent hue, the vividness of color or the saturation of color is called saturation, but for coatings such as automobiles and home appliances, in addition to coating performance such as rust prevention, antifouling properties, and weather resistance. Therefore, improvement in design properties such as saturation is required.

  As a method for realizing a high saturation coating film, a white coating film (Patent Document 1) to which a fluorescent whitening agent is added, a colored coating film (Patent Document 2) using a high saturation pigment, and a multilayer interference platelet are used for the reflectance. An enhanced coating film (Patent Document 3) has been proposed.

  However, there is a limit to the hues that can be realized with the technique using pigments with high saturation, and it is not easy to increase the saturation for all paint colors. In addition, the high-saturation pigment has a problem that the underlying coating film has poor concealability, and depending on the viewing angle, it becomes a blackish coating film, or the variation in color difference due to film thickness variation increases. On the other hand, in the method of increasing the reflectance by the multilayer interference platelet, the hue may vary depending on the interference material.

In any case, it has been difficult for the conventional method to achieve both the enhancement of the saturation and the concealment of the base.
Japanese Patent Laid-Open No. 1-313575 JP 7-286111 A JP 9-508172 A

An object of this invention is to provide the laminated coating film and coating-film formation method which were excellent in high saturation and foundation | background concealing property.
In order to achieve the above object, according to a first aspect of the present invention, a base layer formed on the surface of an object to be coated, a base coating layer formed on the surface of the base layer, and the base coating A laminated coating film having at least a glittering material-containing coating layer formed on the surface of the film layer and containing a glittering material, and a colored coating layer formed on the surface of the glittering material-containing coating layer, There is provided a laminated coating film characterized in that the lightness of the coating film layer is higher than the brightness of the colored coating film layer, and the colored coating film layer contains an atomized colorant having an average particle diameter of 30 nm to 300 nm.

  In order to achieve the above object, according to the second aspect of the present invention, a step of forming a base layer on the surface of the object to be coated, a step of forming a base coating layer on the surface of the base layer, Formation of a multilayer coating film having at least a step of forming a glittering material-containing coating layer containing a glittering material on the surface of the base coating layer and a step of forming a colored coating layer on the surface of the glittering material-containing layer A method, wherein the lightness of the base coating film layer is higher than the lightness of the colored coating film layer, and the colored coating film layer contains an atomized colorant having an average particle size of 30 nm to 300 nm. A method of forming a coating is provided.

  In the present invention, while using the atomized colorant having an average particle size of 30 nm to 300 nm for the colored coating layer formed on the surface side of the laminated coating layer, the saturation is increased, while the base coating layer formed on the lower side thereof By making the lightness of the film higher than the lightness of the colored coating film layer, the concealability is ensured and the color difference due to the film thickness variation is reduced. Thereby, it is possible to obtain a laminated coating film having high saturation and excellent base concealing property. Particularly in the present invention, since it has a glittering material-containing coating film layer containing a glittering material between the base coating film layer and the colored coating film layer, the interference effect of the glittering material occurs when the laminated coating film is observed, and the design It becomes a highly laminated film.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The laminated coating film and the coating film forming method according to the present invention include a colored coating film layer containing an atomized colorant having an average particle size of 30 nm to 300 nm, and a base coating film layer having a brightness higher than the brightness of the colored coating film layer, Any laminated coating film having a glittering material-containing coating layer containing a glittering material formed between the colored coating layer and the base coating layer may be used. Representative embodiments will be described below, but the laminated coating film and the coating film forming method of the present invention are not limited to these embodiments. Therefore, the elements disclosed in these embodiments are The present invention includes all design changes and equivalents belonging to the technical scope of the present invention.

1st Embodiment (FIG. 1) and 2nd Embodiment (FIG. 2)
FIG. 1 is a cross-sectional view showing a laminated coating film according to the first embodiment of the present invention. The laminated coating film according to this embodiment includes an electrodeposition coating film layer 20 formed on the surface of the article 10 to be coated, an intermediate coating film layer 21 formed on the surface of the electrodeposition coating film layer 20, The base coating layer 30 formed on the surface of the intermediate coating layer 21, the glittering material-containing coating layer 70 formed on the surface of the base coating layer 30, and the surface of the glittering material-containing coating layer 70 And a colored coating layer 40 formed on the surface.

  As the article to be coated 10, plastic members can be applied in addition to various metal material members such as steel plates and aluminum plates. This coated object can be used not only for automobile bodies and automobile parts, but also for home appliances.

  The electrodeposition coating layer 20 is formed by immersing the article to be coated 10 in a cation-type electrodeposition paint or an anion-type electrodeposition paint, and applying a predetermined voltage between the article 10 and the electrodeposition paint. An uncured coating film is formed on the surface of the article to be coated 10 by the migration action, and a cured coating film is formed by baking the coating film at 160 to 180 ° C. for 15 to 30 minutes, for example. The film thickness of the electrodeposition coating layer 20 is, for example, 10 to 40 μm, although it depends on the type and purpose of the article 10 to be coated.

  The intermediate coating layer 21 is a thermosetting paint comprising a polyester resin, an acrylic resin, a vinyl acetate vinyl chloride copolymer resin, a urethane resin, a cellulose resin, etc. as a main component, and a colorant or additive added thereto. Alternatively, a room temperature curable coating or a two-component curable coating, which is diluted with a solvent, is applied to the surface of the electrodeposition coating layer 20 using a coating machine such as a spray coating gun. Then, for example, it is formed by baking at 80 to 160 ° C. for 10 to 60 minutes. The thickness of the intermediate coating layer 21 is, for example, 15 to 45 μm, although it varies depending on the type and purpose of the object.

  FIG. 2 is a cross-sectional view showing the laminated coating film according to the second embodiment of the present invention, but in this example, the intermediate coating film layer 21 is omitted and the electrodeposition coating film layer 20 is directly applied to the surface of the electrodeposition coating film 20 later. The base coating layer 30 is formed. Other configurations, the electrodeposition coating layer 20, the base coating layer 30, the bright material-containing coating layer 70, and the colored coating layer 40 are the same as those in the first embodiment.

  Thus, the intermediate coating layer 21 can be omitted depending on the type and purpose of the object to be coated. Alternatively, the electrodeposition coating layer 20 can be omitted, and the intermediate coating layer 21 can be formed directly on the surface of the article 10 to be coated.

  Returning to FIG. 1, the base coating layer 30 is mainly composed of a polyester-based resin, an acrylic resin, a polyvinyl chloride vinyl acetate copolymer resin, a urethane resin, a cellulose resin, and the like, and a colorant and an additive are added thereto. A thermosetting paint, a room temperature curable paint, or a two-part curable paint, which is diluted with a solvent, is applied to the surface of the intermediate coating layer 21 using a coating machine such as a spray coating gun, If it is a thermosetting paint, it is formed by baking at 80 to 160 ° C. for 10 to 60 minutes, for example.

  In particular, the base coating layer 30 according to the present embodiment adjusts the content of a white or black coloring material, for example, so that the brightness of the coating layer 30 becomes higher than the brightness of the colored coating layer 40 described later. I have to. By forming the base coating layer 30, the base coating layer 30 can mask the intermediate coating layer 21 and the electrodeposition coating layer 20 even if the colored coating layer 40 does not have a base concealing property. it can. Note that the film thickness of the base coating layer 30 is, for example, 15 to 45 μm, although it varies depending on the type and purpose of the object to be coated.

  The glitter material-containing coating layer 70 is mainly composed of a polyester resin, an acrylic resin, a vinyl vinyl chloride copolymer resin, a urethane resin, a cellulose resin, and the like, and various additives such as a glitter material and a dispersant are added thereto. A heat curable paint, a room temperature curable paint or a two-component curable paint, which is diluted with a solvent, is applied to the surface of the base coating layer 30 using a spraying machine such as a spray coating gun. If it is a thermosetting paint, it is formed by baking at 80 to 160 ° C. for 10 to 60 minutes, for example.

  The glittering material contained in the glittering material-containing coating layer 70 may be pearl (mica coated with a metal oxide such as titanium dioxide or iron oxide), but has an average particle diameter of 1 to 20 μm and a thickness. It is preferable to use crushed aluminum or vapor-deposited aluminum having a thickness of 0.01 to 0.5 μm, and 1 to 20%, more preferably 1 to 10% by weight based on the resin solid content of the glittering material-containing coating layer 70 It is. If the weight ratio of the glittering material exceeds 20%, the coating film adhesion may be adversely affected. Conversely, if it is less than 1%, the glittering feeling becomes insufficient. The weight ratio here refers to the weight B of the glittering material relative to the resin solid content weight A, that is, B / A (%).

  Examples of additives include waxes such as polyethylene wax and polypropylene wax, and dispersants. Examples of solvents include water, aromatic hydrocarbon solvents or hydrocarbon solvents (ester solvents, ketone solvents). Examples thereof include solvents and alcohol-based solvents.

  Note that the glittering material-containing coating layer 70 of this example has a configuration that does not include a colorant, but if necessary, an atomized colorant having an average particle size of 30 nm to 300 nm, more preferably 30 nm to 200 nm, is used as a resin solid. You may add in the range of 0.05 to 50% by weight ratio with respect to minutes.

  The thickness of the glittering material-containing coating layer 70 is, for example, 15 to 45 μm, although it varies depending on the type and purpose of the object to be coated.

  The colored coating layer 40 is mainly composed of a polyester-based resin, an acrylic resin, a vinyl chloride vinyl acetate copolymer resin, a urethane resin, a cellulose resin, or the like, and a thermosetting paint or a colorant or additive added thereto. A room-temperature curable coating or a two-component curable coating, which is diluted with a solvent, is applied to the surface of the glittering material-containing coating layer 30 using a spraying machine such as a spray coating gun. Then, for example, it is formed by baking at 80 to 160 ° C. for 10 to 60 minutes.

  Examples of additives include waxes such as polyethylene wax and polypropylene wax, and dispersants. Examples of solvents include water, aromatic hydrocarbon solvents or hydrocarbon solvents (ester solvents, ketone solvents). Examples thereof include solvents and alcohol-based solvents.

  In particular, the colored coating layer 40 according to this embodiment includes an atomized colorant having an average particle diameter of 30 nm to 300 nm, more preferably 30 nm to 200 nm. If the average particle size of the atomized colorant is smaller than 30 nm, the weather resistance may be affected depending on the type and grade of the colorant, and if the average particle size exceeds 300 nm, vividness and transparency as the colorant may be obtained. It is damaged and high saturation cannot be realized.

  Generally, the average particle diameter of the colorant used in the paint is 500 nm to 10 μm. When light enters the coating film, white diffuse reflected light is generated, which is considered to be a cause of lowering the saturation. Therefore, in order to increase the saturation using the colorant having such a conventional diameter, it is effective to lower the concentration of the colorant added to the paint. However, if the colorant concentration is decreased, the color difference ΔE with respect to the film thickness variation is reduced. The film thickness becomes severe and the film thickness management becomes severe, and it is called a so-called frame phenomenon (a phenomenon in which the edge of the object to be coated is thicker than the general surface, causing a color difference between the general surface and the edge). There was a problem.

  In this regard, in the colored coating layer 40 according to the present embodiment, the generation of diffuse reflected light that causes a decrease in saturation is suppressed by reducing the particle diameter of the coloring material while maintaining the concentration of the coloring material. Thereby, the variation of the color difference due to the variation of the film thickness can be reduced and the saturation can be increased. In addition, the base coating layer 30 solves the problem of lowering the background hiding property due to the increased saturation.

  Further, the colored coating layer 40 according to the present embodiment includes 0.05 to 50% of the above-described atomized colorant in a weight ratio with respect to the resin solid content. When the weight ratio of the atomized colorant is less than 0.05%, a sufficient coloring effect cannot be obtained, and when the weight ratio of the atomized colorant exceeds 50%, the colored coating layer 40 looks dark.

  Incidentally, the coloring material contained in the colored coating layer 40 is not limited to the atomized coloring material, and the coloring material having an average particle diameter exceeding 300 nm is 0 by weight with respect to the resin solid content of the colored coating layer 40. It may be included in the range of 0.05 to 3%. However, the atomized colorant is required to be contained 1.5 times or more in a solid content ratio with respect to the colorant having an average particle diameter exceeding 300 nm. When the colorant having an average particle diameter of more than 300 nm exceeds 3% by weight or the content ratio of the atomized colorant is less than 1.5 times, the high-saturation coating film which is the object of the present invention is realized. Because you can't.

  The thickness of the colored coating layer 40 is, for example, 15 to 45 μm, although it depends on the type and purpose of the object to be coated.

  In the above-described embodiment, each of the five layers of the electrodeposition coating layer 20 and the intermediate coating layer 21, the base coating layer 30, the glittering material-containing coating layer 70, and the colored coating layer 40 that are the base layers is used. Although baked and cured, two or more layers may be applied wet-on-wet and a plurality of layers may be baked and cured simultaneously. For example, the electrodeposition coating layer 20 and the intermediate coating layer 21, the intermediate coating layer 21 and the base coating layer 30, the base coating layer 30, the glittering material-containing coating layer 70, and the glittering material-containing coating layer 70. The colored coating layer 40, the intermediate coating layer 21, the base coating layer 30, the glittering material-containing coating layer 70, and the like can be exemplified as wet-on-wet coating.

  According to the laminated coating film of this example, since the glittering material-containing coating layer 70 containing the glittering material is provided between the base coating film layer 30 and the colored coating film layer 40, the exterior of the laminated coating film Part of the light incident from the light is reflected by the colored coating layer 40 and the other part passes through the colored coating layer 40 and is reflected by the glittering material of the glittering material-containing coating layer 70. At this time, the direction of the glitter material is different from each other, or in the case of a pearl glitter material or the like, multiple reflection on the transparent base material or reflection on the metal oxide film occurs, so that various reflected lights are generated. On the other hand, another part of the incident light is reflected by the base coating layer 30 through the glittering material of the glittering material-containing coating layer 70 or through the transparent glittering material itself. By producing such various reflected lights, the interference effect of light arises in a laminated coating film, and the laminated coating film which was rich in the design property can be obtained.

3rd Embodiment (FIG. 3) and 4th Embodiment (FIG. 4)
FIG. 3 is a sectional view showing a laminated coating film according to the third embodiment of the present invention. The laminated coating film according to the first embodiment and the second embodiment described above is a laminated coating film that does not form a clear coating film layer on the surface of the colored coating film layer 40, but the laminated coating film of the present invention is a colored coating film. It can also be embodied in a laminated coating film having one or two or more clear coating film layers 60 on the surface of the film layer 40.

  That is, the laminated coating film according to this embodiment shown in FIG. 3 includes an electrodeposition coating layer 20 formed on the surface of the article 10 and an intermediate coating formed on the surface of the electrodeposition coating layer 20. The film layer 21, the base coating layer 30 formed on the surface of the intermediate coating layer 21, the glitter material-containing coating layer 70 formed on the surface of the base coating layer 30, and the glitter material containing It is composed of the colored coating layer 40 formed on the surface of the coating layer 70 and the clear coating layer 60 formed on the surface of the colored coating layer 40, and the point that the clear coating layer 60 exists is described above. This is different from the first embodiment. The electrodeposition coating layer 20, the intermediate coating layer 21, the base coating layer 30, the glittering material-containing coating layer 70, and the colored coating layer 40 are the same as those in the first embodiment described above, and therefore Detailed description is omitted.

  The clear coating layer 60 according to the present embodiment is a thermosetting type comprising, as a main component, a polyester resin, an acrylic resin, a vinyl chloride vinyl acetate copolymer resin, a urethane resin, a cellulose resin, and the like, and an additive added thereto. A paint, a room temperature curable paint, or a two-component curable paint, which is diluted with a solvent, is applied to the surface of the uncured colored coating layer 40 using a coating machine such as a spray coating gun, If it is a thermosetting paint, it is formed by baking at 80 to 160 ° C. for 10 to 60 minutes, for example.

  Examples of additives include waxes such as polyethylene wax and polypropylene wax, and dispersants. Examples of solvents include water, aromatic hydrocarbon solvents or hydrocarbon solvents (ester solvents, ketone solvents). Examples thereof include solvents and alcohol-based solvents.

  In the embodiment described above, the clear coating layer 60 is one layer, but it may be repeatedly applied to form two or more clear coating layers 60.

  In the above-described embodiment, two layers of the colored coating layer 40 and the clear coating layer 60 are applied by wet-on-wet, and a plurality of layers are baked and cured at the same time. However, after the colored coating layer 40 is baked and cured, the clear coating layer 60 may be applied and baked and cured.

  FIG. 4 is a cross-sectional view showing a laminated coating film according to the fourth embodiment of the present invention, but in this example, the intermediate coating film layer 21 is omitted and the electrodeposition coating film layer 20 is directly applied to the surface of the electrodeposition coating film 20 later. The base coating layer 30 is formed. Other configurations, the electrodeposition coating layer 20, the base coating layer 30, the glittering material-containing coating layer 70, the colored coating layer 40, and the clear coating layer 60 are the same as those in the third embodiment.

  Thus, the intermediate coating layer 21 can be omitted depending on the type and purpose of the object to be coated. Alternatively, the electrodeposition coating layer 20 can be omitted, and the intermediate coating layer 21 can be formed directly on the surface of the article 10 to be coated.

5th Embodiment (FIG. 5) and 6th Embodiment (FIG. 6)
FIG. 5 is a cross-sectional view showing a multilayer coating film according to a fifth embodiment of the present invention. The multilayer coating film according to this embodiment includes a glittering material that exhibits a metallic feeling also in the base coating film layer 30. This is an example.

  That is, the laminated coating film according to this embodiment includes an electrodeposition coating layer 20 formed on the surface of the article 10 to be coated, and an intermediate coating layer 21 formed on the surface of the electrodeposition coating layer 20. The base coating layer 30 formed on the surface of the intermediate coating layer 21, the glittering material-containing coating layer 70 formed on the surface of the base coating layer 30, and the glittering material-containing coating layer 70 A clear coating film layer 40 formed on the surface of the film, and a clear coating film layer 60 formed on the surface of the colored coating film layer 40. The point in which the layer 60 exists differs from the first embodiment described above. The electrodeposition coating layer 20, the intermediate coating layer 21, the glittering material-containing coating layer 70, and the colored coating layer 40 have the same configuration as the first embodiment described above, and the clear coating layer 60 Since the configuration is the same as that of the third embodiment described above, detailed description thereof is omitted.

  The base coating layer 30 according to the present embodiment is mainly composed of a polyester resin, an acrylic resin, a vinyl acetate vinyl chloride copolymer resin, a urethane resin, a cellulose resin, and the like, and a colorant or an additive is added thereto. A thermosetting paint, a room temperature curable paint, or a two-part curable paint, which is diluted with a solvent, is applied to the surface of the intermediate coating layer 21 using a coating machine such as a spray coating gun, If it is a thermosetting paint, it is formed by baking at 80 to 160 ° C. for 10 to 60 minutes, for example.

  Examples of additives include waxes such as polyethylene wax and polypropylene wax, and dispersants. Examples of solvents include water, aromatic hydrocarbon solvents or hydrocarbon solvents (ester solvents, ketone solvents). Examples thereof include solvents and alcohol-based solvents.

  In particular, the base coating layer 30 according to the present embodiment adjusts the content of a white or black coloring material, for example, so that the brightness of the coating layer 30 becomes higher than the brightness of the colored coating layer 40 described later. I have to. By forming the base coating layer 30, the base coating layer 30 can mask the intermediate coating layer 21 and the electrodeposition coating layer 20 even if the colored coating layer 40 does not have a base concealing property. it can. Note that the film thickness of the base coating layer 30 is, for example, 15 to 45 μm, although it varies depending on the type and purpose of the object to be coated.

  Further, the base coating layer 30 according to the present embodiment has a glitter material having an average particle diameter of 1 to 20 μm and a thickness of 0.01 to 0.5 μm with respect to the resin solid content of the base coating layer 30. 1 to 20% by weight ratio, more preferably 1 to 10% is contained. If the weight ratio of the glittering material exceeds 20%, the coating film adhesion may be adversely affected.

  In this way, when the bright coating material 30 is also included in the base coating film layer 30 having a high brightness, a metallic feeling can be realized not only in the glittering material-containing coating film layer 70 but also in the base coating film layer 30. Furthermore, it becomes a laminated coating film excellent in design property rich in interference effect. The effect of high saturation can be achieved by the colored coating layer 40 and the base concealing property can be secured by the base coating layer 30.

  FIG. 6 is a cross-sectional view showing the laminated coating film according to the sixth embodiment of the present invention. In this example, the intermediate coating film layer 21 is omitted, and the electrodeposition coating film layer 20 is directly applied to the surface of the electrodeposition coating film 20 later. The base coating layer 30 is formed. Other configurations, the electrodeposition coating layer 20, the base coating layer 30, the glittering material-containing coating layer 70, the colored coating layer 40, and the clear coating layer 60 are the same as those in the fifth embodiment.

  Thus, the intermediate coating layer 21 can be omitted depending on the type and purpose of the object to be coated. Alternatively, the electrodeposition coating layer 20 can be omitted, and the intermediate coating layer 21 can be formed directly on the surface of the article 10 to be coated.

  In the fifth and sixth embodiments described above, one clear coating layer 60 is formed on the surface of the colored coating layer 40, but this is repeatedly applied to form two or more clear coating layers 60. It may be formed. Further, the clear coating layer 60 can be omitted.

  Hereinafter, the present invention will be described more specifically.

Example 1
A galvanized steel plate having a thickness of 0.8 mm and a size of 70 mm × 150 mm is used as an object to be coated, and then a zinc phosphate coating is formed on it. Electrodeposition coating was performed using a top U-600M) so as to have a film thickness of 20 μm, and an electrodeposition coating layer was formed by baking and curing at 160 ° C. for 30 minutes.

  The surface of this electrodeposition coating layer is spray-coated using an intermediate coating (High Epico QX1 manufactured by Nippon Oil & Fats Co., Ltd.) to a film thickness of 30 μm, and baked and cured at 140 ° C. for 30 minutes for intermediate coating. A layer was formed.

  As a base paint constituting the base coating layer, spray coating is performed using a color base white (acrylic / melamine resin manufactured by Nippon B Chemical Co., Ltd., lightness L = 80 to 90) so that the film thickness becomes 30 μm, at 140 ° C. Bake and cure for 30 minutes.

  As a paint constituting the glittering material-containing coating layer, a glittering material (Nippon Bee Chemical Co., Ltd.) made of vapor-deposited aluminum having an average particle diameter of 15 μm and a thickness of 0.1 μm on a clear base (acrylic / melamine resin manufactured by Nippon Bee Chemical) Chemical-deposited aluminum base) was added at 8% by weight with respect to the resin solid content, and diluted with thinner (T-536MB, Nippon Bee Chemical Co., Ltd.) as a solvent. This paint was applied to the surface of the base coating layer so as to have a film thickness of 2 to 5 μm.

  100 parts by weight of acrylic resin (Acridic manufactured by Dainippon Ink and Chemicals), 10 parts by weight of orange pigment (Permanent Orange 3RTN manufactured by Clariant), 5 parts by weight of dispersant (Floren G-700 manufactured by Kyoei Chemical Co., Ltd.) After mixing 230 parts by weight of ethyl acetate, 350 parts by weight of alumina beads having a particle size of 1 mm are added and dispersed for 2 hours with a mixer (TK Auto Homo Mixer manufactured by Tokushu Kika Kogyo Co., Ltd.). It refined | miniaturized to 30 nm. This atomized colorant (orange) was added to clear base (acrylic / melamine resin manufactured by Nippon B Chemical Co., Ltd.) so that the weight ratio to the resin solid content would be 4%, and thinner as a solvent (Nippon B Chemical Co., Ltd.) Spray coating the colored coating material constituting the colored coating layer obtained by dilution with T-536MB) so that the film thickness is 20 μm on the surface of the previously formed uncured glittering material-containing coating layer. did.

  Further, a clear coating (2K clear manufactured by Nippon Bee Chemical Co., Ltd.) was spray-coated on the surface of the uncured colored coating layer so as to have a film thickness of 30 μm, and these glittering material-containing coating layer, colored coating layer and The clear coating layer was baked and cured simultaneously at 140 ° C. for 30 minutes.

  In addition, it was L = 30-70 when the single brightness of the colored coating-film layer was measured separately.

  About the obtained laminated coating film, the saturation is visually evaluated, and “◎” indicates that the saturation is significantly higher than that of the conventional coating film, “○” indicates that the saturation is high, and “×” indicates the equivalent. It was.

  Moreover, about the obtained laminated coating film, the accelerated weathering test (XWOM: xenon weatherometer method) of JIS K5600-7-7 was implemented, and the hue before a test and the hue after a test were evaluated visually. “◎” indicates that the hue change is extremely small, “◯” indicates that the hue change is small, and “x” indicates that the hue change is large.

  In addition, a test piece with a colored coating layer thickness of 25 μm and a test piece with a thickness of 15 μm are separately produced, with the colored coating layer thickness of 20 μm as the center, and the thickness of the colored coating layer is 20 μm. The color difference between the test piece of 15 μm and the test piece of 25 μm was visually evaluated. “◎” indicates that the color difference variation due to film thickness variation is extremely small, “◯” indicates that the color difference variation is small, and “x” indicates that the color difference variation is large.

  Table 1 shows each evaluation of the color difference due to the saturation, accelerated weather resistance, and film thickness variation together with the main coating film conditions.

Example 2
A test piece was prepared under the same conditions as in Example 1 except that the average particle size of the orange atomized colorant to be contained in the colored coating layer was adjusted to 300 nm, and due to the saturation, accelerated weather resistance, and film thickness variation. The color difference was evaluated. The results are shown in Table 1.

Example 3
Example 1 except that the average particle diameter of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm and the weight ratio of the atomized colorant in the colored coating layer is 0.05%. Test pieces were prepared under the same conditions, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Example 4
The same conditions as in Example 1 except that the average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm and the weight ratio of the atomized colorant in the colored coating layer is 50%. Test pieces were prepared and color differences due to saturation, accelerated weather resistance, and film thickness variation were evaluated. The results are shown in Table 1.

Example 5
The average particle diameter of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the orange coloring material prepared to have an average particle diameter of 500 nm is further added to the colored coating layer in a weight ratio of 0.0. A test piece was prepared under the same conditions as in Example 1 except that 05% was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Example 6
The average particle size of the orange atomized colorant to be included in the colored coating layer is adjusted to 150 nm, and the orange colorant whose average particle size is adjusted to 500 nm is further added to this colored coating layer by 3% by weight. A test piece was prepared under the same conditions as in Example 1 except for the addition, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Example 7
The average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the glittering material-containing coating layer has an average particle size of 15 μm and a thickness of 0.1 μm. A test piece was prepared under the same conditions as in Example 1 except that 1% by weight of an aluminum base manufactured by Chemical Co. was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Example 8
The average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the glittering material-containing coating layer has an average particle size of 15 μm and a thickness of 0.1 μm. A test piece was prepared under the same conditions as in Example 1 except that 20% by weight of (Aluminum Base manufactured by Chemical Co., Ltd.) was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Example 9
The average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the base coating layer is a bright material (Nippon B Chemical Co., Ltd.) having an average particle size of 15 μm and a thickness of 0.1 μm. A test piece was produced under the same conditions as in Example 1 except that 1% by weight of (aluminum base) was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Example 10
The average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the base coating layer is a bright material (Nippon B Chemical Co., Ltd.) having an average particle size of 15 μm and a thickness of 0.1 μm. A test piece was prepared under the same conditions as in Example 1 except that 20% by weight of (aluminum base) was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Comparative Example 1
As a comparative example of Example 1, a test piece was prepared under the same conditions as in Example 1 except that the average particle diameter of the orange atomized colorant contained in the colored coating layer was adjusted to 10 nm. The accelerated weather resistance and the color difference due to film thickness variation were evaluated. The results are shown in Table 1.

Comparative Example 2
As a comparative example of Example 2, a test piece was prepared under the same conditions as in Example 1 except that the average particle size of the orange atomized colorant contained in the colored coating layer was adjusted to 500 nm. The accelerated weather resistance and the color difference due to film thickness variation were evaluated. The results are shown in Table 1.

Comparative Example 3
As a comparative example of Example 3, the average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the weight ratio of the atomized colorant in the colored coating layer is 0.04%. A test piece was prepared under the same conditions as in Example 1 except that the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Comparative Example 4
As a comparative example of Example 4, the average particle size of the orange atomized colorant contained in the colored coating layer was adjusted to 150 nm, and the weight ratio of the atomized colorant in the colored coating layer was set to 60%. Except for the above, test pieces were produced under the same conditions as in Example 1, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Comparative Example 5
As a comparative example of Example 5 and Example 6, the average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the average particle size of this colored coating layer is adjusted to 500 nm. A test piece was produced under the same conditions as in Example 1 except that 4% by weight of the orange colorant was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

Comparative Example 6
As a comparative example of Example 7, the average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the glittering material-containing coating layer has an average particle size of 15 μm and a thickness of 0. A test piece was prepared under the same conditions as in Example 1 except that 0.8% by weight of a 1 μm glitter material (aluminum base manufactured by Nippon Bee Chemical Co., Ltd.) was added, and the saturation, accelerated weather resistance, and film thickness variation were The color difference due to was evaluated. The results are shown in Table 1.

Comparative Example 7
As a comparative example of Example 8, the average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the glittering material-containing coating layer has an average particle size of 15 μm and a thickness of 0. A test piece was prepared under the same conditions as Example 1 except that 25% by weight of a 1 μm glitter material (aluminum base manufactured by Nippon B Chemical Co., Ltd.) was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation. Was evaluated. The results are shown in Table 1.

Comparative Example 8
As a comparative example of Example 9, the average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the average particle size is 15 μm and the thickness is 0.1 μm in the base coating layer. A test piece was prepared under the same conditions as in Example 1 except that 0.8% by weight of the luster material (aluminum base manufactured by Nippon B Chemical Co., Ltd.) was added, and color difference due to saturation, accelerated weather resistance, and film thickness variation Was evaluated. The results are shown in Table 1.

Comparative Example 9
As a comparative example of Example 10, the average particle size of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the average particle size is 15 μm and the thickness is 0.1 μm in the base coating layer. A test piece was prepared under the same conditions as in Example 1 except that 25% by weight of the luster material (aluminum base manufactured by Nippon B Chemical Co., Ltd.) was added and evaluated for color difference due to saturation, accelerated weather resistance, and film thickness variation. did. The results are shown in Table 1.

考 察
実施例１，２および比較例１，２より、着色塗膜層に含有させる着色材の平均粒子径を３０ｎｍおよび３００ｎｍとしたときは、彩度、促進耐候性および膜厚変動色差ともに良好であったが、比較例１のように着色材の平均粒子径が１０ｎｍであると促進耐候性に問題があり、また比較例２のように着色材の平均粒子径が５００ｎｍであると彩度が低くなり鮮やかな色相の塗膜が得られなかった。 Comparative Example 10
As a comparative example of Example 1, the test piece was prepared under the same conditions as in Example 1 except that the lightness L of the base coating layer was set to 50 so that the lightness of the base coating layer was smaller than the lightness of the colored coating layer. It was prepared and the color difference due to saturation, accelerated weather resistance and film thickness variation was evaluated. The results are shown in Table 1.

Consideration From Examples 1 and 2 and Comparative Examples 1 and 2, when the average particle size of the coloring material contained in the colored coating layer is 30 nm and 300 nm, the saturation, accelerated weather resistance, and film thickness variation color difference are both good However, if the average particle diameter of the colorant is 10 nm as in Comparative Example 1, there is a problem in accelerated weather resistance, and if the average particle diameter of the colorant is 500 nm as in Comparative Example 2, the saturation is The coating film with a vivid hue could not be obtained.

  From Examples 3 and 4 and Comparative Examples 3 and 4, when the atomized colorant having an average particle size of 150 nm contained in the colored coating layer is 0.05% and 50% by weight, saturation and acceleration Although both weather resistance and film thickness variation color difference were good, a desired orange color could not appear when the weight ratio was 0.04% as in Comparative Example 3, and the weight ratio was as in Comparative Example 4. When it was 60%, the film became dark.

  From Examples 5 and 6 and Comparative Example 5, in addition to containing 4% by weight of the atomized colorant having an average particle diameter of 150 nm in the colored coating layer, 0% by weight of the colorant having an average particle diameter of 500 nm. When the content was 0.05% and 3%, the saturation, accelerated weather resistance, and film thickness variation color difference were all good, but when the content was 4% by weight as in Comparative Example 5, the saturation was low and bright. Orange can not appear.

  From Examples 7 and 8 and Comparative Examples 6 and 7, when a glitter material having an average particle diameter of 15 μm and a thickness of 0.1 μm was added to the glitter material-containing coating layer by 0.8% and 20% by weight. Saturation, accelerated weather resistance, and film thickness variation color difference were all good, but when the weight ratio was 0.8% as in Comparative Example 6, the desired glitter could not be obtained. Thus, there was a problem in adhesion when the weight ratio was 25%.

  From Examples 9 and 10 and Comparative Examples 8 and 9, when a bright material having an average particle diameter of 15 μm and a thickness of 0.1 μm was added to the base coating layer by 0.8% and 20% by weight, However, when the weight ratio was 0.8% as in Comparative Example 8, the desired glitter could not be obtained, and as in Comparative Example 9, When the weight ratio was 25%, there was a problem in adhesion.

  From Example 1 and Comparative Example 1, when the lightness of the base paint film layer was made larger than the lightness of the colored paint film layer, the base concealability was good and a vivid orange color appeared. When the lightness of the coating layer was smaller than the lightness of the colored coating layer, the ground could not be concealed and a vivid hue could not appear.

  In addition, when the external appearance of the laminated coating film of Examples 1 to 10 was observed, it was confirmed that a metallic feeling appeared in the glittering material-containing layer located below the colored coating film layer and exhibited an interference action without using a so-called interference pigment. It was done.

It is sectional drawing which shows the laminated coating film which concerns on 1st Embodiment of this invention. It is sectional drawing which shows the laminated coating film which concerns on 2nd Embodiment of this invention. It is sectional drawing which shows the laminated coating film which concerns on 3rd Embodiment of this invention. It is sectional drawing which shows the laminated coating film which concerns on 4th Embodiment of this invention. It is sectional drawing which shows the laminated coating film which concerns on 5th Embodiment of this invention. It is sectional drawing which shows the laminated coating film which concerns on 6th Embodiment of this invention.

Explanation of symbols

10 ... Coating object 20 ... Electrodeposition coating layer (underlayer)
21 ... Intermediate coating layer (underlayer)
30 ... Base coating layer 40 ... Colored coating layer 60 ... Clear coating layer 70 ... Bright material-containing coating layer

Claims (24)

A base layer formed on the surface of the object to be coated, a base coating layer formed on the surface of the base layer, a glittering material-containing coating layer containing a glittering material formed on the surface of the base coating layer, and A laminated coating film having at least a colored coating layer formed on the surface of the glittering material-containing coating layer,
A laminated coating film, wherein the lightness of the base coating film layer is higher than that of the colored coating film layer, and the colored coating film layer contains a finely divided coloring material having an average particle diameter of 30 nm to 300 nm.   2. The laminated coating film according to claim 1, wherein the glittering material-containing layer contains 1 to 20% by weight of the glittering material with respect to the resin solid content of the glittering material-containing layer.   The laminated coating film according to claim 1 or 2, wherein the glittering material-containing layer has a mean particle diameter of 1 to 20 µm and a thickness of 0.01 to 0.5 µm.   The laminated coating film according to any one of claims 1 to 3, wherein the base coating film layer contains a bright material.   The glittering material of the base coating layer has an average particle diameter of 1 to 20 μm and a thickness of 0.01 to 0.5 μm, and is 1 to the resin solid content of the colored coating layer or the base coating layer. The laminated coating film according to claim 4, which is contained in an amount of ˜20 wt%.   The laminated coating film according to any one of claims 1 to 5, further comprising a clear coating layer formed on a surface of the colored coating layer.   The laminated coating film according to any one of claims 1 to 6, wherein the colored coating layer contains a coloring material having an average particle diameter exceeding 300 nm.   The colorant having an average particle diameter exceeding 300 nm is contained in an amount of 0.05 to 3% by weight based on the resin solid content of the colored coating layer, and the atomized colorant has an average particle diameter exceeding 300 nm. The multilayer coating film according to claim 7, which is contained in a solid content ratio of 1.5 times or more with respect to the coloring material.   The laminated coating film according to claim 6, further comprising a second clear coating film layer formed on a surface of the clear coating film layer.   The laminated paint film according to any one of claims 1 to 9, wherein the atomized colorant is contained in an amount of 0.05 to 50% by weight based on the resin solid content of the colored paint film layer.   The multilayer coating film according to claim 1, wherein the underlayer has an electrodeposition coating film layer formed on a surface of the object to be coated.   The multilayer coating film according to claim 11, wherein the underlayer has an intermediate coating film layer formed on a surface of the electrodeposition coating film layer. A step of forming a base layer on the surface of the object to be coated, a step of forming a base coating layer on the surface of the base layer, and a glittering material-containing coating layer containing a glittering material on the surface of the base coating layer. A method of forming a multilayer coating film comprising at least a step of forming and a step of forming a colored coating film layer on the surface of the glittering material-containing layer,
A method for forming a laminated coating film, characterized in that the lightness of the base coating film layer is higher than the brightness of the colored coating film layer, and the colored coating film layer contains an atomized colorant having an average particle diameter of 30 nm to 300 nm. .   14. The method for forming a laminated coating film according to claim 13, wherein the glittering material-containing layer contains 1 to 20 wt% of the glittering material with respect to the resin solid content of the glittering material-containing layer.   The method for forming a laminated coating film according to claim 13 or 14, wherein the glitter material of the glitter material-containing layer has an average particle diameter of 1 to 20 µm and a thickness of 0.01 to 0.5 µm.   The method for forming a laminated coating film according to any one of claims 13 to 15, wherein the base coating film layer contains a bright material.   The glittering material of the base coating layer has an average particle diameter of 1 to 20 μm and a thickness of 0.01 to 0.5 μm, and is 1 to the resin solid content of the colored coating layer or the base coating layer. The method for forming a laminated coating film according to claim 16, which is contained in an amount of ˜20 wt%.   The method for forming a laminated coating film according to any one of claims 13 to 17, further comprising a step of forming a clear coating film layer on a surface of the colored coating film layer.   The method for forming a laminated coating film according to any one of claims 13 to 18, wherein the colored coating layer contains a colorant having an average particle diameter of more than 300 nm.   The colorant having an average particle diameter exceeding 300 nm is contained in an amount of 0.05 to 3% by weight based on the resin solid content of the colored coating layer, and the atomized colorant has an average particle diameter exceeding 300 nm. 20. The method for forming a laminated coating film according to claim 19, wherein the solid content ratio is 1.5 times or more with respect to the colorant.   The method for forming a laminated coating film according to claim 18, further comprising a step of forming a second clear coating film layer on a surface of the clear coating film layer.   The method for forming a laminated coating film according to any one of claims 13 to 21, wherein the atomized colorant is contained in an amount of 0.05 to 50% by weight based on a resin solid content of the colored coating film layer. .   The method for forming a multilayer coating film according to any one of claims 13 to 22, wherein the step of forming the base layer includes a step of forming an electrodeposition coating film layer on the surface of the object to be coated. The method for forming a multilayer coating film according to claim 23, wherein the step of forming the underlayer includes a step of forming an intermediate coating layer on the surface of the electrodeposition coating layer.

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