JP4543666B2 - High chroma laminated film and coating film forming method - Google Patents

Description

  The present invention relates to a laminated coating film and a coating film forming method excellent in saturation.

  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. Further, 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 is difficult to increase the saturation with the conventional method.
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 saturation.
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 colored coating layer formed on the surface of the film layer, wherein the lightness of the base coating layer is higher than the brightness of the colored coating layer, and the average particle size in the colored coating layer Rutotomoni include atomization colorant diameter 150 nm to 300 nm, the colored coating layer, contains colorant average particle diameter exceeds 300nm, colorants average particle diameter exceeds 300nm, the colored coating layer 0.05 to 3% by weight with respect to the resin solid content, and the atomized colorant is characterized by being contained 1.5 times or more in a solid content ratio with respect to the colorant having an average particle diameter exceeding 300 nm. A laminated coating film is provided.

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, Forming a colored coating layer on the surface of the base coating layer, wherein the lightness of the base coating layer is higher than the brightness of the colored coating layer, and to the colored coating layer contains micronized colorant having an average particle diameter 150nm~300nm the colored coating layer, Rutotomoni contains colorant average particle diameter exceeds 300 nm, the colored coating layer, the average particle size Is contained in a colorant having an average particle diameter of more than 300 nm, 0.05 to 3% by weight based on the resin solid content of the colored coating layer, and the atomized colorant For colorants with an average particle diameter exceeding 300 nm Provided is a method for forming a laminated coating film characterized by being contained at a solid content ratio of 1.5 times or more .

In this invention, while using the atomization coloring material with an average particle diameter of 150 nm-300 nm for the coloring coating film layer formed in the surface side of a laminated coating film, chroma is raised, while the base coating film formed in the lower side By making the lightness of the layer higher than the lightness of the colored coating layer, the light transmitted through the upper colorant is efficiently reflected. Thereby, the laminated coating film excellent in saturation can be obtained.

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 multilayer coating film having any of the above 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 is formed on the surface of the intermediate coating layer 21, and the colored coating layer 40 is formed on the surface of the base coating layer 30.

  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 30 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, 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 30 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 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 base coating layer 30 using a spraying machine such as a spray coating gun. For example, it is formed by baking at 80 to 160 ° C. for 10 to 30 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 diameter of the atomized colorant is smaller than 30 nm, the weather resistance may be affected depending on the type and grade of the colorant. If the average particle diameter exceeds 300 nm, the 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. The weight ratio here refers to the weight B of the atomized colorant relative to the resin solid content weight A, that is, B / A (%).

  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 of more than 300 nm is 0.05 to It may be included in the range of 3% by weight. 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, it is possible to realize the high chroma coating film intended by the present invention. It is not possible.

  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 four layers of the electrodeposition coating layer 20 and the intermediate coating layer 21, the base coating layer 30, and the colored coating layer 40, which are the base layers, is baked and cured. The above 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 and the colored coating layer 40, the intermediate coating layer 21 and the base coating The film layer 30 and the colored coating layer 40 can be exemplified as wet-on-wet coating. In particular, it is more preferable that the base coating layer 30 and the colored coating layer 40 are applied wet-on-wet in the top coating step and these are simultaneously baked in the top coating baking step.

Third embodiment (FIG. 3)
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 present embodiment includes an electrodeposition coating layer 20 formed on the surface of the article 10 to be coated, a base coating layer 30 formed on the surface of the electrodeposition coating layer 20, and the base. The colored coating layer 40 is formed on the surface of the coating layer 30, and the second colored coating layer 50 is formed on the surface of the colored coating layer 40.

  The laminated coating film according to the present embodiment is obtained by adding a second colored coating film layer 50 to the laminated coating film according to the second embodiment shown in FIG. Since 30 and the colored coating layer 40 are the same as those in the second embodiment, detailed description thereof is omitted.

  The second colored coating layer 50 according to the present embodiment is mainly composed of a polyester resin, an acrylic resin, a vinyl chloride vinyl acetate copolymer resin, a urethane resin, a cellulose resin, and the like, and a colorant or an additive is 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 colored coating layer 40 using a spraying gun or other coating machine. If it is a thermosetting paint, it is formed by baking at 80 to 160 ° C. for 10 to 30 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, in the second colored coating layer 50 according to the present embodiment, a coloring material having an average particle diameter exceeding 300 nm is 0.05 to 50% by weight with respect to the resin solid content of the second colored coating layer 50. included. Further, the second colored coating layer 50 may contain a minute amount of atomized colorant having an average particle diameter of 30 nm to 300 nm.

  Thus, even if the second colored coating film layer 50 containing the coloring material having an average particle diameter exceeding 300 nm is formed on the surface of the colored coating film layer 40 containing the atomized coloring material, the effect of high saturation is achieved by the colored coating. While being able to be achieved by the film layer 40, the base concealing property can be secured by the base coating film layer 30.

  In addition, although illustration is abbreviate | omitted, the 3rd coloring containing the coloring material which has the same structure as the said 2nd colored coating film layer 50 further on the surface of the said 2nd colored coating film layer 50, ie, an average particle diameter exceeds 300 nm. A coating layer can also be formed. Further, although not shown, a transparent clear coating layer that does not contain a coloring material may be formed in place of the second colored coating layer 50 or the third colored coating layer.

Fourth embodiment (FIG. 4)
FIG. 4 is a sectional view showing a laminated coating film according to the fourth embodiment of the present invention. The laminated coating film according to the first to third embodiments described above is a so-called solid coating film that does not include a bright material in the coating film, but the laminated coating film of the present invention is in any coating film. It can also be embodied in a so-called metallic coating film containing a bright material.

  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 colored coating layer 40 formed on the surface of the base coating layer 30, and the surface of the colored coating layer 40 The clear coating layer 60 is different from the first embodiment described above in that the colored coating layer 40 includes a glitter material and the clear coating layer 60 exists. Since the electrodeposition coating layer 20, the intermediate coating layer 21 and the base coating layer 30 have the same configuration as that of the first embodiment, detailed description thereof will be omitted.

  The colored coating layer 40 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. By coating the surface of the base coating layer 30 with a coating machine such as a spray coating gun, which is a thermosetting paint, a room temperature curable paint or a two-component curable paint, which is diluted with a solvent. It is formed. In addition, since it paints with the clear coating film layer 60 mentioned later by wet on wet, baking hardening is performed after the clear coating film layer 60 is formed.

  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.

  In addition, the colored coating layer 40 according to the present embodiment has a glittering 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 colored coating layer 40. It is contained in an amount of 1 to 20% by weight, more preferably 1 to 10% by weight. When the weight ratio of the glittering material exceeds 20% by weight, the coating film adhesion may be adversely affected.

  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 contains 0.05 to 50% by weight of the above-described atomized colorant with respect to the resin solid content. If the weight ratio of the atomized colorant is less than 0.05% by weight, a sufficient coloring effect cannot be obtained, and if the weight ratio of the atomized colorant exceeds 50% by weight, the colored coating layer 40 appears 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 of more than 300 nm is 0.05 to It may be included in the range of 3% by weight. 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, it is possible to realize the high chroma coating film intended by the present invention. It is not possible.

  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.

  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 30 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 30 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.

  As described above, when the colored coating layer 40 containing the atomized coloring material contains the glitter material, a metallic feeling can be realized by the colored coating layer 40, and the effect of high saturation is achieved by the colored coating layer 40. In addition, the base concealability can be secured by the base coating layer 30.

  In the above-described embodiment, each of the four layers of the electrodeposition coating layer 20 and the intermediate coating layer 21, the base coating layer 30, and the colored coating layer 40, which are the base layers, is baked and cured. The above 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 and the colored coating layer 40, the intermediate coating layer 21 and the base coating The film layer 30 and the colored coating layer 40 can be exemplified as wet-on-wet coating. In particular, it is preferable that the base coating layer 30, the colored coating layer 40, and the clear coating layer 60 are applied wet-on-wet in the top coating step, and these are simultaneously baked in the top coating baking step.

Fifth embodiment (FIG. 5)
FIG. 5 is a cross-sectional view showing a laminated coating film according to a fifth embodiment of the present invention, and the laminated coating film according to the present embodiment is also a metallic coating film as in the fourth embodiment described above. However, this is an example in which a glittering material exhibiting a metallic feeling is contained in the base coating layer 30 instead of the colored coating layer 40.

  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 colored coating layer 40 formed on the surface of the base coating layer 30, and the surface of the colored coating layer 40 The clear coating layer 60 is different from the first embodiment described above in that the base coating layer 30 includes a glitter material and the clear coating layer 60 is present. The electrodeposition coating layer 20, the intermediate coating layer 21 and the colored coating layer 40 have the same configuration as that of the above-described first embodiment, and the clear coating layer 60 has the same configuration as that of the above-described fourth embodiment. Since it is the same structure, the detailed description is abbreviate | 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 30 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. It is contained in an amount of 1 to 20% by weight, more preferably 1 to 10% by weight. When the weight ratio of the glittering material exceeds 20% by weight, the coating film adhesion may be adversely affected.

  As described above, when a bright material is contained in the base coating layer 30 having a high brightness, a metallic feeling can be realized by the base coating layer 30, and an effect of high saturation is achieved by the colored coating layer 40. In addition, the base concealability can be secured by the base coating layer 30.

  In the above-described embodiment, each of the four layers of the electrodeposition coating layer 20 and the intermediate coating layer 21, the base coating layer 30, and the colored coating layer 40, which are the base layers, is baked and cured. The above 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 and the colored coating layer 40, the intermediate coating layer 21 and the base coating The film layer 30 and the colored coating layer 40 can be exemplified as wet-on-wet coating. In particular, it is preferable that the base coating layer 30, the colored coating layer 40, and the clear coating layer 60 are applied wet-on-wet in the top coating step, and these are simultaneously baked in the top coating baking step.

Sixth embodiment (FIG. 6)
FIG. 6 is a cross-sectional view showing a laminated coating film according to a sixth embodiment of the present invention, and the laminated coating film according to this embodiment is a metallic coating film as in the fifth embodiment described above. It is the example which abbreviate | omitted the intermediate coating film layer 21 which concerns on a form.

  That is, the multilayer coating film according to the present embodiment includes an electrodeposition coating layer 20 formed on the surface of the article 10 to be coated, and a base coating layer 30 formed on the surface of the electrodeposition coating layer 20; The colored coating layer 40 is formed on the surface of the base coating layer 30, and the clear coating layer 60 is formed on the surface of the colored coating layer 40.

  Thus, even if the intermediate coating film layer 21 is omitted and the glittering material is contained in the base coating film layer 30 with high brightness, a metallic feeling can be realized with the base coating film layer 30, and high saturation is achieved. This effect can be achieved by the colored coating layer 40, and the base concealing property can be secured by the base coating layer 30.

Seventh embodiment (FIG. 7)
FIG. 7 is a cross-sectional view showing a laminated coating film according to a seventh embodiment of the present invention. The laminated coating film according to this embodiment is a metallic coating film as in the above-described sixth embodiment. This is an example in which the second colored coating layer 50 is added to the laminated coating layer according to the embodiment, and the electrodeposition coating layer 20, the base coating layer 30, the colored coating layer 40 and the clear coating layer 60 are the sixth embodiment. Since it is the same as a form, the detailed description is abbreviate | omitted.

  The second colored coating layer 50 according to the present embodiment is mainly composed of a polyester resin, an acrylic resin, a vinyl chloride vinyl acetate copolymer resin, a urethane resin, a cellulose resin, and the like, and a colorant or an additive is 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 colored coating layer 40 using a spraying gun or other coating machine. If it is a thermosetting paint, it is formed by baking at 80 to 160 ° C. for 10 to 30 minutes, for example. In addition, when three layers of the colored coating layer 40, the second colored coating layer 50, and the clear coating layer 60 are applied by wet-on-wet, this bake hardening is performed by baking the clear coating layer 60. Done at the same time.

  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, in the second colored coating layer 50 according to the present embodiment, a coloring material having an average particle diameter exceeding 300 nm is 0.05 to 50% by weight with respect to the resin solid content of the second colored coating layer 50. included. Further, the second colored coating layer 50 may contain a minute amount of atomized colorant having an average particle diameter of 30 nm to 300 nm.

  Thus, even if the second colored coating film layer 50 containing the coloring material having an average particle diameter exceeding 300 nm is formed on the surface of the colored coating film layer 40 containing the atomized coloring material, the effect of high saturation is achieved by the colored coating. While being able to be achieved by the film layer 40, the base concealing property can be secured by the base coating film layer 30. Moreover, a metallic feeling can appear in the base coating film layer 30 containing a brilliant material.

  In addition, although illustration is abbreviate | omitted, the 3rd coloring containing the coloring material which has the same structure as the said 2nd colored coating film layer 50 further on the surface of the said 2nd colored coating film layer 50, ie, an average particle diameter exceeds 300 nm. A coating layer can also be formed.

  Hereinafter, the present invention will be described more specifically.

<< Reference Example 1 >> A dull 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 after this, a zinc phosphate coating is formed thereon, a cationic phosphate coating ( An electrodeposition coating layer was formed by performing electrodeposition coating using a power top U-600M manufactured by Nippon Paint Co., Ltd. so as to have a film thickness of 20 μm and 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.

  Color base white (acrylic / melamine resin manufactured by Nippon Bee Chemical Co., Ltd., lightness L = 80 to 90) was used as a base paint constituting the base coating layer, and spray coating was performed so that the film thickness was 30 ± 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 Bee Chemical Co., Ltd.) so that the weight ratio to the resin solid content was 4% by weight, and thinner as a solvent (Nippon Bee Chemical) The colored paint constituting the colored coating layer obtained by diluting with T-536MB) was spray-coated on the surface of the previously formed uncured base coating layer so as to have a film thickness of 20 μm. .

  Further, a clear coating (2K clear manufactured by Nippon Bee Chemical Co., Ltd.) is spray-coated on the surface of the uncured colored coating layer so that the film thickness becomes 30 μm, and these base coating layer, colored coating layer and clear coating are applied. The film 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.

  In addition, an accelerated weathering test (XWOM: xenon weatherometer method) of JIS K5600-7-7 was performed on the obtained multilayer coating film, and the hue before the test and the hue after the test were visually evaluated. “◎” 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 Reference Example 1 except that the average particle size of the orange atomized colorant contained in the colored coating layer was adjusted to 300 nm, and saturation and accelerated weather resistance were prepared. And the color difference due to film thickness variation was evaluated. The results are shown in Table 1.

Example 3 The average particle diameter 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 0.05% by weight. Except for the above, test pieces were prepared under the same conditions as in Reference 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.

<< Example 4 >> 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 50% by weight. Test pieces were produced under the same conditions as in Reference 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.

Example 5 An orange colorant prepared by adjusting the average particle size of the orange atomized colorant to be contained in the colored coating layer to 150 nm, and further adjusting the average particle size to 500 nm in the colored coating layer. A test piece was prepared under the same conditions as in Reference Example 1 except that 0.05% by weight 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 An orange colorant prepared by adjusting the average particle size of the orange atomized colorant to be contained in the colored coating layer to 150 nm, and further adjusting the average particle size to 500 nm in the colored coating layer. A test piece was prepared under the same conditions as in Reference Example 1 except that 3% by weight was added in a weight ratio, 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 colored coating layer is further brightened with 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 Reference Example 1 except that 1% by weight of a material (aluminum base manufactured by Nippon Bee 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 8 The orange atomized colorant contained in the colored coating layer was prepared to have an average particle size of 150 nm, and the colored coating layer was further brightened with 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 Reference Example 1 except that a material (aluminum base manufactured by Nippon Bee Chemical Co., Ltd.) was added at a weight ratio of 20% by weight, 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 >> An orange atomized colorant contained in a colored coating layer has an average particle size of 150 nm, and the base 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 Reference Example 1 except that 1% by weight (aluminum base manufactured by Nippon Bee Chemical Co., Ltd.) was added by weight ratio, 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 >> An orange atomized colorant contained in a colored coating layer has an average particle size of 150 nm, and the base 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 Reference Example 1 except that 20% by weight (aluminum base manufactured by Nippon Bee Chemical Co., Ltd.) was added by weight, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. The results are shown in Table 1.

As a comparative example of "Comparative Example 1" Example 1, except that the average particle diameter of orange atomization colorant to be contained in the colored coating layer was prepared in the 10nm manufacturing a test piece under the same conditions as in Reference Example 1 The color difference due to saturation, accelerated weather resistance and film thickness variation was 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 Reference Example 1 except that the average particle diameter of the orange atomized colorant contained in the colored coating layer was adjusted to 500 nm. The color difference due to saturation, accelerated weather resistance and film thickness variation was evaluated. The results are shown in Table 1.

<< Comparative Example 3 >> As a comparative example of Example 3, 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 set to A test piece was prepared under the same conditions as in Reference Example 1 except that the content was 0.04% by weight, 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 4 >> As a comparative example of Example 4, 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 set to A test piece was produced under the same conditions as in Reference Example 1 except that the amount was 60% by weight, 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 diameter of the orange atomized colorant contained in the colored coating layer is adjusted to 150 nm, and the average particle size is further added to this colored coating layer. A test piece was prepared under the same conditions as in Reference Example 1 except that 4% by weight of an orange colorant having a diameter adjusted to 500 nm was added, and the color difference due to saturation, accelerated weather resistance, and film thickness variation was evaluated. did. 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 average particle size of the colored coating layer is 15 μm. A test piece was prepared under the same conditions as in Reference Example 1 except that a bright material (aluminum base manufactured by Nippon Bee Chemical Co., Ltd.) having a thickness of 0.1 μm was added in a weight ratio, and saturation and accelerated weather resistance were prepared. The color difference due to the property and film thickness variation 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 average particle size of the colored coating layer is 15 μm. A test piece was prepared under the same conditions as in Reference Example 1 except that a bright material (aluminum base manufactured by Nippon Bee Chemical Co., Ltd.) having a thickness of 0.1 μm was added in a weight ratio, and the saturation, accelerated weather resistance and The color difference due to 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 of the base coating layer is 15 μm. A test piece was prepared under the same conditions as in Reference Example 1 except that a bright material having a thickness of 0.1 μm (aluminum base manufactured by Nippon B Chemical Co., Ltd.) was added in a weight ratio, and saturation and accelerated weather resistance were prepared. And the color difference due to 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 of the base coating layer is 15 μm. A test piece was prepared under the same conditions as in Reference Example 1 except that a bright material having a thickness of 0.1 μm (aluminum base manufactured by Nippon B Chemical Co., Ltd.) was added in a weight ratio, and the saturation, accelerated weather resistance, and film The color difference due to thickness variation was evaluated. The results are shown in Table 1.

《考察》参考例１，実施例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。 As a comparative example for "Comparative Example 10" Example 1, except that the brightness of the base coating layer has a lightness L = 50 of the base coating film layer to be less than the lightness of the colored coating layer same as in Reference Example 1 Test pieces were prepared under the conditions, 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 Reference Example 1, Example 2 and Comparative Examples 1 and 2, when the average particle diameter of the coloring material contained in the colored coating layer is 30 nm and 300 nm, saturation, accelerated weather resistance, and film thickness variation Although the color difference was good, when the average particle diameter of the coloring material was 10 nm as in Comparative Example 1, there was a problem in the accelerated weather resistance, and the average particle diameter of the coloring material was 500 nm as in Comparative Example 2. As a result, the saturation was lowered and a 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 average particle size of 150 nm in the colored coating layer, 0.05% and 3% of the colorant having an average particle size of 500 nm by weight are used. %, The saturation, accelerated weather resistance, and film thickness variation color difference were good. However, when 4% by weight was added as in Comparative Example 5, a bright orange color with low saturation appeared. There was also a problem with accelerated weather resistance.

  From Examples 7 and 8 and Comparative Examples 6 and 7, when a bright material having an average particle diameter of 15 μm and a thickness of 0.1 μm was added to the colored coating layer by 0.8% and 20% by weight, However, when the weight ratio was 0.8% as in Comparative Example 6, the desired glitter could not be obtained, and as in Comparative Example 7, When the weight ratio was 25%, there was a problem in accelerated weather resistance and coating film adhesion.

  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 accelerated weather resistance and coating film adhesion.

From Reference Example 1 and Comparative Example 1, when the brightness of the base coating film layer was made larger than the brightness of the colored coating 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.

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. It is sectional drawing which shows the laminated coating film which concerns on 7th 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 50 ... Second colored coating layer 60 ... Clear coating layer

Claims (14)

Laminated coating film having at least 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, and a colored coating layer formed on the surface of the base coating layer Because
The base brightness of the coating layer is higher than the brightness of the colored coating layer and the colored coating layer Rutotomoni contains micronized colorant having an average particle diameter of 150 nm to 300 nm,
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. A laminated coating film characterized by being contained 1.5 times or more in a solid content ratio with respect to a coloring material . The multilayer coating film according to claim 1 , further comprising a second colored coating layer formed on a surface of the colored coating layer and including a coloring material having an average particle diameter exceeding 300 nm. The multilayer coating film according to claim 2 , further comprising a third colored coating layer formed on the surface of the second colored coating layer and including a coloring material having an average particle diameter exceeding 300 nm. The laminated paint film according to any one of claims 1 to 3, 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. At least one of the colored coating layer or the base coating layer contains a glittering material,
The glittering material has an average particle diameter of 1 to 20 μm and a thickness of 0.01 to 0.5 μm, and is contained in an amount of 1 to 20% by weight based on the resin solid content of the colored coating layer or the base coating layer. The laminated coating film according to any one of claims 1 to 4, wherein the laminated coating film is formed. The multilayer coating film according to any one of claims 1 to 5, wherein the foundation layer has an electrodeposition coating film layer formed on a surface of the object to be coated. The multilayer coating film according to claim 6 , wherein the underlayer has an intermediate coating film layer formed on a surface of the electrodeposition coating film layer. Forming a base layer on the surface of the object to be coated;
Forming a base coating layer on the surface of the underlayer;
A step of forming a colored coating film layer on the surface of the base coating film layer, and a method of forming a laminated coating film having at least
The base brightness of the coating layer is higher than the brightness of the colored coating layer and the colored coating layer Rutotomoni contains micronized colorant having an average particle diameter of 150 nm to 300 nm, the colored coating layer, the average A colorant having a particle diameter exceeding 300 nm is included,
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. A method for forming a laminated coating film, comprising a solid content ratio of 1.5 times or more with respect to a colorant . The formation of a multilayer coating film according to claim 8 , further comprising a step of forming a second colored coating film layer containing a coloring material having an average particle diameter of more than 300 nm on the surface of the colored coating film layer. Method. The laminate coating according to claim 9 , further comprising a step of forming a third colored coating layer containing a coloring material having an average particle diameter exceeding 300 nm on the surface of the second colored coating layer. Method for forming a film. 11. The laminated coating film according to claim 8, wherein the atomized colorant is included in an amount of 0.05 to 50% by weight with respect to the resin solid content of the colored coating film layer. Forming method. At least one of the colored coating layer or the base coating layer contains a glittering material,
The glittering material has an average particle diameter of 1 to 20 μm and a thickness of 0.01 to 0.5 μm, and is contained in an amount of 1 to 20% by weight based on the resin solid content of the colored coating layer or the base coating layer. The method for forming a laminated coating film according to any one of claims 8 to 11, wherein: The process of forming the said base layer has a process of forming an electrodeposition coating film layer on the surface of the said to-be-coated object, The formation of the laminated coating film as described in any one of Claims 8-12 characterized by the above-mentioned. Method. The method for forming a multilayer coating film according to claim 13 , wherein the step of forming the base layer includes a step of forming an intermediate coating layer on the surface of the electrodeposition coating layer.

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