JP6156427B2 - Laminated coatings and painted products - Google Patents

Description

  The present invention relates to a laminated coating film and a coated product.

  Generally, a plurality of coating films are stacked on the surface of a base material such as a car body or a car part to protect the base material and improve the appearance. For example, in Patent Document 1, in order to obtain a golden appearance having high saturation and lightness and having a glittering feeling, a clear coating film is added to a glittering base coating film containing a colored aluminum pigment, an aluminum pigment and a coloring pigment. It describes that it is set as the coating-film structure which laminated | stacked. The colored aluminum pigment is a scaly glittering pigment obtained by vapor-depositing a coating component containing iron oxide on aluminum flakes, and when the hue of the colored aluminum pigment is the reference (0 position) of the Munsell hue ring 100, , A pigment having a hue range of −3 to −15, and a pigment having a hue range of +3 to +15, which are represented by counterclockwise −50 and clockwise +50, are included. Moreover, it is said that a colored pigment can be mix | blended with the said clear coating film.

JP 2011-251252 A

  By the way, as shown in FIG. 1, when a colored layer (for example, a color clear layer) 4 having translucency containing a pigment 3 is laminated on a glitter layer 2 containing a glitter material (for example, aluminum flakes) 1. Color unevenness may occur due to uneven thickness of the colored layer 4. That is, the degree of light absorption is different between the thick and thin colored layers 4, and as a result, bright portions and dark portions are formed, resulting in uneven color tone and shading.

  As a countermeasure against this, as shown in FIG. 2, there is known a method of suppressing color unevenness by putting a pigment 3 having the same color as the colored layer 4 in the glittering layer 2. However, as shown in the figure, the pigment 3 is not necessarily uniformly dispersed throughout the glittering layer 2, and the pigment 3 is usually unevenly distributed. For example, in the surface layer portion of the glitter layer 2, a portion where the amount of the pigment 3 on the glitter material 1 is large and a portion where the amount of the pigment 3 on the glitter material 1 is small are generated. In that case, the reflection of the light by the glitter material 1 becomes weak (darker) in the portion where the pigment 3 is large, and the reflection of the light by the glitter material 1 becomes strong (brighter) in the portion where the pigment 3 is small. As described above, even when the pigment 3 is added to the glittering layer 2, the color unevenness is not necessarily eliminated.

  Further, as shown in FIG. 2, due to the uneven distribution of the pigment 3 in the glittering layer 2, the glittering material 1 is not oriented parallel to the surface of the glittering layer 2, and a part of the glittering material 1 is inclined. As a result, there is also a problem that the brightness is lowered entirely or partially.

  Therefore, the present invention suppresses uneven color tone and shading in a laminated coating film having a glitter layer, and improves flip-flop properties.

  In order to solve the above-mentioned problems, the present invention employs special colored flakes for the glitter material of the glitter layer.

The laminated coating film according to the present invention includes a glittering layer containing a glittering material, and the glittering layer is the glittering material, and the surface of the glittering flakes is different from each other in the total light transmittance of visible light. A plurality of kinds of coloring materials containing colored flakes covered with the above coloring material and having different total light transmittances are attached to the surface of the glittering flakes as spots.

  According to this aspect, when light is incident on the glittering layer, light having a wavelength unique to the colorant is reflected by the colorant of the colored flakes, and light having other wavelengths is absorbed by the colorant. Thus, light is strongly absorbed in the portion where the coloring material having a low total light transmittance is attached to the colored flakes, whereas light is transmitted through the coloring material in a portion where the coloring material having a high total light transmittance is attached. Since it is easy to reach the glitter frame, the regular reflection of light by the glitter flakes becomes strong.

Further, in this embodiment, the reflection angle of light (perpendicular and the angle of the reflection direction of the surface of the colored flake) increases, the light reflected by the total light transmittance is low colorant adhering scattered glitter flakes Is blocked, and the reflected light becomes weak. In particular, on the shade side (incidence side where reflected light away from the regular reflection direction is weak) , the reflected light intensity decreases.

  As described above, according to the present invention, the colored flakes of the glittering layer not only have a function of reflecting light but also have a function of absorbing light, so that the colored layer having translucency on the glittering layer. It is not always necessary to overlap (for example, a color clear coating film). Therefore, it is possible to prevent the occurrence of color unevenness due to the uneven thickness of the conventional colored layer. In addition, since the reflected light intensity due to the glitter flakes varies greatly depending on the reflection angle, the flip-flop property is enhanced.

In good preferable embodiment, as the colorant, the total light transmittance with two kinds of colorants are different, the area ratio of the total light transmittance is high coloring material in the coloring flake 25% 80% It is as follows. This makes it possible to increase the FI (flop index) value while using colored flakes, which is advantageous in improving flip-flop properties.

  In a preferred embodiment, the colorant is granular and has an average particle diameter of 300 nm or less. As a result, the colored flakes are less bright due to the granular colorant, and therefore have high brightness, which is advantageous for improving flip-flop properties.

Here, the present invention does not exclude that a colored layer containing a colorant having the same color as the colorant is superimposed on the glitter layer. Even when such a colored layer is provided, the light transmitted through the colored layer and incident on the glittering layer is absorbed and reflected by the colored flakes, so that color unevenness is suppressed.

  In addition, according to the present invention, since color unevenness is suppressed by the colored flakes, it is not always necessary to add a pigment to the glitter layer, but if necessary, a small amount of pigment is prevented from being added to the glitter layer. It is not a thing. However, when a pigment is added to the glittering layer, the pigment concentration is preferably 5.0% or less in terms of PWC. By making the pigment concentration of the glitter layer low or zero, the occurrence of uneven color due to the uneven distribution of the pigment on the glitter material is suppressed, and the orientation of the glitter material is less disturbed by the pigment. This is advantageous for securing the luminance.

  Adopting aluminum flakes obtained by crushing aluminum foil as the glitter flakes, and further vapor deposition with increased surface smoothness obtained by crushing a film in which aluminum is vapor-deposited on a thin substrate It is preferable to use aluminum flakes in order to increase the luminance and obtain a metal texture.

  In a preferred embodiment, the colorant is a dark color system such as red or black (Munsell brightness is 5 or less), particularly a black color system. That is, as shown in FIG. 1 and FIG. 2, when a black pigment is added to the colored layer to develop a black color, the degree of light absorption in the colored layer is partially different depending on the uneven thickness of the colored layer, Unevenness (particularly shading) is likely to occur. From the viewpoint of preventing such color unevenness, it is meaningful to employ a dark color coloring material for the colored frame of the glitter layer.

  In a preferred embodiment, the glitter layer is laminated on a colored underlayer having the same color as the colorant.

  When the thickness of the colored flakes in the glittering layer is thin, the light incident on the laminated coating is transmitted through the colored flakes and reflected by the base. In that case, the color of the base affects the paint color of the appearance. That is, the paint color becomes turbid. Therefore, the underlayer is a colored underlayer having the same color as that of the colored layer. As a result, the turbidity of the coating color is suppressed, and the denseness, depth, and metal texture are enhanced.

Here, in the achromatic color, the same color system means that the lightness difference in the Munsell value of the comparison target color is 5.0 or less . In the chromatic color, the same color system means that the Munsell hue circle is divided into 100 and is the comparison target. one of the hue of the color as a reference (0 position), the left around +50, when viewed in clockwise -50, other hue comparison target color is that in the hue range of ± 10.

  In a preferred embodiment, a transparent clear layer is directly laminated on the glitter layer. That is, the colored layer shown in FIG. 1 and FIG. 2 is omitted, which is advantageous for preventing the occurrence of color unevenness, and acid resistance and scratch resistance can be obtained by the transparent clear layer.

  Examples of the coated object provided with the above-mentioned laminated coating film on the object to be coated include an automobile body, a motorcycle, other vehicle bodies, and other metal products. .

  According to the present invention, the colored flakes of the glittering layer not only have a function of reflecting light but also have a function of absorbing light, so that a colored layer having translucency is superimposed on the glittering layer. Therefore, it is not always necessary. Therefore, it is possible to prevent the occurrence of uneven color due to the uneven thickness of the conventional colored layer, and the reflected light intensity due to the glitter flakes varies greatly depending on the reflection angle. Therefore, it is advantageous for improving the flip-flop property.

Sectional drawing which shows the prior art example of a laminated coating film typically. Sectional drawing which shows another prior art example typically. Sectional drawing which shows typically the laminated coating film which concerns on embodiment of this invention. Sectional drawing which shows an example of colored flakes typically. The top view which shows the same coloring frame typically. Sectional drawing which shows another example of colored flakes typically. The top view which shows the same coloring frame typically. The graph which shows the influence which the aluminum flake exposure area rate and pigment particle size have in the light reflectivity in the exposure type colored flakes using a red pigment. The graph which shows the influence which the aluminum flake exposure area rate and pigment particle size have in the light reflectivity in the exposure-type colored flakes using a black pigment. Explanatory drawing of the reflected light used for calculation of FI value. The graph which shows the influence which the aluminum flake exposed area ratio and pigment particle diameter of exposure type colored flake have on FI value. The figure explaining that the shielding degree of the reflected light by a coloring material changes with reflection angles in exposed colored flakes with an exposed area rate of 40%. The graph which shows the influence which the area ratio of the black pigment 2 and the pigment particle diameter have in the light reflection factor in mixed colored flakes. The graph which shows the influence which the area ratio of the black pigment 2 of mixed-type colored flakes and a pigment particle size have on FI value.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. The following description of the preferred embodiments is merely exemplary in nature and is not intended to limit the invention, its application, or its use.

<Configuration example of laminated coating film>
As shown in FIG. 3, the laminated coating film 12 provided on the surface of the vehicle body (steel plate) 11 of the automobile of this embodiment is formed by laminating a colored underlayer 14, a glittering layer 15 and a transparent clear layer 16 in this order. An electrodeposition coating (undercoat) 13 is formed on the surface of the vehicle body 11 by cationic electrodeposition coating, and the laminated coating 12 is provided on the electrodeposition coating 13. In this laminated coating film 12, the colored underlayer 14 corresponds to an intermediate coating, and the glitter layer 15 and the transparent clear layer 16 correspond to an overcoat.

A dark pigment 21 is dispersed in the colored underlayer 14. In the glittering layer 15, colored flakes 22 as a glittering material are dispersed. As the pigment 21, for example, pigments of various hues such as black pigments such as carbon black, perylene black, and aniline black having an average particle diameter of 300 nm to 500 nm or red pigments such as perylene red can be employed. As the coloring material of the colored flakes 22, a pigment having the same color as that of the pigment 21 of the colored underlayer 14 is employed.

  The colored flakes 22 of the glitter layer 15 are oriented so as to be substantially parallel to the surface of the glitter layer. After the paint containing the colored flakes 22 is applied on the colored base layer 14, the colored flakes 22 are physically arranged in a flat manner by utilizing the fact that the coating film is contracted and thinned by evaporation of the solvent by baking. .

  As the resin component of the colored underlayer 14, for example, a polyester-based resin can be used. As the resin component of the glittering layer 15, for example, an acrylic resin can be used, and the resin of the transparent clear layer 16. As the component, for example, an acid epoxy curable acrylic resin can be employed.

<Colored flakes>
Next, the colored flakes 22 will be described. The former of the “exposed colored flakes” and “mixed colored flakes” described below is a colored flake according to a reference form, and the latter is a colored flake according to an embodiment of the present invention.

[Exposed colored flakes]
4 and 5 show a colored flake 22A as an example of the colored flake 22. FIG. The colored flakes 22A are particles in which the granular colorant (pigment) 26 is scattered and attached to the surface of the aluminum flakes 25 as glitter flakes, and the aluminum flakes 25 are partially exposed. The entire aluminum flake is covered with the resin coat layer 27. Since the colored flakes 22A are partially exposed, the aluminum flakes are referred to as “exposed colored flakes” for convenience. The exposed colored flakes 22A can be manufactured, for example, by the following immersion method or vapor deposition method.

[Dipping method]
A coloring material, a silane coupling agent, and a solvent are mixed and dispersed by a ball mill. An aluminum flake paste and a solvent are added to the dispersion, and further, a dispersion treatment by a ball mill is performed. Solvent is added to the resulting slurry to remove the dispersing holes and left as it is to precipitate the aluminum flakes to which the coloring material has adhered, and the solvent is removed.

  Next, in order to coat the obtained aluminum flakes with a resin, monomers such as acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate and the like are dispersed in a slurry in which the colored aluminum flakes are dispersed in a hydrocarbon or alcohol solvent. A polymerization initiator such as benzoyl peroxide or isobutyl peroxide is added, and the mixture is heated and stirred to polymerize the monomer, thereby precipitating on the surface.

  In the above immersion method, carbon black is used as a coloring material, 1 g of carbon black, 0.5 g of silane coupling agent, 10 g of solvent (mineral split), aluminum flake paste (aluminum flake; average particle size: 30 μm, When the average thickness was set to 10 g, carbon black was scattered and adhered to the aluminum flakes, and the exposed area ratio of the aluminum flakes was 60%.

[Vapor deposition method]
This is a method in which a coloring material is evaporated and adhered to aluminum flakes while fluidizing the aluminum flakes in a vacuum vessel equipped with a powder fluidizing device and a resistance heating device. As the powder fluidizer, for example, a rotary fluidizer equipped with a barrel-type rotary vacuum chamber is used. The resistance heating device includes, for example, a DC power source, a pair of copper electrodes, and a stainless steel resistor, and the copper electrode is connected to a wire drawn from the DC power source into the vacuum chamber. The stainless steel resistor is bolted to the copper electrode so that it is located in the center of the vacuum chamber.

A slurry in which aluminum flakes are dispersed in acetone is subjected to suction filtration, and then dried with hot air at 200 ° C. to obtain a dry powder of aluminum flakes. Fill the vacuum chamber with aluminum flakes and wrap the colorant in a stainless steel mesh. The vacuum degree in the vacuum chamber is lowered to 10 ⁻⁴ torr or less. A vacuum chamber is rotated by a rotor, and while flowing aluminum flakes, an electric current is applied to the electrodes to heat and evaporate the pigment. After the evaporation is complete, the aluminum flakes are cooled to near room temperature. Thereby, the aluminum flake which the colorant scattered and adhered is obtained.

  Next, in order to coat the obtained aluminum flakes with a resin, monomers such as acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate and the like are dispersed in a slurry in which the colored aluminum flakes are dispersed in a hydrocarbon or alcohol solvent. A polymerization initiator such as benzoyl peroxide or isobutyl peroxide is added, and the mixture is heated and stirred to polymerize the monomer, thereby precipitating on the surface.

  In the above vapor deposition method, carbon black is used as a colorant, carbon black is 10 g, aluminum flakes (average particle size: 30 μm, average thickness: 1 μm) is 20 g, current supply to the electrode is 10 V, 40 A, and heat evaporation When the time was 60 minutes, carbon black was scattered and adhered to the aluminum flakes, and the exposed area ratio of the aluminum flakes was 50%.

  In the above immersion method and vapor deposition method, a coloring material and translucent beads such as acrylic beads may be mixed and adhered to the aluminum flakes so as to cover the entire surface. Even in this case, the coloring material is scattered and attached to the aluminum flakes, and the portion of the aluminum flakes to which the light-transmitting beads are attached is in a state where the aluminum flakes are optically exposed through the light-transmitting beads. The flakes can be called exposed colored flakes.

[Mixed colored flakes]
6 and 7 show a colored flake 22B as another example of the colored flake 22. FIG. In the colored flakes 22B, the surface of the aluminum flakes 25 is covered with two kinds of granular coloring materials 28 and 29 having different total light transmittances of visible light, and the entire aluminum flakes to which the coloring materials 28 and 29 are adhered are resin. It is covered with the coat layer 27. Two kinds of coloring materials 28 and 29 having different total light transmittances adhere to the surface of the aluminum flakes 25 as spots. Since these colored flakes 22B are mixed with a plurality of kinds of coloring materials, they are referred to as “mixed colored flakes” for convenience.

  This mixed colored flake 22B can also be prepared by the dipping method or the vapor deposition method. When adopting the dipping method, it is different from the case of exposed colored flakes in that multiple types of coloring materials are mixed with a silane coupling agent and a solvent and subjected to dispersion treatment with a ball mill. Colored flakes can be prepared. When the vapor deposition method is employed, mixed colored flakes can be prepared in the same manner except that a plurality of kinds of coloring materials are mixed and wrapped in a stainless steel mesh, which is different from the case of exposed colored flakes.

  In the dipping method, carbon black and aniline black, which have different total light transmittance, are used as coloring materials, carbon black 0.5g, aniline black 0.5g, silane coupling agent 0.5g, solvent (mineral split) ) And 10 g of aluminum flake paste (aluminum flake; average particle size: 30 μm, average thickness: 1 μm), carbon black and aniline black adhere to the flakes and occupy the surface of the aluminum flakes The area ratio of aniline black was 60%.

  In the vapor deposition method, carbon black and aniline black are used as coloring materials, carbon black is 15 g, aniline black is 15 g, aluminum flakes (average particle size: 30 μm, average thickness: 1 μm) is 20 g, and the electrode is energized. When the heating evaporation time was 60 minutes with 10V and 40A, carbon black and aniline black adhered to the aluminum flakes, and the area ratio of aniline black occupying the surface of the aluminum flakes was 50%.

  Here, the refractive index of carbon black is 1.8, and the refractive index of aniline black is 1.58. Since the total light transmittance is higher when the refractive index is smaller, the reflected light characteristics of the mixed colored flakes can be adjusted by controlling the occupation area ratio of the colorant having a different refractive index in the aluminum flakes.

<Light reflection characteristics of exposed colored flakes>
Regarding the exposed colored flakes, the influence of the exposed area ratio of the aluminum flakes and the colorant particle size on the light reflectance was investigated. The light reflectivity is a regular reflectivity (reflection angle 10 °) at an incident angle of 10 ° with respect to the perpendicular of the surface of the colored flakes, and the wavelength of the incident light is 630 nm.

  FIG. 8 shows a case using perylene red having a refractive index of 2.02 as a red pigment, and FIG. 9 shows a case using carbon black having a refractive index of 1.8 as a black pigment. In any case, the reflectivity increases as the exposed area ratio increases, and the reflectivity greatly decreases when the average particle size exceeds 200 nm.

<Effect of exposed area ratio of exposed colored flakes on FI value>
Two types of carbon black with an average particle diameter of 200 nm and carbon black with an average particle diameter of 400 nm are prepared as coloring materials, aluminum flakes are prepared as glitter flakes, and a plurality of types of exposed coloring with different exposed area ratios. Created flakes. Using these exposed colored flakes, a glitter layer was formed on the substrate, and a plurality of samples were formed on which a transparent clear layer was formed. The glitter layer was formed by spraying an acrylic base paint in which colored flakes were dispersed. The colored flakes were oriented substantially parallel to the surface of the glitter layer, and the substrate was not exposed between the individual colored flakes. The transparent clear layer was formed by spraying an acrylic clear paint.

  The obtained samples differ in the average particle diameter of the coloring material of the exposed colored flakes contained in the glitter layer and the exposed area ratio of the aluminum flakes. Then, the FI (flop index) value of each sample was measured.

  As shown in FIG. 10, the FI value is reflected light inclined by 45 ° from the regular reflection direction toward the incident direction when light is incident on the surface of the sample 31 at an angle inclined by 45 ° from the normal to the surface. Lightness index L * 45 ° of (45 ° reflected light), brightness index L * 15 ° of reflected light (15 ° reflected light) tilted 15 ° from the regular reflection direction to the incident direction side, and incident direction from the regular reflection direction Based on the lightness index L * 110 ° of the reflected light (110 ° reflected light) tilted 110 ° to the side, the value is obtained by the following equation.

FI = 2.69 × (L * 15 ° −L * 110 °) ^1.11 / L * 45 ° ^0.86
The measurement results are shown in FIG. In both cases where the average particle size is 200 nm and 400 nm, the FI value increases as the exposure area ratio increases from zero, and exposure occurs after the FI value reaches a peak near the exposure area ratio of 50% to 60%. The FI value tended to decrease as the area ratio increased.

  The FI value increases as the exposure area ratio increases from zero. It is recognized that the reflected light increases by 15 ° as the exposed area of the aluminum flakes increases. On the other hand, the FI value peaks at around the exposed area ratio of 50% to 60%, and then the FI value decreases as the exposed area ratio increases. When the exposure of the aluminum flakes becomes too large, the coloring material This is considered to be due to a decrease in the degree of shielding of 110 ° reflected light due to.

  Here, the degree of shielding of reflected light by the colorant will be examined. FIGS. 12A to 12D are diagrams for explaining that the degree of shielding of reflected light by the colorant varies depending on the reflection angle. Assuming that the colorants are all spherical and have a uniform particle size, glass balls were employed as a colorant model. A plurality of glass balls were arranged on the plate at substantially equal intervals so that the exposed area ratio of the plate was 40%. Then, the dip angle was changed, and the size of the plate looking through between the glass balls at each dip angle was examined by photographing. 12A shows a case with a depression angle of 20 ° (115 ° reflected light direction), FIG. 12B shows a case with a depression angle of 30 ° (105 ° reflected light direction), and FIG. FIG. 12 (d) shows a case with a depression angle of 90 ° (direction of 45 ° reflected light).

  According to FIG. 12, as the dip angle becomes smaller, the plate surface viewed from between the glass balls becomes smaller, and the plate becomes invisible at the dip angle of 20 ° (115 ° reflected light direction). The fact that the plate becomes harder to see as the dip angle becomes smaller can be considered by replacing it with colored flakes. For example, 110 ° reflected light from aluminum flakes is blocked by the coloring material, and the reflected light intensity is considerably reduced. Therefore, the FI value is large (the flip-flop property is strong).

  Thus, FIG. 12 shows a case where the exposed area ratio is 40%, but as the exposed area ratio increases, the degree of shielding of the reflected light by the colorant decreases accordingly. For this reason, as shown in FIG. 11, it is recognized that when the exposed area ratio exceeds 60%, the FI value tends to decrease. When the exposed area ratio is 100%, the FI value of the aluminum flake itself is obtained.

  In FIG. 11, when the average particle size is 200 nm, the FI value is larger than the FI value when the average particle size is 400 nm. The smaller the particle size, the easier the light passes through the colorant. This is because the diffuse reflection of light is weakened.

  According to the result of FIG. 11, in order to realize a large FI value, the exposed area ratio is set to 20% or more and 85% or less (FI value is 30 or more at an average particle size of 200 nm), and coloring is performed. It can be seen that it is preferable to reduce the average particle size of the material, for example, 300 nm or less.

<Light reflection characteristics of mixed colored flakes>
Regarding two types of colorant mixed type colored flakes, the area ratio of the colorant having a high total light transmittance (the area ratio of the colorant occupying the surface area of the aluminum flakes) and the particle size of the two kinds of colorants are the light reflectance. The effects on the The conditions for measuring the light reflectance are the same as those for the exposed colored flakes.

  FIG. 13 shows a case where carbon black having a refractive index of 1.8 is used as a coloring material having a low total light transmittance, and aniline black having a refractive index of 1.58 is used as a coloring material having a high total light transmittance. Also in this case, the reflectance increases as the area ratio of aniline black increases, and when the average particle size increases beyond 200 nm, the reflectance decreases greatly.

<Effects of coloring material area ratio of mixed colored flakes on FI value>
Prepare carbon black and aniline black each having an average particle diameter of 200 nm as colorants, and carbon black and aniline black each having an average particle diameter of 400 nm, and prepare aluminum flakes as glitter flakes. A plurality of types of carbon black / aniline black mixed colored flakes having different area ratios of aniline black were prepared. Using these exposed colored flakes, a glitter layer was formed on the substrate, and a plurality of samples were formed on which a transparent clear layer was formed. The glitter layer was formed by spraying an acrylic base paint in which colored flakes were dispersed. The colored flakes were oriented substantially parallel to the surface of the glitter layer, and the substrate was not exposed between the individual colored flakes. The transparent clear layer was formed by spraying an acrylic clear paint.

  In the obtained samples, the average particle diameter of the coloring material of the exposed colored flakes contained in the glittering layer and the area ratio of aniline black are different. Then, the FI value of each sample was measured.

  The measurement results are shown in FIG. In both cases where the average particle diameter is 200 nm and 400 nm, the FI value increases as the area ratio of aniline black increases from zero, and after the FI value peaks at an area ratio of 50% to 60%. The FI value tended to decrease as the area ratio increased.

  The FI value increases as the area ratio of aniline black increases from zero. This is because the reflected light from aluminum flakes increases as the area occupied by aniline black, which has high total light transmittance, increases. . On the other hand, the FI value peaks at an area ratio of about 50% to 60%, and thereafter the FI value decreases as the area ratio increases. When the area occupied by aniline black becomes too large, the aluminum flakes This is because the degree of shielding of the reflected light by carbon black decreases.

  Further, as in the case of the exposed colored flakes, when the average particle size is 200 nm, the FI value is larger than the FI value when it is 400 nm.

  According to the result of FIG. 14, in order to realize a large FI value, the area ratio of the colorant having a high total light transmittance is set to about 25% or more and 80% or less (the FI value is 30 at an average particle size of 200 nm). It is understood that it is preferable to reduce the average particle diameter of the colorant, for example, 300 nm or less.

  In addition, although the said embodiment is an example which uses a red pigment or a black pigment as a coloring material, this invention can also employ | adopt the coloring material of hues other than red and black.

11 Car body (steel plate)
DESCRIPTION OF SYMBOLS 12 Laminated coating film 13 Electrodeposition coating film 14 Colored underlayer 15 Glossy layer 16 Transparent clear layer 21 Pigment 22 Colored flake 22A Colored flake 22B Colored flake 25 Aluminum flake (glossy flake)
26 Colorant 27 Resin Coat Layer 28 Colorant (Low Total Light Transmittance)
29 Colorant (High total light transmittance)

Claims (9)

A laminated coating film comprising a glittering layer containing a glittering material,
The glitter layer contains, as the glitter material, colored flakes in which the surface of the glitter flake is covered with a plurality of kinds of coloring materials having different total light transmittance of visible light,
A multilayer coating film, wherein the plurality of kinds of coloring materials having different total light transmittances are adhered to the surface of the glitter flakes in spots. In claim 1 ,
As the colorant, it comprises two kinds of colorants having different total light transmittances,
The laminated coating film, wherein an area ratio of the coloring material having a high total light transmittance in the colored flakes is from 25% to 80%. In claim 1 or claim 2 ,
The above-mentioned colorant is granular and has an average particle diameter of 300 nm or less. In any one of Claim 1 thru | or 3 ,
A laminated coating film, wherein the glitter flakes are aluminum flakes. In any one of Claims 1 thru | or 4 ,
The above-mentioned colorant is a dark color system having a Munsell brightness of 5 or less . In claim 5 ,
A laminated coating film, wherein the colorant is black. In any one of Claims 1 thru | or 6 ,
The glitter layer is laminated on a colored underlayer of the same color as the colorant ,
The same color system means that, in the case of an achromatic color, the lightness difference in the Munsell value of the comparison target color is 5.0 or less, and in the case of a chromatic color, the Munsell hue circle is divided into 100 and the comparison target color One of the hues of the above is the reference (0 position), and when the counterclockwise +50 and clockwise -50 are displayed, the other hue of the comparison target color is in the hue range of ± 10. film. In any one of Claims 1 thru | or 7 ,
A laminated coating film, wherein a transparent clear layer is directly laminated on the glitter layer. A coated article comprising the laminated coating film according to any one of claims 1 to 8 .