JP2003201445A - Hologramic metallic coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic coating material forming a metallic coated film with new appearance enabling a hilight part to have excellent luster color, and two or more colors in a rainbow pattern at a shade part to be seen clear without causing whitely opaque state by the light interference, and having good appearance quality, and to provide a method for forming a double layered coated film using the metallic coating material. <P>SOLUTION: This hologramic metallic coating material contains alumina flakes covered with magnesium fluoride, and alumina flakes covered with a metal oxide as essential components. The method for forming the double layered coated film comprises using the hologramic coating material as a metallic coating material when forming the double layered coated film by coating the metallic coating material and a clear coating material. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a novel design property in which a highlight portion has excellent brilliance, and a shade portion allows a plurality of colors to be clearly seen without a rainbow-like striped pattern becoming white and cloudy. And a method for forming a multi-layer coating film using the same, which forms a metallic coating film having excellent appearance quality.

[0002]

2. Description of the Related Art Metallic paints for forming a coating film showing a rainbow-like striped pattern are already known. For example, a very fine groove (usually a pitch width of 0.7 to 1 μm) is formed by embossing on the surface of a light reflecting substrate such as a vapor-deposited aluminum sheet.
m, pitch height 0.1 to 0.2 μm), and the surface of which is covered with a transparent resin film has a size of 20 to 150.
There is known a metallic paint containing a hologram pigment obtained by cutting into a thickness of 5 μm and a thickness of 5 to 10 μm.

In general, when a coating film containing a holographic pigment is irradiated with light, a diffraction phenomenon of light occurs due to a groove having the same wavelength as the wavelength of light on the substrate, so that the shade region on the opposite side of the incident angle is exposed. A light dispersion phenomenon due to light diffraction is observed, which causes a rainbow-like striped pattern to be obtained as a light design effect. More specifically, when light is incident on the coating film from the direction of -45 degrees, +4 on the opposite side.
At around 5 degrees, specular reflection light from which the incident light source is visible appears. If the angle is 0 degree, ± 10 degrees in the vicinity of 0 degree ~
Approximately 30 degrees is called the highlight color, and ± 5 outside of it
Iridescent light can be seen as a design effect in the shade region of 0 to about 60 degrees.

The appearance angle at which the rainbow appears can be calculated by the following formula.

D × sin θ × m = m × λ (where d is the pitch width, θ is the diffraction angle, and m is the diffraction order (m = 1, 2 ,.
(N order), λ is the wavelength of light) Usually, the 1st order diffracted light has the highest intensity and good visibility, so m is considered to be 1. For example, visible light (400 ~
If the representative light is 560 nm at the center of (700 nm), the diffraction angle θ is 59 degrees when the pitch width d = 0.65 μm, which is theoretically and phenomenologically due to the light dispersion phenomenon due to diffraction in the shade region. I can see a rainbow.

Flake pigments such as mica pigments, aluminum flakes, and plate-shaped iron oxide (PIO) exhibit interference colors in the mica pigments in the highlight region, metallic flakes in the aluminum flakes and PIO, and dark shades. However, since the above-mentioned holographic pigment is colored by diffraction, metallic highlights from the aluminum vapor deposition film of the base material and rainbows are observed in the shade area in the highlight portion.

However, the above-mentioned hologram pigment is formed by cutting a sheet in which both surfaces of vapor-deposited aluminum are coated with a resin film into squares by cutting.
Since the thickness is large (usually 5 to 10 μm) and the length of one side is also long (20 to 100 μm), when a coating material containing such a large particle hologram pigment is applied, a part of the particle protrudes from the coated surface. There is (cue). Further, even if a clear paint is applied on the coated surface, a flickering phenomenon may occur at the cue portion and the appearance of the coating film may be deteriorated. In addition, this cueing may deteriorate the finish appearance such as gloss and smoothness of the clear coating film. In addition, there is a defect that the rainbow color in the shade portion of the coating film containing the hologram pigment becomes cloudy and unclear.

It is also possible to form a multilayer coating film by applying a clear paint containing the above-mentioned hologram pigment on the coating surface of a metallic base paint containing aluminum flake or mica flake pigment, and then applying a top clear paint. It has been proposed (JP 2000-33334). However, the thickness of the hologram pigment used in this method is large, and the standard film thickness (15
˜20 μm), the hologram pigment is not sufficiently covered with the resin, and the hologram pigment has a defect that it pops out from the coated surface (heading) and reflects light flickeringly at that portion to cause poor finishability. Further, the metallic base coating film containing the mica pigment is said to be able to see the interference color due to the mica pigment in the highlight region and the rainbow in which the light from the hologram pigment is dispersed in the shade region. Due to the diffusion of light by the mica pigment, the rainbow becomes cloudy in white, resulting in a marked loss of design.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to eliminate the above-mentioned defects, the highlight portion has excellent brilliance, and the shade portion has a plurality of rainbow-like striped patterns that are clouded white due to light interference. Form a coating film with a new design that can be seen clearly without forming a clear coating film on the coated surface, and form a metallic coating film with excellent finished appearance such as smoothness. The objective is to develop a metallic paint that can be used and a method for forming a multilayer coating film using the same.

As a result of intensive studies, aluminum flakes coated with magnesium fluffer were used as hologram pigments for forming a coating film in which a plurality of colors look like a rainbow-like stripe pattern due to light interference in the shade portion.
Further, they have found that the object can be achieved by using alumina flakes coated with a metal oxide together, and have completed the present invention.

That is, the present invention comprises a holographic metallic paint (hereinafter, referred to as the following), which contains aluminum flakes whose surface is coated with magnesium fluoride and alumina flakes whose surface is coated with a metal oxide as essential components. "This paint") is provided.

The present invention further provides a method for forming a multi-layer coating film, which comprises using the above-mentioned coating material as a metallic paint when the metal coating material and the clear coating material are applied to form the multi-layer coating film. Hereinafter, the "present paint") is provided.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The "aluminum flakes whose surface is coated with magnesium fluoride" (hereinafter, abbreviated as "FMg-coated aluminum flakes") used in the present coating has excellent glitter in the highlight portion and has a shade. It is a holographic pigment that forms a new design coating film in which a plurality of colors become striped like a rainbow due to light interference and can be seen clearly.

The FMg-coated aluminum flake is a flake pigment in which both sides of the aluminum flake are coated with magnesium fluoride (MgF ₂ ). For example, a plastic film having fine grooves formed on the surface by embossing or the like is placed in a vacuum container. It is obtained by depositing magnesium fluoride, aluminum, and magnesium fluoride in this order on the film surface to form at least three vapor deposition layers, then peeling the vapor deposition layers from the film and crushing. be able to. It is preferable that the fine flake particles have a thickness of 3 μm or less, preferably 0.1 to 1 μm, and a side length (or diameter) of 30 μm or less, preferably 5 to 20 μm.

Magnesium fluoride (refractive index 1.38,
Since the layer having a melting point of 1248 ° C. and a boiling point of 2260 ° C. is transparent and the vapor deposition film thickness can be arbitrarily controlled in nanometer units, it is easy to reduce the thickness of the coating on the aluminum surface. Further, since magnesium fluoride itself is an inorganic substance, it can be easily crushed with rigidity and can be made into any size, so that the particle size distribution can be controlled narrowly. The holographic pigment, which has been conventionally used by coating both sides of vapor-deposited aluminum with plastic films, cannot be thinned as a reinforcing plastic film and has plasticity, so it should be crushed to a small particle size and narrow distribution. Was difficult.

Since a rainbow color is generated in the shaded area due to the dispersion of light due to the diffraction of light by the hologram pigment, in the present coating material, the alumina flakes coated with metal oxide (hereinafter , "Metal oxide-coated alumina flakes") is used as an essential component, and aluminum flakes and uncoated alumina flakes can be used in combination.

The metal oxide-coated alumina flakes are pigments obtained by coating the surface of the alumina flakes with a metal oxide, and the average particle diameter of the metal oxide-coated alumina flakes is 2.
It is preferably in the range of -50 μm, particularly 5-20 μm. The metal oxide coating the surface of the alumina flakes is preferably titanium dioxide, iron monoxide or diiron trioxide, and the coating thickness of the metal oxide is 0.01 to 1 μm, particularly 0.05 to
0.5 μm is preferable. The metal oxide-coated alumina flakes have a bright feeling, are light-transmissive, and have an interference effect due to the metal oxide layer.

The alumina flakes used to prepare the metal oxide coated alumina flakes are aluminum oxide (Al
₂ O ₃ ), which has a flaky shape and a thickness of 0.
It is preferable that the length is 1 to 1.0 μm, particularly 0.3 to 0.7 μm, and the longitudinal dimension is 2 to 50 μm, particularly 5 to 20 μm. This product can be prepared, for example, by crystal growth by the electric melting method, and the particle size distribution can be narrowed, so there are few diffuse light components, there is almost no white turbidity in the shade part, and white blur occurs. Can also be prevented. Also, since the surface is smooth due to crystal growth, the intensity of the light reflected there is large, and the glittering and glittering feeling is strong, and when the surface is coated with titanium oxide, the thin film interference of the titanium oxide layer causes Interference light with high saturation can be obtained.

Among the metal oxide-coated alumina flakes, the alumina flakes coated with titanium oxide have good transparency, while the iron oxide coating is translucent, so that they all have weak hiding power, so that they are used for coloring pigments, aluminum flakes, etc. It is preferable to use a metallic pigment together. In the case of deep-colored coating with low lightness, it is preferable to use a light-absorbing pigment such as carbon black, a phthalocyanine-based pigment, or a perylene pigment as a coloring pigment. On the other hand, for high-brightness coating color, it is preferable to use aluminum flake having a hiding power in addition to the color pigment. In this case, the highlight is metal reflected light from the aluminum flake and the metal oxide coated alumina. Interfering light from the flakes is obtained and the shade may be dark with aluminum flakes.

This coating material is aluminum flakes coated with magnesium fluoride (FMg-coated aluminum flakes).
And a hologram metallic paint characterized by containing, as an essential component, alumina flakes coated with a metal oxide (alumina flakes coated with a metal oxide).
Specifically, it is a liquid paint obtained by mixing and dispersing FMg-coated aluminum flakes, metal oxide-coated alumina flakes and a thermosetting resin composition in an organic solvent, and further, if necessary, an aluminum flake pigment, a coloring pigment, a light pigment. Interfering pigments, extender pigments and the like can be included.

The thermosetting resin composition is, for example, one or more functional groups selected from a hydroxyl group, a carboxyl group, a silicon-containing group, an epoxy group, an optionally blocked isocyanate group and the like. One or more base resins selected from acrylic resins, vinyl resins, polyester resins, alkyd resins, urethane resins and the like, and melamine resins, urea resins, which may be blocked with these functional groups, even if blocked A mixture of one or more cross-linking agents selected from good polyisocyanate compounds, carboxyl group-containing compounds, epoxy group-containing compounds and the like can be mentioned. The ratio of the base resin to the crosslinking agent is 50 to 50 based on the total weight of both components.
90%, in particular 65 to 85%, 50 to 10%, in particular 35 to 15%, are suitable crosslinkers.

As the aluminum flake pigment, a usual metallic aluminum flake metallic pigment can be used,
The major axis is 10 to 40 μm in major axis and 5 to 30 μ in minor axis.
m and thickness of 0.3 to 2.0 μm are suitable.

Achromatic and chromatic color pigments can be used, for example, titanium oxide, micro titanium oxide,
Inorganic pigments such as zinc white, carbon black, cadmium red, molybdenum red, molybdenum red, chrome ero, chromium oxide, Prussian blue, cobalt blue and the like; azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, slene pigments, perylene Examples include organic pigments such as pigments. These may be used alone or in combination of two or more.

Examples of the light-interfering pigment include mica, titanium oxide-coated mica, iron oxide-coated mica, and their sizes are 10-40 μm in major axis and 5-3 in minor axis.
Those having a thickness of 0 μm and a thickness of 0.3 to 2.0 μm are suitable.

Examples of the organic solvent include hydrocarbon solvents such as hexane, heptane, xylene, toluene and cyclohexane; ester solvents such as methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate and diethylene glycol monomethyl ether acetate; Ether system such as isopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether; alcohol system such as ethyl alcohol, butyl alcohol, hexyl alcohol; methyl isobutyl ketone, methyl ethyl ketone, isophorone , Ketone-based compounds such as acetophenone; and the like.

In the present coating composition, the composition ratio of the above-mentioned components is not particularly limited and can be arbitrarily selected according to the purpose.
For example, 1 to 10 parts by weight of FMg-coated aluminum flakes, particularly 3 to 7 parts by weight, and 1 to 1 part of metal oxide-coated alumina flakes per 100 parts by weight (solid content) of the thermosetting resin composition.
-15 parts by weight, particularly 1-10 parts by weight is preferred. Further, per 100 parts by weight (solid content) of the thermosetting resin composition, the aluminum flake pigment is 20 parts by weight or less, particularly 3 to 10 parts by weight, and the color pigment is 20 parts by weight or less, particularly 1 to 1 part.
0 parts by weight, the light interference pigment is 20 parts by weight or less, particularly 1 to 1
A range of 0 parts by weight is suitable. The ratio of the FMg-coated aluminum flakes to the metal oxide-coated alumina flakes is 10 to 70 for the former, based on the total weight of both pigments.
%, Especially 20-50%, the latter 90-30%, especially 80
It is preferably within the range of 50%.

The present coating composition can be prepared by mixing and dispersing the above-mentioned components in an organic solvent, and the solid content at the coating is 20 to 60% by weight, preferably 25 to 50% by weight.
Then, the concealment film thickness is 15 μm or more, preferably 20 to 50 μm.
m, viscosity 10 to 30 seconds / fod cup # 4/20 ° C
It is preferable to adjust it to.

The concealed film thickness is JISK54007.2.
(2) A black-and-white checkered masking power test paper specified in (f) is attached to a mild steel plate, the coating material (A) is obliquely coated so that the film thickness continuously changes, and after drying and curing, a diffusing daytime is applied. It is a value obtained by visually observing the coated surface under light and measuring the minimum film thickness (μm) at which the black and white checkered pattern of the hiding power test paper becomes invisible with an electromagnetic film thickness meter.

This paint is applied directly to a metal or plastic object to be coated such as an automobile outer panel, or by applying an undercoat paint such as a cationic electrodeposition paint or an ordinary middle coat paint (optional),
Applying a coating on the cured product with an air sprayer, an airless sprayer, or an electrostatic coating machine so that the film thickness based on the cured coating film is a concealing film thickness or more, for example, 15 or more, 20 to 50 μm. You can This coating is 100-160
Crosslinking and curing can be carried out by heating at ℃, preferably 120 to 150 ℃ for about 10 to 40 minutes.

The present invention relates to a method for forming a multi-layer coating film, characterized in that, when a metallic coating material and a clear coating material are applied to form a multi-layer coating film, the above-mentioned main coating material is used as a metallic coating material.

In the present method, the above-mentioned present paint can be used as the metallic paint.

As the clear paint, a known paint that forms a colorless transparent or colored transparent coating film can be used. Specifically, it is a liquid coating material prepared by mixing and dispersing a thermosetting resin composition in an organic solvent, and may further contain a coloring pigment, an extender pigment, etc., if necessary.

The thermosetting resin composition is, for example, one or more functional groups selected from a hydroxyl group, a carboxyl group, a silicon-containing group, an epoxy group, an optionally blocked isocyanate group and the like. One or more base resins selected from acrylic resins, vinyl resins, polyester resins, alkyd resins, urethane resins and the like, and melamine resins, urea resins, which may be blocked with these functional groups, even if blocked A mixture of one or more cross-linking agents selected from good polyisocyanate compounds, carboxyl group-containing compounds, epoxy group-containing compounds and the like can be mentioned. The ratio of the base resin to the crosslinking agent is 50 to 50 based on the total weight of both components.
90%, in particular 65 to 85%, 50 to 10%, in particular 35 to 15%, are suitable crosslinkers.

As the organic solvent and the coloring pigment, the pigments exemplified in the above paint of the present invention can be preferably used.

The clear paint can be prepared by mixing and dispersing the above-mentioned components in an organic solvent. The solid content at the time of coating is 20 to 60% by weight, preferably 25 to 50% by weight, and the viscosity is 10 to 30 seconds. / Food cup # 4/20 ℃
It is preferable to adjust it to.

The clear coating is applied to the uncured or cured coating surface of the main coating applied to the object to be coated with an air sprayer, an airless sprayer, an electrostatic coating machine or the like, and the film thickness based on the cured coating film is 20 or more, It can be coated preferably to 30 to 80 μm. Then, heat at 100 to 160 ° C, preferably 120 to 150 ° C for about 10 to 40 minutes,
The present method can be achieved by crosslinking and curing the clear coating alone or the coating composition and the multilayer coating composition of the clear coating composition.

In this method, it is also possible to apply a top coat paint such as a solid color paint, a metallic paint or a light interference paint in advance prior to the painting of the present paint, and to apply the present paint to these coated surfaces. Is. Further, it is also possible to apply a clear paint as described above and, after curing or not curing the coating film, further apply a clear paint having excellent acid resistance and scratch resistance.

[0038]

EFFECTS OF THE INVENTION The highlight portion has a good brilliance, and the shade portion is a coating film having a novel design in which a plurality of colors can be clearly seen without turbidity of white stripes such as rainbow due to light interference. We were able to develop a metallic paint that formed. Moreover, it was possible to develop a method for forming a metallic multi-layered coating film capable of forming a metallic coating film having a good finish appearance such as smoothness without the gloss of the clear coating film coated on the metallic coating surface. .

[0039]

EXAMPLES Examples and comparative examples relating to the present invention will be described below. All parts and% are based on parts by weight. The compounding amount is a solid content. Coating thickness is for cured coatings.

1. Sample preparation 1) Base metallic paint a): Hydroxyl group-containing acrylic resin (hydroxyl value 120, acid value 5, number average molecule 13000) 75 parts, butyl etherified melamine resin 25 parts (number average molecular weight 1000), blue pigment ( Note 1) 3 parts, black pigment (Note 2) 1 part, interference blue mica (Note 3) 7 parts, interference blue synthetic mica (Note 4) 5 parts, interference blue alumina flake (Note 5) 7 parts, aluminum flake ( Note 6) 5
Parts are organic solvents (ethyl acetate / xylene = 1/1 weight ratio)
To obtain a colored metallic paint (a) having a solid content of 50%, a viscosity of 13 seconds / fod cup # 4/20 ° C., and a hiding film thickness of 15 μm.

(Note 1) Blue pigment: Phthalocyanic pigment (Note 2) Black pigment: Carbon black (Note 3) Interference blue mica: Merck Japan KK, trade name, "225W2", thickness 0.8 μm, Average particle size 19.
6 μm (Note 4) Interference blue synthetic mica: manufactured by Nippon Koken Co., Ltd., trade name, “Ultimica SB-100SO”, thickness 0.
8 μm, average particle size 12.7 μm (Note 5) Interference blue alumina flakes: Merck Japan KK, trade name, “Xirallic Blue”,
Thickness 0.9 μm, average particle size 17.6 μm (Note 6) Aluminum flakes: manufactured by Toyo Aluminum Co., Ltd.,
Product name, "7680NS", thickness 0.3 μm, average particle size 13.1 μm 2) Clear paint a) Hydroxyl group-containing acrylic resin (hydroxyl value 85, acid value 3,
75 parts of number average molecular weight 12000) and 25 parts of butyl etherified melamine resin (number average molecular weight 1000) are mixed and dispersed in an organic solvent (ethyl acetate / xylene = 1/1 weight ratio) to give a solid content of 40% and a viscosity. A clear coating (a) of 20 seconds / fod cup # 4/20 ° C. was obtained.

2. Examples and Comparative Examples Example 1 75 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 120, acid value 5, number average molecule 13000), butyl etherified melamine resin 25 parts (number average molecular weight 1000), hologram pigment (Note 7). 5 parts, blue pigment (Note 1) 4 parts, black pigment (Note 2)
1 part and 5 parts of interference blue alumina flakes (Note 5) were mixed and dispersed in an organic solvent (ethyl acetate / xylene = 1/1 weight ratio) to give a solid content of 50%, a viscosity of 13 seconds / fod cup # 4 / A hologram paint (a) having a temperature of 20 ° C. was obtained. The concealed film thickness is 15 μm.

(Note 7) Hologram pigment: manufactured by US Flex Products Co., Ltd., trade name, "SpectraFlai"
r ”, thickness 2 μm, average particle size 20 μm, aluminum flakes coated with magnesium fluoride.

Example 2 75 parts of hydroxyl group-containing acrylic resin (hydroxyl value 120, acid value 5, number average molecule 13000), butyl etherified melamine resin 25 parts (number average molecular weight 1000), hologram pigment (Note 7) 5 parts , Blue pigment (Note 1) 2 parts, black pigment (Note 2)
0.5 parts, 6 parts of aluminum flakes (Note 6) and 5 parts of interference blue alumina flakes (Note 5) were mixed and dispersed in an organic solvent (ethyl acetate / xylene = 1/1 weight ratio) to obtain a solid content of 50.
%, A viscosity of 13 seconds / fod cup # 4/20 ° C. to obtain a hologram coating (b). The concealed film thickness is 15 μm.

Comparative Example 1 Hydroxyl group-containing acrylic resin (hydroxyl value 120, acid value 5, number average molecule 13000) 75 parts, butyl etherified melamine resin 25 parts (number average molecular weight 1000), hologram pigment (Note 7) 5 parts , Blue pigment (Note 1) 4 parts, black pigment (Note 2)
1 part and 5 parts of blue interference mica (Note 3) were mixed and dispersed in an organic solvent (ethyl acetate / xylene = 1/1 weight ratio) to obtain a solid content of 50%, a viscosity of 13 seconds / fod cup # 4/20. ℃
To obtain the hologram paint (c). The concealed film thickness is 15 μm.

Comparative Example 2 75 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 120, acid value 5, number average molecule 13000), butyl etherified melamine resin 25 parts (number average molecular weight 1000), hologram pigment (Note 7) 5 parts , Blue pigment (Note 1) 4 parts, black pigment (Note 2)
1 part and 5 parts of interference blue synthetic mica (Note 4) were mixed and dispersed in an organic solvent (ethyl acetate / xylene = 1/1 weight ratio) to give a solid content of 50%, viscosity of 13 seconds / foad cup # 4 / Two
The hologram paint (d) of 0 degreeC was obtained. Concealment film thickness is 15μ
m.

Comparative Example 3 Hydroxyl group-containing acrylic resin (hydroxyl value 120, acid value 5, number average molecule 13000) 75 parts, butyl etherified melamine resin 25 parts (number average molecular weight 1000), hologram pigment (Note 7) 5 parts , Blue pigment (Note 1) 2 parts, black pigment (Note 2)
0.5 parts, 6 parts of aluminum flakes (Note 6), and 5 parts of blue interference mica were mixed and dispersed in an organic solvent (ethyl acetate / xylene = 1/1 weight ratio) to obtain a solid content of 50% and a viscosity of 13 seconds /
A hologram paint (e) having a hood cup of 4/20 ° C. was obtained. The concealed film thickness is 15 μm.

Comparative Example 4 75 parts of hydroxyl group-containing acrylic resin (hydroxyl value 120, acid value 5, number average molecule 13,000), butyl etherified melamine resin 25 parts (number average molecular weight 1000), hologram pigment (Note 8) 5 parts , Blue pigment (Note 1) 4 parts, black pigment (Note 2)
1 part and 5 parts of interference blue alumina flakes (Note 5) were mixed and dispersed in an organic solvent (ethyl acetate / xylene = 1/1 weight ratio) to give a solid content of 50%, a viscosity of 13 seconds / fod cup # 4 / A hologram paint (f) at 20 ° C was obtained. The concealed film thickness is 15 μm.

(Note 8) Hologram pigment: manufactured by Diamond Industry Co., Ltd., trade name, "Diamond Hologram HG-S5EP", very fine grooves are formed on the surface of a vapor-deposited aluminum sheet by embossing, and the surface is covered with a transparent resin film. And then cut. The size is 110 μm and the thickness is 5 μm.

Examples 3 to 5 and Comparative Examples 5 to 9 Metal plate (size 100 × 80 × 0.8 mm) and cationic electrodeposition coating (“Electron 9200”, manufactured by Kansai Paint Co., Ltd., trade name, epoxy resin type) In addition, the base metallic paint a) is air-sprayed onto an object to be coated and cured by coating an intermediate coating (“ES primer-TP37”, manufactured by Kansai Paint Co., Ltd., trade name, polyester resin / melamine resin type).
After coating, the mixture was left standing at room temperature for 5 minutes, and then cured by heating at 140 ° C. for 30 minutes. Next, apply the hologram paint in the same manner as above, leave it at room temperature for 5 minutes, and then apply the clear paint (a),
After left at room temperature for 5 minutes, the two-layer coating film was simultaneously cured by heating at 140 ° C. for 30 minutes to obtain a three-layer composite coating film (3C
2B).

A hologram paint was applied to the above-mentioned object in the same manner as above, left at room temperature for 5 minutes, then a clear paint (a) was applied, left at room temperature for 5 minutes, and then heated at 140 ° C. for 30 minutes. The two-layer coating film was simultaneously cured to obtain a two-layer coating film (2
C1B).

Table 1 shows these coating steps and the design performance of the obtained coating film.

[0053]

[Table 1] The test method is as follows.

Y15 (Highlight brightness feeling): The brightness value is a portable gonio-spectrophotometer "MA68" manufactured by X-Rite, Inc. in the United States.
After measuring the spectral reflectance of 15 degrees on the highlight side (the angle is displayed as an opening angle with the specular reflection light as 0 degree) measured by "-2", J
The tristimulus values XYZ were obtained using IS Z8701, and of these, the Y value representing the brightness was defined as the Y15 value, which was the value representing the sense of brightness. The larger the value is, the larger the brightness value is, and the higher the brightness is by visual observation.

C * 15 (saturation of highlight): "MA6
Saturation of 15 degrees on the highlight side measured with 8-2 ”is L * c
* H * A value represented by the saturation c * of the color system. The larger the value, the higher the saturation and the better.

L * 75 (shade lightness): "MA68
The lightness of 75 degrees on the shade side measured with "-2" is L * a * b
* Value expressed by lightness L * of the color system. The smaller the value, the better the whiteness in the shade is.

Intensity of rainbow in shade area: The intensity of rainbow coloring of diffracted light in the shade area was visually evaluated. ○ indicates a strong rainbow color, △ indicates a rainbow color whose intensity is slightly smaller than that of ○,
× indicates that the color of the rainbow is small.

Glitter feeling: In the highlight region, the microscopic glitter feeling of the light from the glitter material was visually evaluated. ◯ indicates that the brightness of the glittering points is high and good, Δ indicates that the glitter feeling is inferior, and x indicates that the glitter feeling is further inferior.

Shade whiteness: The blackness in the shade area was visually evaluated. ○ is the impression that it becomes black and the color is tight,
Δ indicates that there is a slight white blur, and x indicates that the white blur is large.

Finished appearance: The presence or absence of the flicker phenomenon due to the reflection of light from the convex portion of the clear coated surface was visually observed. ○: smooth with no protrusions, no flicker phenomenon observed, △: some protrusions were observed, some flicker phenomenon occurred, ×: some ridges were observed, some flicker phenomenon occurred Show.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4D075 AE03 CA02 CA33 CA44 CA48                       CB04 CB06 CB08 CB13 DA06                       DB01 DB31 DC11 EA07 EA43                       EB22 EB32 EB35 EB36 EB38                       EB45 EC02 EC05 EC10 EC23                 4J038 CF001 CG001 DA142 DA162                       DD121 DG001 DG231 GA06                       GA07 HA066 HA166 KA03                       KA08 NA19

Claims (2)

[Claims] 1. A holographic metallic paint comprising, as essential components, aluminum flakes coated with magnesium fluoride and alumina flakes coated with a metal oxide. 2. When forming a multi-layer coating film by applying a metallic paint or a clear paint, the holographic metallic paint according to claim 1 is used as the metallic paint, thereby forming a multi-layer coating film. Method.