JPH09323064A - Formation of bright coating film and coated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a bright coating film excellent in glittering brightness due to multiple reflection and exhibiting a three- dimensional brightness and to furnish a coated material. SOLUTION: A base coating film contg. a brightener is formed on a base material to be coated. Subsequently, at least one layer of a brightener-contg. clear coating film is formed which contg. 0.005-0.1 pts.wt. per 100 pts.wt. of resin solid component of at least one kind of brightener among an aluminum flake pigment having 20±+5μm average grain diameter (D50 ), 0.5-1.5μm grain average thickness and >=2.5 gradient (n) in the Rosin-Rammler diagram or a syntheticmica pigment coated with a metal oxide. Then a material coated by this film forming method is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the formation of a glittering metallic coating film which gives a strong glittering feeling and a three-dimensional glittering feeling suitable for industrial coating, for example, for automobiles, bicycles, home electric appliances and parts thereof. A method and a coated article.

[0002]

2. Description of the Related Art A metallic paint containing aluminum powder or mica powder has been conventionally used as a glittering paint for forming a metallic coating film having metallic luster, for example, JP-A-50-89426. Is a transparent paint containing one or more powders selected from aluminum powder having a particle size of 5 to 40 μm, titanium dioxide-coated mica powder, copper powder and mica powder, and a resin solid content of 100.
A transparent metallic coating composition prepared by blending 0.05 to 5 parts by weight with respect to parts by weight is disclosed in Japanese Unexamined Patent Publication No. Sho 50-89435, in which solid enamel is applied onto a substrate which has been subjected to a base treatment, and then A metallic finish coating method is disclosed in which a clear coating containing either aluminum powder, mica powder or titanium dioxide coated mica powder is applied.

Further, JP-A-3-270768 discloses a transparent or colored metallic coating layer containing 0.1 to 30 parts by weight of a glittering material on the surface of an article to be coated and a metallic coating layer. At least two transparent or colored metallic coating layers containing 0.1 to 30 parts by weight of a glittering material which differs from the glittering material used in at least one of type, particle size and content are laminated. Metallic coating structures have been proposed.

However, in these prior arts, since no consideration is given to the particle size characteristics of the glittering material used, for example, when the particle size of aluminum powder or mica is small, a turbid feeling or a glittering phenomenon occurs. The feeling is lowered, and a glittering feeling cannot be obtained. If the particle size is large, the luster of the luster material becomes too strong,
There are drawbacks such as giving a feeling of foreign matter such as dust. Further, when the amount of the glittering material added is 0.1 parts by weight or more, the glittering feeling is improved, but there is a drawback that the feeling of foreign matter is increased and the color tone is lowered.

Japanese Unexamined Patent Publication (Kokai) No. 52-107039 discloses a metallic coating method in which a metallic paint is applied to an object to be coated, and then a clear paint is applied wet-on-wet, in which aluminum powder is mixed with aluminum powder. It is disclosed that a clear paint is used and the particle size of the aluminum powder mixed in the clear paint is equal to or larger than the particle size of the aluminum powder in the metallic paint. However, by specifying that the particle diameter of the aluminum powder in the clear paint is equal to or larger than that of the aluminum powder in the metallic paint, it is an effect of further increasing the brightness while maintaining the hue of the metallic paint. It is not possible to obtain a glittering sensation and a three-dimensional sensation due to multi-directional reflection due to the uniform particle size distribution of the aluminum flake pigment in the clear paint.

Further, in Japanese Patent Application Laid-Open No. 2-160079, a first metallic coating film containing aluminum powder formed on the surface of an object to be coated, and a metallic luster layer formed on the surface of the first metallic coating film are provided. A metallic coating film has been proposed which is composed of a second metallic coating film containing scaly glass powder and a clear coating film formed on the surface of the second metallic coating film. However, the glass flake powder is expensive and has a drawback that it tends to become cloudy and the luster is deteriorated.

[0007]

In general, the glittering material in the coating film is easy to be arranged in parallel and oriented so as to be stacked on the vehicle. Therefore, when the glittering material in the form of flakes or foil is used, it is three-dimensional. There is a problem that it is difficult to obtain a bright feeling.

The present inventors have conducted research to solve these problems, and as a result, formed a base coating film containing a luster on a base coating film formed on the surface of a base material to be coated, and By using an aluminum flake pigment having a specific range of particle properties and a synthetic mica powder pigment coated with a metal oxide as a bright material for a clear coating containing a bright material to be formed on It was found that a coating film having a strong feeling and a high brilliance can be formed. Also, since the addition amount of the glitter material is small, the glitter material is not arranged in a layer in the coating film, but is randomly oriented and reflected in multiple directions, and the viewing angle is slightly changed, resulting in a glittering feeling and depth. It was found that a three-dimensional color feeling was developed.

The present invention was developed on the basis of these findings, and its purpose is to use an aluminum flake pigment and a synthetic mica powder pigment coated with a metal oxide as a glittering material, and to provide a strong glittering feeling and a three-dimensional color feeling. It is to provide a method for forming a glittering coating film and a coated article capable of forming an excellent glittering coating film having

[0010]

Means for Solving the Problems The method for forming a glittering coating film according to the present invention for achieving the above-mentioned object is described in the following (1) to
The structural feature is that the coating film forming step (2) is sequentially performed. (1) A step of forming a glittering material-containing base coating film on a substrate to be coated. (2) At least one glittering material of the following (A) or (B) is added to 0.005 to 100 parts by weight of resin solid content. Step of forming at least one clear coating film containing a bright material containing less than 0.1 part by weight (A) Average particle diameter (D ₅₀ ) is 20 ± 5 μm, average particle thickness is 0.5 to 1.5 μm, rosin- Aluminum flake pigment having a gradient n of 2.5 or more in Lambler diagram (B) Synthetic mica powder pigment coated with metal oxide. Furthermore, the coated article according to the present invention is coated by the above-mentioned method for forming a glittering coating film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate to be coated according to the present invention includes, for example, metals including iron, aluminum, copper or alloys thereof, inorganic materials such as glass, cement and concrete, Plastic materials such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyamide, polyacryl, polyester, ethylene-polyvinyl alcohol copolymer, vinyl chloride resin, vinylidene chloride resin, polycarbonate, polyurethane and various FRP. , Wood, fiber materials and the like. It is optional to perform appropriate undercoating or precoating treatment on the substrate to be coated in advance. After forming a colored undercoat on these coated substrates, a glitter material-containing base coating film forming step and a glitter material-containing clear coating film forming step are sequentially performed. Although the coating can be performed directly on the substrate to be coated, for example, in automobile coating, etc., usually, after surface chemical conversion treatment, an undercoat with an electrodeposition paint or the like, an intermediate coating (polyester / melamine-based) coating,
It is preferable to apply the coating after the coating film is cured.

(1) Glitter-containing base coating film forming step: This step is for forming a colored coating film containing a glittering material.
This is a process of forming a metallic coating film and a pearl coating film.

[Metallic Coating] One or more of an aluminum flake pigment, an interference mica pigment, a plate-shaped synthetic iron oxide crystal pigment, and a metal-plated mica pigment are used as a glittering material.
Inorganic system commonly used in general paints to achieve the desired hue,
A colored metallic coating film is formed by using various organic color pigments together. The vehicle resin is at least one thermosetting resin selected from acrylic resin, polyester resin, alkyd resin, fluororesin, polycarbonate resin and modified resins thereof, and amino resin and / or (block) polyisocyanate compound. A mixture with the crosslinking agent of is used. These resins are not limited to one type, but 2
It is also possible to use a combination of two or more species. In addition,
A two-component polyurethane resin, silicone resin or the like that can be cured by drying at room temperature may be used. The metallic coating film is preferably formed so that the thickness after drying is 10 to 30 μm.

[Pearl coating] A color intermediate coating composition is applied to a substrate to be coated so as to have a film thickness after drying of 20 to 40 µm to form a coating, on which a particle diameter range is 1 to 60 µm.
m, preferably 1 to 40 μm and having an average particle size of 15 to 2
Coating of pearl mica pigment with interference effect by coating a thin film of titanium dioxide, iron oxide and other metal oxides such as chromium, cobalt, tin and zirconium on the surface of natural muscovite and synthetic mica in the range of 5 μm It is a coating film in which a pearl-based coating film is formed by mixing at a ratio of 1 to 10 parts by weight with respect to 100 parts by weight of the formed resin solid content. The pearl coating film is preferably formed so that the film thickness after drying is 10 to 20 μm.

(2) Bright material-containing clear coating film forming step: In this step, a coating material in which an aluminum flake pigment and a synthetic mica powder pigment are mixed in a vehicle is applied and dried to form a bright material-containing clear coating film. is there. Aluminum flake pigment (A) as a luster material has an average particle diameter D ₅₀ of 20 ± 5.
The particles having a particle size of .mu.m, an average particle thickness of 0.5 to 1.5 .mu.m, and a gradient n in the Rosin-Rammler diagram of 2.5 or more are selectively used. What is the average particle diameter D ₅₀ ?
It is the 50% value of the particle size distribution measured by a laser diffraction type particle size distribution measuring device. The average particle thickness (μm) is [40
00 / water surface area (cm ² / g)] The value is obtained by the formula, and the measuring method is, for example, “Aluminum Handbook” (published April 15, 1972, 9th edition, Japan Light Metal Association; Asakura Shoten). ), P. 1243. In addition, the Rosin-Rammler diagram is [R
= 100exp (-bD ⁿ )] (where R is the cumulative weight% from the maximum particle size to the particle size D, D is the particle size, and b and n are constants). And the gradient n means the n value of the rosin-Rammler formula represented by a straight line connecting the cumulative weight% from the maximum particle size to the particle size D in the particle size diagram. A specific measurement method is to obtain a particle size distribution using a laser diffraction type particle size distribution measuring device, plot the obtained cumulative distribution for each particle size on a rosin-Rammler diagram, and translate the straight line in parallel to an extreme point ( Calculate n by extrapolating from Pol P).

The average particle diameter D ₅₀ of the aluminum flake pigment is 1
If it is less than 5 μm, the particles become too fine and the glittering feeling does not appear sufficiently, and if it exceeds 25 μm, the particles become large, and the presence of the particles becomes too conspicuous, and the base of the metallic coating or pearl coating contains the glittering base. This is to reduce the hue and color appearance of the coating film. The average particle thickness is 0.5 to 1.5
The range of μm is relatively thicker than conventional aluminum flake pigments, it is difficult to deform and has excellent surface smoothness, and when it is used as a coating film, diffuse reflection is suppressed and it plays a function of enhancing the glitter feeling. If the average particle thickness is less than 0.5 μm, it is not possible to enhance the brilliance, and if it exceeds 1.5 μm, the aluminum flake pigment protrudes due to defective orientation, resulting in poor coating film appearance. The particle properties with a gradient n of 2.5 or more in the Rosin-Rammler diagram are characterized by a narrow particle size distribution of the aluminum flake pigment, and particles with a uniform particle size suppress diffuse reflection due to fine particles and give a bright feeling. With increasing, coarse particles are also reduced, leading to the formation of a good coating appearance. If this slope n is below 2.5,
The particle size distribution becomes wider, and the particles on the fine side strengthen the grayish white peculiar to aluminum flakes, giving a reduced glittering feeling and a turbid bottom, and a reduced depth feeling. The gradient n in the Rosin-Rammler diagram is preferably in the range of 2.7 to 3.5.

As the aluminum flake pigment having the above-mentioned particle properties, for example, atomized aluminum spherical powder whose particle size is selected in advance by primary classification or the like is pulverized with a pulverization aid, an aliphatic or aromatic hydrocarbon solvent. It can be obtained by performing wet pulverization treatment with a pulverizer in the coexistence of a medium, sieving in the wet state, and then performing solid-liquid separation with a filter press or the like. The particle shape has a macroscopically circular or rounded flat shape, and has a very small number of uneven fracture surfaces existing at the flake ends.

On the other hand, as the synthetic mica powder pigment (B) coated with a metal oxide, titanium dioxide, iron oxide or other chromium, cobalt, tin, zirconium, etc. are formed on the surface of synthetic mica such as fluorophlogopite or fluorotetrasilicon mica. Which is a pearl mica pigment coated with a thin film of a metal oxide of No. 6, which has an interference color effect, and has an average particle diameter (D ₅₀ ) of 20 to 60 μm.
Scale-like particles in the m 2 range are preferably used. More preferably, it is 20 to 50 μm.

Unlike natural muscovite, synthetic mica does not contain a trace amount of iron or mud as impurities, so that, for example, when titanium oxide is coated and baked to coat a titanium dioxide film, Iron and mud are oxidized to give a pale yellow or a slightly yellowish brown color, which does not give the sensation of cloudiness at the bottom, shows clear interference coloring, and is a bright material with an excellent reflective feeling. These aluminum flake pigments (A) and synthetic mica powder pigments (B) can be used alone or in combination of two or more, but only (A) is used, or (A) and (B) are used together. It is preferable to use them together. In addition,
The mixing ratio of the aluminum flake pigment and the synthetic mica powder pigment is appropriately set according to the purpose.

The amount of the glitter material used is set in the range of 0.005 to less than 0.1 part by weight per 100 parts by weight of the resin solid content forming the coating film. If the amount used is less than 0.005 parts by weight, the reflection effect of the glittering material is insufficient, and if it is 0.1 parts by weight or more, the three-dimensional glittering feeling increases, but the presence of glittering material particles is too conspicuous. The aluminum flake pigment or synthetic mica powder pigment particles are conspicuous on the base coating film containing the bright material, which is a base, and a foreign substance feeling such as dust appears, resulting in a metallic coating film or a pearl coating. This is to reduce the hue and color appearance of the film. Preferably 0.005-
It is 0.08 part by weight.

The vehicle resin used in the coating material for forming a clear coating film containing a glittering material includes at least one thermosetting resin selected from acrylic resins, polyester resins, alkyd resins, fluororesins, polycarbonate resins and modified resins thereof. A mixture of a polymerizable resin and a crosslinking agent such as an amino resin and / or a (block) polyisocyanate compound is used. These resins are not limited to one type, and two or more types can be used in combination. In addition, a two-component polyurethane resin, silicone resin or the like that can be cured by drying at room temperature may be used.

Further, the coating material for forming the clear coating material containing the brightening material may contain a color pigment or other components within a range not impairing the transparency and the bright feeling. At least one layer of the coating film thus formed is formed, and the film thickness after drying is preferably set to 20 to 50 μm. The clear coating film may be further coated on the bright material-containing clear coating film to form a clear coating film having a film thickness (dry film thickness) of 30 to 60 μm to further enhance the appearance.

In the coating material for forming a base coating film containing a bright material and the coating material for forming a clear coating film containing a bright material, other additives such as a curing catalyst such as dodecylbenzenesulfonic acid, a benzotriazole-based ultraviolet absorber, Benzophenol-based antioxidants, surface modifiers such as silicones and organic polymers, anti-sagging agents, thickening agents, anti-settling agents, crosslinkable polymer particles (microgels), etc. are appropriately used.
These components can generally improve the performance of paints and coatings in amounts of 5 parts by weight or less based on 100 parts by weight of the resin for forming a coating.

The paint for forming a glittering coating film having the above component composition is generally an organic solvent type, but is not limited to this, and various types such as non-aqueous dispersion type, aqueous solution type and water dispersion type are available. The paint can be configured as a form. At the time of coating, it is diluted with a solvent such as an organic solvent or water to a viscosity suitable for coating, and the solid content during production is preferably 30 to 70% by weight, and the solid content during coating is preferably 10 to 50% by weight.

For formation of the bright material-containing base coating film, the bright material-containing clear coating film and the clear coating film, an atomization type coating method such as air spray coating or electrostatic coating or a roll coater type coating method is applied. The coating is applied so that the dried film has a predetermined film thickness. The coating film is formed by wet-on-wet coating with a bright material-containing clear coating material for baking on a two-coat / one-bake method, or on the base coating material with a wet-on-wet coating containing a bright material. After coating and baking the film coating, the coating for the clear coating is further applied and baked, and the coating for the base coating is wet-on-wet and the coating for the clear coating containing the luster material is further applied. Apply clear coating paint on-wet and bake at the same time 3
It can be formed by an appropriate method such as a coat 1 bake method.

A metallic coating film or a pearl coating film containing a glitter material has a glittering glittering feeling due to the glitter material, but since the glitter material in the coating film is relatively large, the glitter materials may be stacked in parallel in the coating film. Is easy to orient, and the glittering feeling becomes stronger as it approaches the direction of regular reflection of light (flip-flop effect)
Tend. Therefore, the glittering feeling becomes dull in the shade direction, and it is not possible to obtain a glittering feeling with a three-dimensional depth.

According to the method for forming a glittering coating film of the present invention, an aluminum flake pigment having a specific particle property with a uniform particle diameter distribution, transparency and smoothness are provided on the glittering material-containing base coating film to be the base coat. A metal oxide having a large size and a high interference effect, for example, a synthetic mica powder pigment coated with titanium dioxide is used as a glittering material, and 0.005 to 100 parts by weight of resin solid content is used.
Since a very small amount of less than 0.1 parts by weight is added, the glitter material can be randomly distributed and oriented in the clear coating film, and a glittering feeling can be exhibited even when viewed in the shade direction. . In particular, if the average particle size of the aluminum flake pigment is 20 ± 5 μm and the average particle size of the synthetic mica powder pigment coated with metal oxide is in the range of 20 to 60 μm, the size of the luster pigment particles is controlled to be the presence of individual particles. Is less noticeable, and a sense of unity with the base coating film containing the luster material of the lower layer is brought out, and even if the viewpoint angle is changed, a glittering sparkle and a three-dimensional glittering feeling with depth can be exhibited. Furthermore, the brightness (L ^* ) of the base coating film containing the luster material is 70
It is preferable to set to the following dark color system because a more excellent glitter feeling can be obtained. More preferably lightness (L ^* )
Is set to 60 or less. The lightness (L ^* ) is JIS
It is a value specified by Z8730.

The preferred embodiments of the present invention are listed below. A glittering material-containing base coating film is formed, and (1) the average particle diameter (D ₅₀ ) is 20 ± 5 μm, the average particle thickness is 0.5 to 1.5 μm, and the rosin-Rammler diagram A method for forming a glittering coating film, comprising forming a glittering material-containing clear coating film containing an aluminum flake pigment having a gradient n of 2.7 or more. (2) A method for forming a glittering coating film, which comprises forming a glittering material-containing clear coating film containing a synthetic mica powder pigment having an average particle size of 20 to 50 μm coated with a metal oxide. (3) A method for forming a glittering coating film, which comprises forming a glittering material-containing clear coating film containing an aluminum flake pigment and a synthetic mica powder pigment, and then forming a clear coating film. (4) The slope n in the Rosin-Rammler diagram is 2.7-
A method for forming a glittering coating film, comprising forming a glittering material-containing clear coating film containing the 3.5 aluminum flake pigment. (5) A glittering material composed of aluminum flake pigment and / or synthetic mica powder pigment is added to 0.0 per 100 parts by weight of resin solid content.
A method for forming a glittering coating film, which comprises forming a glittering material-containing clear coating film with a coating material blended in an amount of 05 to 0.08 parts by weight. (6) The average particle size (D ₅₀ ) coated with a metal oxide is 20 to
A method for forming a glittering coating film, comprising forming a glittering material-containing clear coating film containing a synthetic mica powder pigment of 50 μm. (7) A method for forming a glittering coating film, wherein the brightness (L ^* ) of the glittering material-containing base coating film is set to 60 or less. (8) A coated article coated by any of the above (1) to (7).

[0029]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples.

Examples 1 to 6 and Comparative Examples 1 to 5 (1) Preparation of base material to be coated: On a 0.8 mm thick dull steel plate base material which has been subjected to chemical conversion treatment with zinc phosphate, a cationic electrodeposition coating [Nippon Paint] "Power Top U-50" manufactured by K.K. Co., Ltd. was applied so that the dry coating film had a thickness of 25 .mu.m.
Baked for minutes. "Olga S-90 Sealer" manufactured by Nippon Paint Co., Ltd. was applied as an intermediate coating on the surface of the electrodeposition coating film by air spray coating so that the dry coating film had a thickness of 40 .mu.m.
And baked for 30 minutes to prepare a test plate as a base material to be coated. However, in each of Example 4 and Comparative Examples 4 and 5, a test plate having a color intermediate coating film containing the following primary color coating material for intermediate coating manufactured by Nippon Paint Co., Ltd. in place of the above intermediate coating material was used. Olga S-90 Sheila Tomoiro White / Olga S-90 Sheila Tomoiro Black / Olga S-90 Sheila Tomoiro Ocher / Olga S-90 Sheila Tomoiro Anchor Red = 97/2 / 0.3 / 0 .7 (ratio by weight of paint).

(2) Preparation of a coating material for forming a base film containing a glittering material; acrylic resin (styrene / methyl methacrylate / ethyl acrylate / hydroxyethyl methacrylate / methacrylic acid copolymer, number average molecular weight of about 20)
000, hydroxyl value 45, acid value 15, solid content 50%) 75
100 parts by weight of a vehicle resin in which 25 parts by weight of solid content and 25 parts by weight of melamine resin [“Uban 20SE” manufactured by Mitsui Toatsu Chemicals, Inc., solid content 60%] are mixed with aluminum flake pigment [Asahi Kasei Metals Co., Ltd. "Asahi Kasei Aluminum Paste MH-9901" (Average particle size 2
1 μm)], pearl mica pigments (“Exterior Marlin Highlight Red”, “Exterior Marlin Highlight Green” manufactured by Marl Co., Ltd., and “Iriodin 103WII” manufactured by Merck Co. Ltd.) in different quantitative ratios. Also,
The color pigment is "Carbon Black FW-20" manufactured by Degussa.
0 ", Sanyo Pigment Co., Ltd." Shani Blue G314 ", Ciba Geigy" Sincassia Red Y-RT759 "
D ”, Toyo Ink Mfg. Co., Ltd.“ Rionol Green 6 ”
Y "was used.

(3) Preparation of clear coating material containing a bright material; acrylic resin (styrene / styrene / vehicle resin)
Ethylhexyl methacrylate / hydroxyethyl methacrylate / methacrylic acid copolymer, number average molecular weight 8000, hydroxyl value 70, acid value 20, solid content 55
%) 70 solid parts by weight and melamine resin (“Uban 20SE” manufactured by Mitsui Toatsu Chemicals, Inc., solid content 60%) 30 solid parts by weight mixed resin was used. To 100 parts by weight of this vehicle resin, the following aluminum flake pigment and synthetic mica powder pigment were blended in different amount ratios as a glittering material. Aluminum flake pigment; (a) Average particle size (D ₅₀ ) 20 μm, average particle thickness 0.
7 μm, gradient n of rosin-Rammler diagram is 3.0 (b) average particle diameter (D ₅₀ ) 18 μm, average particle thickness of 0.
4 μm, gradient n of rosin-Rammler diagram 2.3 (c) average particle diameter (D ₅₀ ) 30 μm, average particle thickness 1.
0 μm, rosin-Rammler diagram gradient n is 2.6 synthetic mica powder pigment coated with metal oxide; (d) average particle size (D ₅₀ ) 21 μm, titanium dioxide coated synthetic mica powder pigment [Topy Industry Co., Ltd. (E) Average particle size (D ₅₀ ) 50 μm, titanium dioxide coating synthetic mica powder pigment (manufactured by Topy Industries Co., Ltd., interference color; silver)

The coating material for a base coating film containing a bright material and the coating material for a clear coating film containing a bright material were applied on a test plate by a wet-on-wet method and baked at 140 ° C. for 30 minutes to form a bright coating film.

With respect to the coating film thus formed, the composition of the base coating material containing the bright material is shown in Tables 1 and 2 and the composition of the clear coating material containing the bright material is shown in Tables 3 to 4. In addition, the formed coating film was visually evaluated according to the following criteria to evaluate the appearance of the coating film. The obtained evaluation results are also shown in Tables 3 to 4. Iridescent sensation ◎ ... Strong rainbow-colored glittering ○: Iridescent glittering is observed △… Iridescent glittering is hardly observed Foreign-body feel ○… There is a sense of unity that can not be felt ×… The glittering material looks like foreign matter like dust (white dots)

[0035]

[Table 1] (Note) * 1 Asahi Kasei Metals KK “Asahi Kasei Aluminum Paste MH-9901” * 2 I Marl “Exterior Marlin Highlight Red” II Marl “Exterior Marlin Highlight Green” III Merck “Iriodin 103WII "* 3 (1)" Carbon black FW-200 "manufactured by Degussa (2)" Shani blue G314 "manufactured by Sanyo Pigment Co., Ltd. (3)" Sincassia Red Y-RT759D "manufactured by Ciba-Geigy (4) Toyo Ink "Rionol Green 6Y" manufactured by Manufacture Co., Ltd. * 4 Measured using an SM color computer SM-5 [manufactured by Suga Test Instruments Co., Ltd.].

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

From the results shown in Tables 1 to 4, the coating films formed by the respective examples satisfying the conditions of the present invention have excellent brilliance as compared with the coating films formed by the comparative examples. I understand. For example, in Comparative Examples 3 and 5 in which the amount of the brightening agent is large, although a strong rainbow-colored glittering feeling is exhibited, the dust-like foreign body feeling is increased, resulting in poor color tone and color feeling. Further, in the case of Comparative Examples 1 and 4 having a small gradient n in the rosin-Rammler diagram of the aluminum flake pigment, that is, having a wide particle size distribution, or Comparative Example 2 having a large average particle size, the glittering rainbow-colored brilliance was inferior. It can be seen that the sensation of foreign matter in the glitter material particles is increased and an excellent glitter feeling cannot be obtained.

[0040]

As described above, according to the method for forming a glittering coating film of the present invention, a glittering material-containing base coating film is formed, on which an aluminum flake pigment having a specific particle property or a metal oxide is added as a glittering material. At least one of coated synthetic mica powder pigments
Since it forms a bright material-containing clear coating film containing seeds,
Even if the blending amount of the glittering material is small, a glittering coating film having excellent transparency and glittering feeling can be obtained, and since the blending amount of the glittering material is small, it is randomly aligned without being oriented in a layered state in the coating film,
With a slight change in the viewing angle, it is possible to bring out a sparkling three-dimensional brilliance. Therefore, it is extremely useful as a glittering coating film forming method and a coated product capable of forming a coating film having an excellent glittering feeling on automobiles, bicycles, home electric appliances and other industrial parts.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eizo Niimi 4-1-1-15 Minami-Shinagawa, Shinagawa-ku, Tokyo Inside Nippon Paint Co., Ltd.

Claims (5)

[Claims] 1. A method for forming a glittering coating film, which comprises sequentially performing the following coating film forming steps (1) to (2). (1) A step of forming a glittering material-containing base coating film on a substrate to be coated. (2) At least one glittering material of the following (A) or (B) is added to 0.005 to 100 parts by weight of resin solid content. Step of forming at least one clear coating film containing a bright material containing less than 0.1 part by weight (A) Average particle diameter (D ₅₀ ) is 20 ± 5 μm, average particle thickness is 0.5 to 1.5 μm, rosin- Aluminum flake pigment having a gradient n of 2.5 or more in Lambler diagram (B) Synthetic mica powder pigment coated with metal oxide. 2. The bright material of the clear coating film containing a bright material comprises: (A) an average particle diameter (D ₅₀ ) of 20 ± 5 μm, an average particle thickness of 0.5 to 1.5 μm, and a gradient in a Rosin-Rammler diagram. An aluminum flake pigment having n of 2.5 or more, or (A) an average particle size (D ₅₀ ) of 20 ± 5 μm, a particle average thickness of 0.5 to 1.5 μm, and a gradient n in the Rosin-Rammler diagram of 2 0.5 or more aluminum flake pigment and (B) a metal oxide-coated synthetic mica powder pigment,
The method for forming a glittering coating film according to claim 1. 3. The synthetic mica powder pigment coated with a metal oxide has an average particle diameter (D ₅₀ ) of 20 to ₆₀ μm.
Or the method for forming a glittering coating film according to 2. 4. The method for forming a glittering coating film according to claim 1, 2 or 3, wherein the brightness (L ^* ) of the glittering material-containing base coating film is 70 or less. 5. A coated article coated by the method for forming a glittering coating film according to any one of claims 1 to 4.