JP2002273330A - Coating film forming method and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant coating film forming method for forming a silky metallic coating film having an extremely high weatherability and depth, and a coated article. SOLUTION: In the brilliant coating film forming method, a brilliant coating film layer is formed on a base material using a brilliant coating material containing brilliant a pigment comprising bismuth oxychloride crystals and vehicle and a top color clear coating film layer is further formed thereon using a color clear coating material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a glittering coating film capable of providing a silky metallic coating film having sufficient weather resistance, and a coated article.

[0002]

2. Description of the Related Art Pigments containing bismuth oxychloride crystals are:
It has been used as a cosmetic because it has a smooth silky feeling, transparency, and glitter. For example, Japanese Patent Application Laid-Open No. Hei 5-2
JP 39375 describes the use of pigments coated with a cerium compound on bismuth oxychloride crystals having a pearly luster for cosmetics.

On the other hand, a technique using bismuth oxychloride pigment for painting and finishing automobiles and metal parts is disclosed in JP-A-7-68.
No. 215. This publication discloses a plate-like average particle size of bismuth oxychloride crystal particles of 5 to 25.
By coating a base coat paint containing a gloss pigment of μm and a color pigment on the object to be coated, and then applying a clear paint, a novel pearly feeling, flip-flop property, transparency, and finished appearance are excellent. It discloses a method for obtaining a coating film having a design property.

However, bismuth oxychloride changes from gray to black due to ultraviolet rays (called darkening).
Stabilization has been performed in combination with an ultraviolet absorber. However, such a measure is not sufficient when exposed to intense sunlight, as in the case of a coating film on an automobile outer panel. For example, the average particle size used in the examples of JP-A-7-68215 described above. Bismuth oxychloride crystal coated with cerium hydroxide (Mearlite RadiantPear) having a diameter of 13 μm, a particle size range of 11 to 15 μm, a thickness of 0.06 μm.
(STL) as a pigment gave a ΔL value of about 13 after 48 days of exposure in Florida, USA, which was not very usable.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for forming a brilliant coating film and a coated product which form a silky-tone metallic coating film having extremely high weather resistance and having a large depth. is there.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, have reached the present invention. 1. On the base material, a glittering coating layer containing a glittering pigment comprising bismuth oxychloride crystals and a glittering paint containing a vehicle is formed, and a top color clear coating layer with a color clear paint is further formed thereon. A method for forming a glittering coating film to be formed. 2. The above-mentioned method for forming a glittering coating film, wherein the glitter pigment comprising bismuth oxychloride crystals has a particle size in the range of 7 to 11 μm, and the thickness of the crystals is less than 60 nm. 3. The above-described method for forming a glitter coating film, wherein the glitter pigment comprising the bismuth oxychloride crystal is coated with cerium hydroxide. 4. The above-described method for forming a glittering coating film, wherein the glittering pigment comprising bismuth oxychloride crystals is used in combination with a glittering pigment and / or a coloring pigment other than the pigment. 5. The above glittering coating film forming method, wherein the top color clear coating layer has a visible light transmittance of 10 to 90%. 6. The above method for forming a glittering coating film, wherein the color clear paint is a paint containing a carboxyl group-containing polymer and an epoxy group-containing polymer. 7. A coated article obtained by the above-described method for forming a glittering coating film.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

[0008] The method for forming a glittering coating film is a method for forming a coating film according to the present invention, comprising: using a glittering paint containing a glittering pigment composed of bismuth oxychloride crystals and a vehicle on a substrate; A top color clear coating layer is formed by a color clear coating.

Substrates The above-mentioned substrates are not limited, and metals such as iron, aluminum, copper or alloys thereof; inorganic materials such as glass, cement, concrete, etc .; polyethylene resins, polypropylene resins, ethylene- Resins such as vinyl acetate copolymer resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin and various plastic materials such as FRP; natural materials such as wood, paper and cloth fiber materials Or a synthetic material. In the glittering coating film forming method of the present invention, the glittering pigment composed of bismuth oxychloride crystals and a vehicle are directly contained on the base material or through the undercoating layer and, if necessary, the intermediate coating layer. The glitter coating layer is formed by using a glitter paint. When the paint obtained by the glitter coating film forming method of the present invention is an automobile body or a part, the base material is previously degreased or converted. It is preferable to apply undercoating such as treatment, electrodeposition coating, or further intermediate coating. The intermediate coating is performed for hiding the underlayer, imparting chipping resistance, and ensuring adhesion with the overcoat.

Formation of a glitter coating layer The intermediate coating layer in the glitter coating film forming method of the present invention comprises:
If necessary, it can be formed on the substrate on which the electrodeposition coating layer or the intermediate coating layer is formed by wet-on-wet (W / W) or wet-on-dry (W / D). The above-mentioned W / W is a method of forming a lower coating layer, drying the coating layer by air drying or the like, and coating the lower coating layer in an uncured or semi-cured state.
/ D is a method of coating a lower coating layer baked and cured. The glitter coating layer is formed of a glitter paint containing a glitter pigment composed of bismuth oxychloride crystals and a vehicle.

The glitter pigment used in the glitter paint is as follows:
It is composed of bismuth oxychloride crystals, and preferred examples of the glittering pigment composed of bismuth oxychloride crystals used in the present invention (hereinafter referred to as bismuth glittering pigments) from the viewpoint of weather resistance include bismuth nitrate and the like. A water-soluble bismuth compound, hydrochloric acid or a mixture of hydrochloric acid and nitric acid, and a base or a base precursor such as an amine or urea are simultaneously injected into an acidic aqueous solution to hydrolyze the bismuth compound and to adjust the pH to about 1, Crystals are precipitated at 50 to 100 ° C to obtain a slurry, which is dried to obtain a bismuth glittering pigment. Further, the bismuth glitter pigment is preferably coated with cerium hydroxide from the viewpoint of weather resistance.

When bismuth oxychloride crystals are coated with a rare earth metal compound such as cerium hydroxide, a predetermined amount of a rare earth metal salt solution is added to the above-mentioned slurry having a pH of about 1 and the pH value is stirred. To about 10 to precipitate cerium hydroxide crystals,
Coating the surface of bismuth oxychloride crystals.

In the bismuth glittering pigment contained in the coating composition of the present invention, the content of bismuth oxychloride crystals is preferably 90% or more. The particle size is preferably from 7 to 11 μm, more preferably from 8 to 10 μm, and these can be obtained by adjusting the above precipitation conditions. The thickness of the crystal is preferably less than 60 nm, more preferably 20 to 50 nm. As the number of crystals having a particle size of less than 7 μm increases, the paint stability may decrease. On the other hand, when the number of crystals exceeding 11 μm increases, the silky tone may decrease. The preferred ranges of the particle size and the crystal thickness are the same when coated with a rare earth metal. In this case, the size of the bismuth oxychloride crystal is reduced accordingly.

Therefore, the weather resistance of the coating film formed from the coating material containing the bismuth glittering pigment is significantly higher than that of the conventional coating material containing bismuth oxychloride crystals. In other words, the ΔL after exposure for 48 days in Florida, USA, can be reduced from about 13 in the conventional product to the range of 0 to 3. Exposure in Florida is very severe as a coating film test, as compared to exposure in Japan, for example, in Okinawa, where the average amount of ultraviolet light per day and the number of annual solar radiation days are large.

The above ΔL indicates the difference between the L value before and after the coating film is exposed, and the L value is defined by JIS Z8722.
Means the lightness index in the Hunter's color difference equation determined from the tristimulus values X, Y, and Z defined in (1). The color difference can be measured with a spectrophotometer (for example, SM Computer, manufactured by Suga Test Instruments Co., Ltd.).

The amount of the bismuth glittering pigment to be added to the glittering paint is preferably 0.01 to 30% by PWC (mass ratio of the solid content of the pigment to 100 parts by mass of the solid content of the paint). If the PWC is less than 0.01%, it is difficult to obtain a silky coating film, and if it exceeds 30%, a highly glossy coating film may not be obtained. More preferable PWC is 0.1 to 20% in the case of lowering the hiding power of the glittering coating film and forming a color in combination with the hue of the undercoating. Is 0.5 to 30%.

The glitter paint of the present invention can be prepared by using a glitter pigment and / or a coloring pigment other than the bismuth glitter pigment together with the bismuth glitter pigment as long as the above effects of the bismuth glitter pigment are not impaired. Design,
For example, it is possible to form a coating film exhibiting design properties by combining the glitter and the like of the aluminum flake pigment.

Examples of such pigments include aluminum flake pigment, metal oxide-coated alumina flake pigment, metal oxide-coated silica flake pigment, graphite pigment, interference mica pigment, colored mica pigment, metal titanium flake pigment, and stainless flake. At least one brilliant pigment selected from the group consisting of pigments, plate-like iron oxide pigments, metal-plated glass flake pigments, metal oxide-coated plated glass flake pigments, hologram pigments, and flake-like pigments composed of cholesteric liquid crystal polymers, and azo lakes Pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments,
At least one color pigment selected from the group consisting of perylene pigments, phthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, yellow iron oxide, red iron oxide, carbon black, titanium dioxide and the like. Is mentioned.

When the above-mentioned bismuth glittering pigment is used in combination with a glittering pigment and / or a coloring pigment other than this pigment, the content (PWC) is preferably less than 50%, more preferably 30%.
Less than is more preferable. If it exceeds 50%, the appearance of the coating film may be reduced.

In the method for forming a glittering coating film of the present invention, the vehicle contained in the glittering paint used to form the glittering coating layer comprises a resin for forming a coating film and, if necessary, a crosslinking agent. Examples of the resin for forming a coating film include (a) an acrylic resin, (b) a polyester resin, (c) an alkyd resin, (d) a fluororesin, (e) an epoxy resin, (f) a polyurethane resin, and (g) a polyether. And the like. These can be used alone or in combination of two or more, and are preferably an acrylic resin or a polyester resin.

The acrylic resin (a) includes a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Examples of the acrylic monomer that can be used for the copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl and t-acrylate of acrylic acid or methacrylic acid.
-Butyl, 2-ethylhexyl, lauryl, phenyl,
Esterified products such as benzyl, 2-hydroxyethyl and 2-hydroxypropyl; ring-opened adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate; glycidyl acrylate; glycidyl methacrylate;
Acrylamide, methacrylamide, N-methylolacrylamide, (meth) acrylic esters of polyhydric alcohols and the like can be mentioned. Other ethylenically unsaturated monomers copolymerizable therewith include styrene,
α-methylstyrene, itaconic acid, maleic acid, vinyl acetate and the like.

Examples of the polyester resin (b) include saturated polyester resins and unsaturated polyester resins, and examples include condensates obtained by heating and condensing a polybasic acid and a polyhydric alcohol. As the polybasic acid, phthalic anhydride, terephthalic acid, saturated polybasic acids such as succinic acid,
And unsaturated polybasic acids such as maleic acid, maleic anhydride and fumaric acid. Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol and diethylene glycol, and trihydric alcohols such as glycerin and trimethylolpropane. In addition, the resin for forming a coating film includes:
There are a curable type and a lacquer type, and usually a curable type is used.

The alkyd resin (c) includes, in addition to the above polybasic acids and polyhydric alcohols, fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), and natural resins (rosin, amber, etc.). An alkyd resin obtained by reacting the above-mentioned modifier can be used.

The fluorine resin (d) may be any one of vinylidene fluoride resin and ethylene tetrafluoride resin or a mixture thereof, a fluoroolefin and a hydroxy-containing polymerizable compound, and other copolymerizable vinyl resins. Examples include resins made of various fluorine-based copolymers obtained by copolymerizing a monomer mixture made of a compound.

Examples of the epoxy resin (e) include resins obtained by the reaction of bisphenol and epichlorohydrin. Examples of the bisphenol include bisphenols A and F. As the bisphenol type epoxy resin, for example, Epicoat 8
28, Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009 (all trade names, manufactured by Shell Chemical Co., Ltd.), and those obtained by chain-extending these with an appropriate chain extender can also be used.

Examples of the polyurethane resin (f) include resins having a urethane bond obtained by reacting various polyol components such as acryl, polyester, polyether and polycarbonate with a polyisocyanate compound. As the polyisocyanate compound,
2,4-tolylene diisocyanate (2,4-TD
I), 2,6-tolylene diisocyanate (2,6-T
DI), and mixtures thereof (TDI), diphenylmethane-4,4′-diisocyanate (4,4′-MD
I), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), and mixtures thereof (MDI)
Naphthalene-1,5-diisocyanate (NDI),
3,3'-dimethyl-4,4'-biphenylene diisocyanate, xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HD
I), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (HXDI) and the like.

The above (g) polyether resin is a polymer or copolymer having an ether bond, and is a polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether, or bisphenol. Examples include polyether resins having at least two hydroxyl groups per molecule, such as polyethers derived from aromatic polyhydroxy compounds such as A or bisphenol F. The above polyether resin and succinic acid, adipic acid, sebacic acid,
Examples thereof include polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid, and carboxyl group-containing polyether resins obtained by reacting with a reactive derivative such as an acid anhydride thereof.

In the case of a type having curability, amino resins, (block) polyisocyanate compounds, amines, polyamides, imidazoles, imidazolines,
It is used by mixing with a crosslinking agent such as a polyvalent carboxylic acid, and the curing reaction can proceed at heating or at room temperature. Also,
It is also possible to use a lacquer type coating film forming resin having no curability and a type having curability in combination.

When the above-mentioned vehicle contains a crosslinking agent, the ratio of the coating film forming resin to the crosslinking agent is 90 to 50% by mass and the crosslinking agent is 10 to 50% by mass in terms of solid content. Preferably, the coating film forming resin is 85 to 60% by mass, and the crosslinking agent is 15 to 40% by mass. If the amount of the crosslinking agent is less than 10% by mass (the amount of the resin for forming a coating film exceeds 90% by mass), the crosslinking in the coating film is insufficient. On the other hand, if the crosslinking agent exceeds 50% by mass (the
), The storage stability of the coating material is reduced and the curing speed is increased, so that the appearance of the coating film is deteriorated.

In addition to the above-mentioned components, the above-mentioned intermediate coating composition comprises a polyamide wax which is a lubricating dispersion of an aliphatic amide, a polyethylene wax which is a colloidal dispersion mainly composed of polyethylene oxide, an antisettling agent, a curing catalyst, an ultraviolet ray. Absorbents, antioxidants, leveling agents, surface conditioners such as silicone and organic polymers, anti-sagging agents, thickeners, defoamers, lubricants, cross-linkable polymer particles (microgels), etc. can do. These additives are usually, for example, based on 100 parts by mass of the vehicle (based on solid content),
By blending each in a proportion of 15 parts by mass or less,
The performance of paints and coatings can be improved.

The glittering paint can take various forms such as a solvent type, an aqueous type and a powder type. As the solvent-based paint or the water-based paint, a one-pack paint may be used, or a two-pack resin such as a two-pack urethane resin paint may be used.

When the glittering paint is a solvent-type or water-based paint, the above components are usually provided in a form dissolved or dispersed in a solvent. Any solvent may be used as long as it dissolves or disperses the vehicle, and an organic solvent and / or water may be used. Organic solvents include those commonly used in the field of coatings. For example, toluene,
Hydrocarbons such as xylene, ketones such as acetone and methyl ethyl ketone, ethyl acetate, cellosolve acetate,
Esters such as butyl cellosolve, alcohols and the like can be exemplified. When the use of an organic solvent is regulated from the viewpoint of the environment, it is preferable to use water. In this case, an appropriate amount of a hydrophilic organic solvent may be contained.

The dry film thickness of the glitter coating layer is preferably from 5 to 50 μm per coat, and if it is less than 5 μm, calm glitter cannot be sufficiently exhibited, and if it exceeds 50 μm, the appearance of the coating film deteriorates. There is fear. More preferably 1
0 to 30 μm.

Formation of Top Color Clear Coating Layer In the glittering coating film forming method of the present invention, after forming the glittering coating layer, at least one layer is further formed thereon by W / W or W / D. To form a top color clear coating layer. The formation of this top color clear coating layer
It is preferable to carry out with W / W.

In this case, the top color clear coating layer does not hide the glittering coating layer, and the top color clear coating layer has a visible light transmittance of 10 to 90%.
It is preferred that Here, the light transmittance in the visible region is an average value of the light transmittance at a wavelength of 400 to 800 nm, and is measured as follows. First, a free film having a dry film thickness of 30 μm is prepared, and the light transmittance of the free film having a wavelength of 400 to 800 nm is integrated with an integrating sphere spectrophotometer. Next, light transmittance 100%
Is obtained in the same wavelength range, and this integrated value is set to B. At this time, the light transmittance is expressed as light transmittance (%) = (A
/ B) × 100. In order to make the light transmittance within the above range, it can be obtained by selecting the type and amount of the above color pigment.

The top color clear coating layer is formed of a color clear coating. Examples of the color clear coating include those commonly used for overcoating. A mixture of a resin for use and a crosslinking agent can be used.

These clear top paints may contain additives such as extenders, modifiers, ultraviolet absorbers, leveling agents, dispersants, defoamers, etc., as needed, as long as the transparency is not impaired. It is possible to

A clear top paint containing a carboxyl group-containing polymer and an epoxy group-containing polymer described in Japanese Patent Publication No. Hei 8-19315 was coated with a top color clear coating film layer by taking measures against acid rain and wet-on-wet. In this case, it is preferably used from the viewpoint of not disturbing the orientation of the bismuth glittering pigment.

The top clear coating layer is a solvent type,
It can take various forms such as an aqueous or powder type. As the solvent-based paint or the water-based paint, a one-pack paint may be used, or a two-pack resin such as a two-pack urethane resin paint may be used.

The dry film thickness of the top clear coating layer is as follows:
The thickness is preferably from 10 to 50 μm, and if it is out of this range, the appearance of the coating film may be insufficient. More preferably 20-4
0 μm.

The method of forming each coating layer is not particularly limited, but a spray method or a roll coater method is used for applying a solvent-type paint or an aqueous paint, and an electrostatic coating is used for applying a powder paint. preferable. Drying conditions are 120-1
It is baked at 80 ° C. for a predetermined time to obtain a coating film.

Coated product The coated product of the present invention is obtained by the above-described method for forming a glitter coating film. After forming a glitter coating film layer containing a bismuth glitter pigment on a substrate, the top color clear is formed. A multilayer coating film having a coating layer formed thereon is formed. The coated article on which these multilayer coating films are formed has very high weather resistance and expresses a deep silky metallic feeling.

[0043]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the compounding amount represents a mass part unless there is particular notice. The names of raw materials, paints, and equipment represent trade names unless otherwise specified.

Examples 1 to 10 and Comparative Example 1 A pre-treated dull steel plate (300 mm in length, 100 mm in width and 0.8 mm in thickness) was degreased and then treated with zinc phosphate ("Surfdyne SD2000", Japan And then a cationic electrodeposition coating ("Power Top U-50", manufactured by Nippon Paint Co., Ltd.) with a dry film thickness of 25 [mu] m.
And baked at 160 ° C. for 30 minutes. Then, an intermediate coating ("Olga S-90", manufactured by Nippon Paint Co., Ltd.) was applied by air spraying so as to have a dry film thickness of 40 [mu] m, and baked at 140 [deg.] C. for 30 minutes to form an intermediate coating film layer.

Preparation of glitter paint Acrylic resin (styrene / methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate /
Methacrylic acid copolymer, number average molecular weight about 20,000,
A hydroxyl value of 45, an acid value of 15, and a solid content of 50% by mass) and a melamine resin (“Uban 20SE”, manufactured by Mitsui Chemicals, Inc., solid content of 60% by mass) are blended at a solid content mass ratio of 80:20 to obtain. Bismuth brilliant pigment coated with 3 parts by mass of cerium hydroxide per 100 parts by mass of bismuth oxychloride crystal (manufactured by Engelhard Co., particle size of 8 to 10 μm)
m, which account for 99% of the crystal, and a crystal thickness of 50 nm), and if necessary, other glittering pigments and coloring pigments in the types and proportions shown in Table 1. Then, the organic solvent (toluene / xylene / ethyl acetate / butyl acetate mass ratio = 7)
0/15/10/5) with a dissolver so as to obtain an appropriate coating viscosity, thereby preparing a glittering paint.

Bright coating layer and top color clear coating layer
Formation of Layer The glitter paint obtained above was spray-coated on the pretreated base material so that the dry film thickness became 15 μm. Coating was performed using an electrostatic coating machine (“Auto REA”, manufactured by ABB Industries) at an atomization pressure of 2.8 kg / cm ² . Atmosphere of the booth during painting is temperature 25 ℃, humidity 75%
Held. After the coating, the coating was set for 3 minutes, the color clear coating was applied to a dry film thickness of 35 μm, set at room temperature for 10 minutes, and baked at a temperature of 140 ° C. for 30 minutes. The color clear paint used was an acrylic / melamine resin-based color clear paint 1 ("Super Lac O-130 Color Clear") having the light transmittance shown in Table 1 in the amount of the coloring pigment of the kind shown in Table 1 and the compounding amount.
Nippon Paint Co., Ltd.) or a color clear coating material 2 containing a color pigment of the type shown in Table 1 and a carboxyl group-containing polymer and an epoxy group-containing polymer having the light transmittance shown in Table 1 in the compounding amount ("Macflow O"). -520 Color Clear ", manufactured by Nippon Paint Co., Ltd.). The weather resistance and design of the obtained coating film were evaluated by the following methods. Table 1 shows the results.

The light transmittance of a free film having a dry film thickness of 30 μm was prepared using a color clear paint, and this free film was measured at a wavelength of 400 to 80 using an integrating sphere spectrophotometer.
The light transmittance at 0 nm is integrated, the integrated value is set to A, then the integrated value when the light transmittance is 100% is obtained in the same wavelength region, the integrated value is set to B, and the light transmittance (%) = ( A /
B) It was determined by the formula of × 100.

Evaluation Method <Weather Resistance> The difference ΔL between the L value before and after the test after the test plate was subjected to a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) for 2000 hours was determined. The L values before and after the test were measured using an SM computer manufactured by Suga Test Instruments Co., Ltd. <Design> Each coated plate of the above Examples and Comparative Examples was visually evaluated. 3: Silky metallic coating film with no feeling of particles 2: Silky metallic coating film with a slight feeling of particles 1: Silky metallic coating film with a slight feeling of particle

[0049]

[Table 1]

As is evident from the results in Table 1, the coated articles formed by the examples had ΔL of 2 or less, and no discoloration could be visually observed. On the other hand, the painted material of the comparative example had a high ΔL of 3 or more. From the above, the painted object of the present embodiment is compared with the conventional painted object,
It is clear that it has sufficient weather resistance.

[0051]

According to the present invention, a glitter coating film containing a bismuth glitter pigment is formed on a substrate, and then a top color clear coating layer is formed on the glitter coating layer. Very high weather resistance, and it is possible to develop a deep silky metallic feeling, and as a result, it is possible to form a coating film having high weather resistance that can obtain a more luxurious glitter. It became so. In addition, since the coating film obtained by the present invention exhibits the above-mentioned brilliant feeling and has high weather resistance, it is required to have brilliant feeling and high weather resistance such as automobile outer plates, outer surfaces of vehicles such as motorcycles, outer surfaces of containers, coil coating, and the home appliance industry. It is preferably used in the field where

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) C09D 201/06 C09D 201/06 201/08 201/08 F term (reference) 4D075 BB92Z CA32 CA48 CB04 CB06 CB13 DA06 DA23 DB01 DB11 DB18 DB20 DB21 DB31 DB61 DC11 EA02 EA06 EA07 EB07 EB16 EB22 EB32 EB33 EB35 EB36 EB37 EB38 EB52 EB55 EB56 EB57 EC01 EC11 EC53 EC54 4J038 CD091 CG141 DB001 DD001 DD121 GA01 NA01 012 001 001 PC04 PC06 PC08 PC10

Claims (7)

[Claims] 1. A glitter coating film layer is formed on a substrate by using a glitter pigment containing bismuth oxychloride crystals and a glitter paint containing a vehicle, and a top color is further formed thereon by a color clear paint. A method for forming a bright coating film for forming a clear coating layer. 2. The method according to claim 1, wherein the glitter pigment comprising bismuth oxychloride crystals has a particle size in the range of 7 to 11 μm and a crystal thickness of less than 60 nm. 3. The method according to claim 1, wherein the glitter pigment comprising bismuth oxychloride crystals is coated with cerium hydroxide. 4. The glittering coating film formation according to claim 1, wherein a glittering pigment comprising the bismuth oxychloride crystal and a glittering pigment and / or a coloring pigment other than the pigment are used in combination. Method. 5. The method according to claim 1, wherein the top color clear coating layer has a visible light transmittance of 10 to 90%. 6. The method according to claim 1, wherein the color clear coating is a coating containing a carboxyl group-containing polymer and an epoxy group-containing polymer. 7. A coated article obtained by the method for forming a glittering coating film according to claim 1.