JP2002121493A - Brilliant coating composition, method for forming coating film and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant coating composition capable of manifesting such a design as to emphasize high chromatic feeling at the highlight part and metallic feeling at the shade part. SOLUTION: This brilliant coating composition comprises a vehicle, at least two flake pigments each coated with a metal oxide and an interferential mica pigment having dark region; wherein, of the at least two flake pigments, a certain one is set as reference, and its hue is set at hue 0 in the Munsell color system, and when represented at counterclockwise +50 and clockwise -50 based on the Munsell hue circle 100, the hue H of the other flake pigment(s) is 0 to +25 or 0 to -25.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brilliant coating composition, a method for forming a coating film, and a coated product coated by this method.

[0002]

2. Description of the Related Art In a field requiring a high design such as an automobile body, a coating film using a brilliant paint composition containing a brilliant material is required. As one of them, a metal oxide-coated alumina flake pigment is known. Japanese Patent Application Laid-Open No. 10-183033 discloses a method for forming a multilayer coating film which is excellent in the brightness of highlight portions and has high chroma in shade portions. Here, when applying a colored paint, an interference paint and a clear paint, it is described that the interference paint is an organic solvent-based paint containing a metal oxide-coated alumina flake pigment and a mica powder coated with a metal oxide. Have been.

[0003] However, this method of forming a coating film has a problem in that the glitter at the shade portion is insufficient.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a design using two or more kinds of metal oxide-coated flake pigments, in which a high chroma feeling in a highlight part and a metal feeling in a shade part are emphasized. An object of the present invention is to provide a glitter coating composition, a coating film forming method, and a coated article capable of forming a coating film that can exhibit a higher-grade glitter that can be expressed.

[0005]

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. A coating composition comprising a vehicle, two or more metal oxide-coated flake pigments, and an interference mica pigment having a dark area, wherein one or more of the two or more metal oxide-coated flake pigments is used as a reference. The hue of the flake pigment coated with the metal oxide as a reference is defined as a hue 0 in the Munsell display system.
A brilliant coating composition in which the hue H of a metal oxide-coated flake pigment other than the standard is 0 to +25, or 0 to -25 when indicated by 0, clockwise -50. 2. The above glittering coating composition, wherein the hue H of the metal oxide-coated flake pigment in the Munsell display system other than the above-mentioned standards is in the hue range of 0 to +10 or 0 to -10. 3. The mass ratio between the two or more metal oxide-coated flake pigments and the interference mica pigment having the dark area is 99 /
The glittering coating composition as described above, which is 1 to 50/50. 4. A method for forming a coating film in which a base coat layer is formed on a substrate using the above-mentioned glitter coating composition, and then a top coat layer is formed using a clear paint. 5. The above-mentioned coating film forming method, wherein the clear coating contains a carboxyl group-containing polymer and an epoxy group-containing polymer. 6. A coated article to be coated by the above-mentioned coating film forming method. 7. The above coated article, wherein the lightness L value of the coating film is 50 or less.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail. Glitter coating composition The glitter coating composition of the present invention is a coating composition containing a vehicle, two or more metal oxide-coated flake pigments, and an interference mica pigment having a dark area, wherein the two or more When one kind of the metal oxide-coated flake pigment is used as a reference, the hue of the metal oxide-coated flake pigment is set to hue 0 in the Munsell display system. When displayed, the hue H of the metal oxide-coated flake pigment other than the reference
Is a paint having a hue range of 0 to +25 or 0 to -25.

Metal oxide-coated flake pigment The metal oxide-coated flake pigment contained in the glitter coating composition of the present invention includes both a metal oxide-coated alumina flake pigment and a metal oxide-coated glass flake pigment. . In the glitter coating composition of the present invention, the metal oxide-coated flake pigment is contained in two or more types, and these are metal oxide-coated alumina flake pigment alone, metal oxide-coated glass flake pigment only, or Alternatively, a mixture of a metal oxide-coated alumina flake pigment and a metal oxide-coated glass flake pigment may be used. In consideration of coloring power, it is preferable that at least one kind of alumina flake pigment coated with a metal oxide is contained.

The hue of the metal oxide-coated flake pigment based on one of the two or more metal oxide-coated flake pigments is defined as hue 0 in the Munsell display system. In contrast, counterclockwise +5
0, when displayed in a clockwise direction of -50, the hue H of the metal oxide-coated flake pigment other than the reference is in the hue range of 0 to +25, or 0 to -25, preferably 0 to +10,
Alternatively, the hue range is set to 0 to -10. By setting each hue in this range, polychromaticity in which the hue looks different depending on the angle at which the coating film is viewed is exhibited. The metal oxide-coated alumina flake pigment has a surface of aluminum oxide (A1 ₂ O ₃ ) formed of Fe ₂ O ₃ , Ti
It is coated with a metal oxide such as O ₂ , SnO ₂ and ZrO ₂ and has an average particle diameter of 3 to 60 μm, preferably 5 to 3 μm.
0 μm, thickness 0.1-0.8 μm, preferably 0.2
.About.0.4 .mu.m. In addition, the average particle diameter in the present invention means the average particle diameter of the major axis. In addition, by having a high surface smoothness and a sharp particle size distribution, scattering by reflected light can be reduced.

Further, when the surface of a flaky alumina flake pigment having an aspect ratio (particle diameter / thickness) of 20 or more is coated with the above-mentioned metal oxide, a pigment having a pearly (pearl luster) is obtained. The used coating film shows a strong shine that cannot be obtained with the conventional mica powder from both the positions of the highlight portion and the shade portion, and can express a three-dimensional impression with transparency. On the other hand, the above-mentioned metal oxide-coated glass flake pigment is a glitter pigment in which the surface of glass flake is coated with titanium oxide as a metal oxide. The metal oxide-coated glass flake pigment has an average particle diameter of 10 to 80 μm when coated with titanium oxide.
m, more preferably 10 to 60 μm. When the average particle size is less than 10 μm, it is difficult to exhibit a glittering effect exhibiting the interference color effect, and when the average particle size is 80 μm or more, the appearance of the coating film is poor. The thickness is 0.1 to 10 μm, preferably 0.1
５5 μm. When the thickness is less than 0.1 μm, an excessive share is applied at the time of coating circulation, and the glittering pigment is deformed or broken, causing a problem that the coating is discolored with time. Might be. The metal oxide-coated flake pigment can obtain a desired hue by adjusting the type and amount (coating thickness) of the metal oxide to be coated.

The content of the metal oxide-coated flake pigment in the glittering coating composition (the ratio of the solid content of the pigment to 100 parts by weight of the solid content of the coating: PWC) is 0.01.
-30% is preferable, and 1-15% is more preferable. 0.
If it is less than 01%, it is difficult to exhibit a brilliant effect exhibiting the interference color effect, and if it exceeds 30%, the appearance of the coating film may be deteriorated.

Interference Mica Pigment Having a Dark Area The glitter coating composition of the present invention, by containing an interference mica pigment having a dark area, exhibits a three-dimensional glitter by the interference mica pigment having a dark area. As a synergistic effect with the metal oxide-coated flake pigment, a design in which a high chroma feeling in a highlight portion and a metal feeling in a shade portion are emphasized can be exhibited. This three-dimensional glitter, in the coating film obtained from the glitter coating composition of the present invention, by interference mica pigment having a dark area,
A phenomenon in which a three-dimensional effect as if the hue of the metal oxide-coated flake pigment has emerged is visually recognized.

The interference mica pigment having the dark area is
The interference color is black or almost black.
Specifically, a material in which the surface of flaky mica particles is coated or deposited with various substances in a dark region is applied.
For example, (A) an interference mica black pigment coated with black iron oxide having a chemical composition of Fe ₃ O ₄ , (B) an interference mica pigment coated with a titanium compound containing lower titanium oxide and then coated with titanium dioxide, C) After coating the surface with a titanium dioxide layer, use at least one kind of interference mica pigment in which a metal titanium portion and a lower titanium oxide portion obtained by partially reducing the titanium dioxide film are scattered on the surface by sputtering metal titanium. be able to. Among the above (A) to (C), preferred is (B). The interference mica pigment having the dark region has a particle size range of 1 to 44 μm, preferably 5 to 4 μm.
A scale-like material having a diameter of 0 μm and an average particle diameter of 15 to 25 μm can be used.

The content (PWC) of the interference mica pigment having the dark region is preferably 0.5 to less than 20%,
More preferably, it is less than 15%. If it is less than 0.5%, the intended design may not be obtained, and if it exceeds 20%, the appearance of the coating film may be reduced. Further, in order for the coating film formed from the glittering coating composition of the present invention to exhibit the intended design, it is preferable that the hue is a deep color. In order to exhibit a deep color, the type and amount of the interference mica pigment having a dark area, and a coloring pigment described later can be used in combination as needed. The L value as lightness is preferably 50 or less, more preferably 30 or less. The combined mass ratio of the two or more differently colored metal oxide-coated flake pigments and the interference mica pigment having the dark area is preferably 99/1 to 50/50, more preferably 90/10 to 60/40. It is. The above ratio is 99 /
If it exceeds 1, the three-dimensional glitter will decrease, and if it is less than 50/50, the glitter will be insufficient.

Further, the total content (PWC) of the metal oxide-coated flake pigment and the interference mica pigment having a dark area in the glittering coating composition of the present invention is preferably less than 25%, more preferably less than 20%. If it exceeds 25%, the appearance of the coating film deteriorates.

Other brilliant pigments The brilliant coating composition of the present invention has been conventionally used in paints as a brilliant pigment other than the above-mentioned metal oxide-coated flake pigment and interference mica pigment having a dark area. Can be contained. Examples of such a material include aluminum flakes, mica pigments other than interference mica pigments having a dark area, metal titanium flakes, stainless flakes, plate-like iron oxide, phthalocyanine flakes, and metal-plated glass flakes. The other glittering pigments may be contained in amounts not to impair the effects of the metal oxide-coated flake pigment and the interference mica pigment having a dark area.

Color pigment The glitter coating composition of the present invention may further contain a color pigment. Examples of such a material include those conventionally used for paints.
Examples of the organic pigments include, for example, azo lake pigments, phthalocyanine pigments, indico pigments, berylen pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, and the like. Examples of the inorganic pigment include, for example, graphite, yellow iron oxide, red iron oxide, titanium dioxide, carbon black, and the like. The amount of the color pigment to be added is such that the lightness L of the coating film to be formed is 5 as long as the effect of the metal oxide-coated flake pigment and the interference mica pigment having the dark area is not impaired.
It is preferable to set the color so as to be 0 or less. Also, various extender pigments and the like can be used in combination. The total content (PWC) of all the pigments in the paint is as follows:
It is preferably less than 50%, more preferably less than 30%. 5
If it exceeds 0%, the appearance of the coating film deteriorates.

Vehicle The vehicle contained in the glitter coating composition of the present invention is one in which the two or more kinds of metal oxide-coated flake pigments and the interference mica pigment having a dark area are dispersed. It is composed of a resin and, if necessary, a crosslinking agent.

Examples of the resin for forming a coating film constituting the vehicle include (a) an acrylic resin, (b) a polyester resin, (c) an alkyd resin, (d) a fluororesin,
(E) epoxy resin, (f) polyurethane resin, (g)
Polyether resins and the like are mentioned, and acrylic resins and polyester resins are particularly preferably used. These can be used in combination of two or more. In addition, the resin for forming a coating film includes a curable type and a lacquer type, and usually, a curable type is used. In the case of a type having curability, it is used by being mixed with a cross-linking agent such as an amino resin or a (block) polyisocyanate compound, an amine-based, a polyamide-based, or a polyvalent carboxylic acid. Let it proceed. It is also possible to use a non-curable type coating film forming resin in combination with a curable type.

(A) Acrylic resin Examples of the acrylic resin include a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Acrylic monomers that can be used for the copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, acrylic acid or methacrylic acid.
2-ethylhexyl, lauryl, phenyl, benzyl,
Examples include esterified products such as 2-hydroxyethyl and 2-hydroxypropyl, ring-opened adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate, acrylamide, methacrylamide and N-methylolacrylamide. Other ethylenically unsaturated monomers copolymerizable therewith include styrene, α-methylstyrene, itaconic acid, maleic acid, vinyl acetate and the like.

(B) Polyester resin Examples of the polyester resin include saturated polyester resins and unsaturated polyester resins. Examples thereof include condensates obtained by heat-condensing a polybasic acid and a polyhydric alcohol. Examples of the polybasic acids include saturated polybasic acids and unsaturated polybasic acids. Examples of the saturated polybasic acids include phthalic anhydride, terephthalic acid, and succinic acid. Examples of the acid include maleic acid,
Maleic anhydride, fumaric acid and the like can be mentioned. Examples of polyhydric alcohols include dihydric alcohols and trihydric alcohols. Examples of dihydric alcohols include ethylene glycol and diethylene glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane. And the like.

(C) Alkyd Resins The alkyd resins include polybasic acids and polyhydric alcohols as well as 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 and denaturing a denaturing agent such as) can be used.

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

(E) Epoxy resin Examples of the epoxy resin include a resin obtained by a reaction between bisphenol and epichlorohydrin. Examples of the bisphenol include bisphenol A and F. Examples of the bisphenol type epoxy resin include, for example, Epicoat 828, Epicoat 1001, Epicoat 1004, Epicoat 10
07 and Epicoat 1009 (both manufactured by Shell Chemical Co., Ltd.), and those obtained by chain-extending these with an appropriate chain extender can also be used.

(F) Polyurethane Resin Examples of the polyurethane resin include resins having a urethane bond obtained by a polyisocyanate compound with various polyol components such as acryl, polyester, polyether and polycarbonate. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and a mixture thereof (TDI), diphenylmethane-4,4 ′. -Diisocyanate (4,4'-MDI), diphenylmethane-
2,4′-diisocyanate (2,4′-MDI), and a mixture thereof (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,
4'-biphenylene diisocyanate (TODI), xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (HXDI), etc. Can be mentioned.

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

When the 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. Yes, preferably 85 to 60% by mass of the resin for forming the coating film and 15 to 40% by mass of the crosslinking agent. 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 not sufficient. On the other hand, when the cross-linking agent exceeds 50% by mass (when the resin for forming a coating film is less than 50% by mass), the storage stability of the coating composition is reduced and the curing speed is increased.

Ingredients Other than the Above The glitter coating composition of the present invention may further comprise, in addition to the above ingredients, 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, and the like. Anti-settling agents, curing catalysts, UV absorbers, antioxidants, leveling agents, surface conditioners such as silicon and organic polymers, anti-sagging agents, thickeners, defoamers, lubricants,
Crosslinkable polymer particles (microgel) and the like can be appropriately added. These additives are usually used in the vehicle 10 described above.
By blending at a ratio of 15 parts by mass or less with respect to 0 parts by mass (based on solid content), the performance of a paint or a coating film can be improved.

The glitter coating composition of the present invention is provided in a form in which the above-mentioned components are usually 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. Examples of the organic solvent include those commonly used in the field of coatings. Examples thereof include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ether ketone, esters such as ethyl acetate, cellosolve acetate, and butyl cellosolve, and alcohols. 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 coating film forming method of the present invention is obtained by coating the above-mentioned glitter coating composition on a substrate to form a glitter coating film as a base coat layer, and then obtaining the glitter coating film. At least one clear coating is applied as a top coat layer on the glittering coating film to form a top coat layer.

The above-mentioned substrate is not limited, and metals such as iron, aluminum, copper and alloys thereof; inorganic materials such as glass, cement, concrete, etc .; polyethylene resin, polypropylene resin, ethylene-vinyl acetate Copolymer resin, polyamide resin, acrylic resin,
Examples include resins such as vinylidene chloride resin, polycarbonate resin, polyurethane resin and epoxy resin, and plastic materials such as various FRPs; natural and synthetic materials such as wood and fiber materials (paper, cloth, etc.).

In the method for forming a coating film of the present invention, the glitter coating composition of the present invention is applied to the above-mentioned substrate directly or via an undercoating film. When the object is an automobile body or a part, it is preferable to previously apply undercoating, intermediate coating, or the like by chemical conversion treatment, electrodeposition coating, or the like. The intermediate coating is performed for concealing the base, imparting chipping resistance, and ensuring adhesion with the top coat, and forms a coating film using the intermediate coating.

In the method for forming a coating film according to the present invention, first, the above-mentioned brilliant coating composition is applied to the above-mentioned substrate as a base coat layer.

In the case where the base material is one coated with a base coat, an intermediate coat or the like, a base coat is applied on the base coat by a wet-on-wet (W / W) method or a wet-on-dry (W / D) method. The luster coating composition can be applied by a method. The W / W method is a method in which a base coat is applied, then dried by air drying or the like, and applied to an uncured or semi-cured base coat.
The method is a method in which a base coat is baked and applied to a cured base coat.

The method of applying the glitter coating composition on the substrate is not particularly limited, but a spray method, a roll coater method or the like is preferable, and the coating can be performed a plurality of times. The dry film thickness of the base coat layer coated with the glitter coating composition is preferably 5 to 50 μm per coat,
10-30 micrometers is more preferable.

On the base coat layer thus formed, at least one clear coating film is formed as a top coat layer. When there are many glittering pigments in the base coat layer, the glossiness of the surface can be improved by applying two or more clear paints.

As the clear paint used in the coating film forming method of the present invention, those which are generally used for overcoating can be used. For example, acrylic resins, polyester resins, fluororesins, epoxy resins, polyurethane resins, A mixture of at least one thermosetting resin selected from polyether resins and modified resins thereof and the above-mentioned crosslinking agent can be used.
When a clear paint containing a carboxyl group-containing polymer and an epoxy group-containing polymer described in US Pat. No. 19315 is coated with a coating having a large difference in solubility between the base coating layer and the acid rain resistance and W / W method, It is preferably used from the viewpoint of not disturbing the orientation of the glitter in the base coat layer. In addition, these clear paints, if necessary, as long as the transparency is not impaired, a coloring pigment, an extender, a modifier, an ultraviolet absorber, a leveling agent,
Additives such as dispersants and defoamers can be blended.

The application of the clear paint on the coating film of the present invention can be carried out after simultaneously curing the base coat layer and, if necessary, the layer formed from the intermediate paint. It is preferable to use the W / W method described above for the semi-cured base coat layer. In the case of applying the clear paint a plurality of times, the clear paint may be applied and baked at the same time after the final clear paint is applied. Thus, using the clear paint, W
/ W method together with the base coat layer and, if necessary,
It is baked at 60 ° C. for a predetermined time to obtain a coating film. The dry thickness of the top coat layer is preferably from 10 to 80 μm per coat, more preferably from 20 to 50 μm.

Coated product The coated product of the present invention is obtained by forming a glittering coating film as a base coat layer on a substrate by the above-mentioned coating film forming method, and then applying a top coating on the glittering coating film thus obtained. At least one clear top coat layer is formed as a coat layer. Further, the brightness L value of the glittering coating film is 50.
If it is 30 or less, preferably 30 or less, it shows polychromaticity and three-dimensional brilliancy in which the hue is different depending on the angle at which the coating film is viewed, and at the same time, it has a high chroma feeling in the highlight part and a metallic feeling in the shade part. Can exhibit a design that is further emphasized.

[0039]

EXAMPLES Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the compounding amount represents a mass part unless there is particular notice.

Examples 1 to 11 and Comparative Examples 1 to 3 Preparation of Substrates Dull steel plates (length 300 mm, width 100 mm and thickness 0.8 mm) were treated with a zinc phosphate treating agent ("Surfdyne SD2
000 "(manufactured by Nippon Paint Co., Ltd.), and then a cationic electrodeposition paint (" Power Top U-50 ", manufactured by Nippon Paint Co., Ltd.) was electrodeposited so as to have a dry film thickness of 25 [mu] m. Then, after baking at 160 ° C. for 30 minutes, an intermediate coating (“Olga S-90 Sealer Gray”,
(Nippon Paint Co., Ltd.) was applied by air spray coating so as to have a dry film thickness of 40 μm, and baked at 140 ° C. for 30 minutes to form an intermediate coating film, which was used as a substrate.

Preparation of glitter coating composition 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. Alumina flake pigment coated with metal oxide, glass flake pigment coated with metal oxide, interference mica pigment having a dark area, and if necessary, other brilliant pigments and coloring pigments in the type and proportion shown in Table 1 did. Next, the mixture was stirred and mixed with an organic solvent (mass ratio of toluene / xylene / ethyl acetate / butyl acetate = 70/15/10/5) so as to obtain a coating proper viscosity by a stirrer to prepare a glittering coating composition.

Formation of Glittering Coating Film The glittering coating composition obtained above was coated on the surface to be coated of the above-mentioned substrate 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 . The atmosphere in the booth during coating was maintained at a temperature of 25 ° C. and a humidity of 75%. After the coating, the coating was set for 3 minutes, the 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 obtained coating film was evaluated for polychromaticity, three-dimensional glitter, high chroma in a highlight portion, and metallic feeling in a shade portion by the following evaluation methods. The results are shown in Table 1. The clear paint used was an acrylic / melamine resin clear paint 1 ("Super Lac O-130 Clear", manufactured by Nippon Paint Co., Ltd.)
Alternatively, there are two types of clear paints 2 ("Macflow O-520 Clear", manufactured by Nippon Paint Co., Ltd.) containing a carboxyl group-containing polymer and an epoxy group-containing polymer. Table 1 shows the evaluation results.

Evaluation Method Polychromaticity: It was visually evaluated whether or not the hue was different when the test plate was viewed from almost directly in front (highlight portion) and when the test plate was viewed from oblique (shade portion). did. 3: noticeably different hue 2 ... slightly different hue 1 ... no change in hue Three-dimensional brilliancy: between metal oxide-coated flake pigment in coating film after coating film formation and interference mica pigment having dark area Among them, a phenomenon visually recognized as a three-dimensional effect as if the hue of the metal oxide-coated flake pigment was raised was visually evaluated. 3: There is a remarkable three-dimensional effect 2 ... There is a three-dimensional effect 1 ... There is no three-dimensional effect High saturation feeling in the highlight part: 3 ... There is a high saturation feeling 2 ... There is a high saturation feeling 1 ... There is no high saturation feeling Shade part Metallic feeling in: 3 ... Metallic feeling is remarkable 2 ... Metallic feeling 1 ... No metallic feeling

[0044]

[Table 1]

As is evident from the results in Table 1, Examples 1 to 11 were obtained by forming a coating film by the glittering coating film forming method of the present invention. Not
A brilliant coating film exhibiting a high chroma feeling in the highlight part and a metallic feeling in the shade part was obtained. On the other hand, Comparative Examples 1 to 3
The result was that a glittering coating film satisfying all of polychromaticity, three-dimensional glitter, high chroma in highlights, and metal in shades could not be obtained.

[0046]

According to the present invention, a coating film of a metal oxide-coated flake pigment can be formed by simultaneously defining the hue difference of two or more metal oxide-coated flake pigments and using an interference mica pigment having a dark area. The hue is different depending on the viewing angle, and the three-dimensional radiance of the interference mica pigment having a dark area is expressed, and as a synergistic effect of these, high saturation feeling in the highlight area and shade area Thus, it is possible to form a coating film capable of exhibiting a design that emphasizes the metallic feeling and a higher-grade glittering feeling. In addition, since the coating film obtained by the present invention strongly exhibits the above-mentioned brilliant feeling, automobiles,
Vehicle outer panels such as motorcycles, container outer surfaces, coil coating,
It is preferably used in painted products requiring glitter, such as in the home appliance industry.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09C 1/00 C09C 1/00 3/06 3/06 C09D 5/00 C09D 5/00 Z 7/12 7 / 12 F term (Reference) 4D075 CB13 DB02 DC12 EA02 EA05 EA43 EB22 EB33 EC02 EC04 EC54 4J037 AA25 AA30 CA09 DD05 DD09 DD10 EE03 FF09 4J038 CD091 CG141 CH031 DB061 DD041 DD181 DE001 DG08 GA06 NA1919

Claims (7)

[Claims] 1. A coating composition comprising a vehicle, two or more metal oxide-coated flake pigments, and an interference mica pigment having a dark area, wherein one of the two or more metal oxide-coated flake pigments is used. The hue of the metal oxide-coated flake pigment used as a reference is defined as a hue 0 in the Munsell display system, and when displayed with a counterclockwise rotation of +50 and a clockwise rotation of −50 with respect to the Munsell hue circle 100, other than the reference hue. The hue H of the metal oxide-coated flake pigment is 0 to +2
5 or a glitter coating composition having a hue range of 0 to -25. 2. The hue H of the metal oxide-coated flake pigment other than the above-mentioned reference in the Munsell display system is 0 to +1.
The glittering coating composition according to claim 1, wherein the composition has a hue of 0 or 0 to -10. 3. The glittering paint according to claim 1, wherein the mass ratio of the two or more metal oxide-coated flake pigments to the interference mica pigment having the dark region is 99/1 to 50/50. Composition. 4. A coating film formed by forming a base coat layer on a substrate using the glitter coating composition according to claim 1 and then forming a top coat layer using a clear paint. Method. 5. The method according to claim 4, wherein said clear paint contains a carboxyl group-containing polymer and an epoxy group-containing polymer. 6. A coated article applied by the coating film forming method according to claim 4. 7. The coated article according to claim 6, wherein the lightness L value of said coating film is 50 or less.