JP2001232285A - Brilliant multilayered coating film forming method and coated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant multilayered coating film forming method for forming a film provided with stereoscopic feeling in addition to the glittering brilliant feeling generated by the multi-directional reflection of an alumina flake pigment coated with a metal oxide and also provide a coated material thereof. SOLUTION: The alumina flake pigment coated with the metal oxide and a specified brilliant pigment are contained in a brilliant base coating material composition, and the hue of the alumina flake pigment coated with the metal oxide is set in the specific range in which the hue of the brilliant pigment is set as a reference. A coloring pigment of the hue in the specified range in which the hue of the alumina flake pigment coated with the metal oxide is set as the reference is contained in a clear coating material composition forming a clear film to be overlapped on a base film.

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 brilliant multilayer coating film and a coated product. More specifically, the present invention relates to a method for forming a brilliant multilayer coating film capable of providing a brilliant coating film capable of enhancing a three-dimensional effect in addition to a brilliant feeling, and a coated article coated by this method.

[0002]

2. Description of the Related Art In a field requiring high designability such as an automobile body, a coating film using a glittering base coating composition containing a glittering material is required. As one of the materials, a metal oxide-coated alumina flake pigment is known. Since the metal oxide-coated alumina flake pigment has high particle brightness, when a strong light such as sunlight is irradiated on a highlight portion in particular, the coating film exhibits a strong glitter. Furthermore, when the viewing angle is changed, it appears as if the glittering particles move in conjunction with it. The pigment can have a specific color by changing the thickness of the metal oxide coating.

In connection with the above problem, Japanese Patent Laid-Open No. 10-183
In No. 033, the brilliancy of the highlight part is excellent,
A method for forming a multi-layer coating film having a high saturation at the metal part is disclosed. Here, when applying the colored paint, the interference paint and the color clear paint, the interference paint is an organic solvent-based paint containing aluminum oxide powder coated with metal oxide and mica powder coated with metal oxide. It is stated that there is.

[0004]

However, Japanese Patent Application Laid-Open No.
According to the technique disclosed in Japanese Patent No. 183033, it is possible to increase the brilliancy and the saturation of a shade portion, but no consideration has been given to obtaining a three-dimensional effect. Therefore, an object of the present invention is to provide a glittering multilayer coating film capable of forming a coating film having a three-dimensional appearance, in addition to the glittering glittering caused by multi-directional reflection of the metal oxide-coated alumina flake pigment. An object of the present invention is to provide a forming method and a coated object.

[0005]

According to the present invention, there is provided a method for forming a brilliant multilayer coating film comprising a vehicle, a metal oxide-coated alumina flake pigment, a colored mica pigment, an interference mica pigment, a colored aluminum pigment, and a metal oxide. A glitter base coating composition comprising at least one glitter pigment selected from a coated silica flake pigment and a metal oxide-coated glass flake pigment, wherein the metal oxide-coated alumina flake pigment is in a Munsell display system. hue H ₁ is to Munsell hue circle 100 hue of H ₂ the bright pigment 0
When displayed in the counterclockwise direction +50 and clockwise direction -50, +
A brilliant base coating composition having a hue range of 25 to +50 or -25 to -50 is applied to a substrate to form a brilliant base coating layer, and a vehicle and
A color clear coating composition containing a color pigment, wherein the color pigment has a hue H in a Munsell display system.
_3, the hue H ₁ of the metal oxide coated alumina flake pigment and 0 to Munsell hue circle 100, the counterclockwise +5
0, clockwise -50, H ₁ -10 ≦ H ₃ ≦ H
A color clear coating composition having a hue range of ₁ + 10 is applied to form a color clear coating layer.

The above metal oxide-coated alumina flake pigment
Hue H in Munsell display system₁Is preferably +3
The hue range is from 3 to +50, or from -33 to -50.
Further, the hue H of the above color pigment in the Munsell display system is_Three
Is preferably H₁−5 ≦ H_Three≤H₁+5 hue range
You. Further, the above metal oxide-coated alumina flake pigment
And the glitter pigment has a mass ratio of 90/10 to 10/90.
It is preferred that In addition, the above color clear paint
The vehicle of the composition contains a carboxyl group-containing polymer and
And an epoxy group-containing polymer. The present invention
The coated product is coated by the method for forming a glittering multilayer coating film described above.
It was dressed. The above hue H ₁, H_Twoand
H_ThreeIndicates the hue exhibited when the coating film is formed.
You.

[0007]

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

Vehicle The vehicle contained in the glittering base coating composition and the color clear coating composition used in the present invention comprises a resin for forming a coating film 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.

When the resin for forming a coating film is curable, the resin is mixed with an amino resin, a (block) polyisocyanate compound, a crosslinker such as an amine, a polyamide or a polycarboxylic acid, and used for heating. Alternatively, the curing reaction can proceed at room temperature. 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. Polybasic acids include saturated polybasic acids and unsaturated polybasic acids.Examples of saturated polybasic acids include phthalic anhydride, terephthalic acid, and succinic acid.Examples of unsaturated polybasic acids include: Maleic acid, maleic anhydride and fumaric acid are included. Examples of the polyhydric alcohol include dihydric alcohols and trihydric alcohols. Examples of the dihydric alcohol include ethylene glycol and diethylene glycol, and examples of the trihydric alcohol include glycerin and trimethylolpropane. Can be

(C) Alkyd Resins The alkyd resins include the above-mentioned 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 As the fluororesin, any one of vinylidene fluoride resin and ethylene tetrafluoride resin or a mixture thereof, a fluoroolefin and a hydroxyl group-containing polymerizable compound and other copolymerizable vinyl Examples include resins made of various fluorine-based copolymers obtained by copolymerizing monomers made of a series 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 bisphenols A and F. Examples of the bisphenol-type epoxy resin include, for example, Epicoat 828, Epicoat 1001, Epicoat 1004, Epicoat 100
7, Epicoat 1009 (all manufactured by Shell Chemical Co., Ltd.), and those obtained by chain-extending these with an appropriate chain-extending agent can also be used.

(F) Polyurethane Resin Examples of the polyurethane resin include resins having a urethane bond obtained by various polyol components such as acryl, polyester, polyether and polycarbonate and a polyisocyanate compound. 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 above polyether resin is a polymer or copolymer having an ether bond, and is a polyoxyethylene polyether, a polyoxypropylene polyether, a 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 cross-linking agent, the ratio of the resin for forming a film to the cross-linking agent is 90 to 50% by mass and the content of the cross-linking 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.

However, the vehicle of the color clear paint includes a combination of a carboxyl group-containing polymer and an epoxy group-containing polymer described in JP-B-8-19315. This polymer is used to prevent acid rain, and
When the coating is applied by a wet-on-wet method with a large difference in solubility from the glittering base coating layer, it is preferably used from the viewpoint of not disturbing the orientation of the glitter contained in the glittering base coating layer.

The vehicle may be the same or different in the glitter base coating composition and the color clear coating composition used in the method of the present invention.

Metal oxide-coated alumina flake pigment The metal oxide-coated alumina flake pigment contained in the glittering base coating composition used in the present invention is composed of flake-like aluminum oxide (A1 ₂ O ₃ ), Fe ₂ O ₃ , TiO ₂ ,
The average particle size coated with a metal oxide such as SnO ₂ or ZrO ₂ is 3 to 60 μm, preferably 5 to 30 μm, and the thickness is 0.1 μm.
The particles have a size of 1 to 0.8 μm, preferably 0.2 to 0.4 μm. Among them, those having a high surface smoothness and a sharp particle size distribution can reduce scattering by reflected light. 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 exhibiting a pearly (pearl luster) is obtained. Presents a strong brilliance that cannot be obtained with conventional mica powder from both the highlight and shade positions, and can express a three-dimensional impression with transparency. As such a metal oxide-coated alumina flake pigment, for example, “Xirallic T60-20WII Su” sold by Merck Japan Ltd.
"Xirall" such as "nbeam Gold" (trade name)
ic "series.

The above-mentioned metal oxide-coated alumina flake pigment can obtain a desired hue by adjusting the type and coating thickness of the metal oxide to be coated. The hue H ₁ metal oxide coated alumina flake pigment, hue in the Munsell display system, the hue of H ₂ bright pigment in combination to Munsell hue circle 100 to 0, the left around +50, clockwise -5
+25 to +50 or -25 to -5 when displayed as 0
0, preferably +33 to +50, or -33 to -50
By setting the hue range as described above, mutual coloring with the glitter pigment used in combination occurs, and a three-dimensional three-dimensional glitter can be exhibited. The three-dimensional glitter, in the coating film obtained from the glitter base paint composition used in the present invention, of the metal oxide-coated alumina flake pigment and the glitter pigment, of the metal oxide-coated alumina flake pigment A phenomenon in which a three-dimensional effect as if the hue has emerged is visually recognized.

The hue H _{1 of the} metal oxide-coated alumina flake pigment means the interference color of this pigment, and the hue H ₂ of the glittering pigment is the same as that of the pigment which produces the interference color. Let the color be the hue.

The content of the metal oxide-coated alumina flake pigment in the glittering base coating composition (solids content of 10
(Ratio of solid content by mass of pigment to 0 mass part: PWC)
Is preferably 0.01% to 20%, more preferably 1% to 15%, and still more preferably 3% to 10%. If it exceeds 20%, the appearance of the coating film is reduced, and if it is less than 0.01%, the glittering glitter is reduced.

Glitter Pigment The glitter pigment contained in the glitter base coating composition used in the present invention includes colored mica pigments, interference mica pigments,
Colored aluminum pigments, metal oxide coated silica flake pigments and metal oxide coated glass flake pigments are included. More specifically, colored mica pigments are coated with metal oxides such as titanium dioxide, iron oxide, chromium oxide, cobalt oxide, tin oxide, and zirconium oxide on the surface of mica made from natural muscovite or synthetic mica. Further, a pigment or a dye is further coated thereon. The colored mica pigment emits both a reflection color of the metal oxide layer and an absorption color of the pigment or dye. Further, the interference mica is obtained by coating titanium dioxide on the mica surface more thickly than the colored mica pigment, and emits different interference colors depending on the thickness of the metal oxide layer. Both colored mica and interference mica have a particle size range of 1 to 60 μm
, Preferably 1 to 40 μm, and an average particle size of 15 to 25.
μm scale-like ones can be used.

The colored aluminum pigment is obtained by chemically adsorbing the colored pigment on the surface of an aluminum flake treated with a fatty acid such as oleic acid or stearic acid, or coating the chemically adsorbed surface with a resin. The colored aluminum pigment is scaly and has an average particle size of 1 to 100 μm.
m, further 5 to 50 μm, average thickness 0.1 to 5 μm,
Further, those having a thickness of 0.2 to 4 μm are suitable for use.

The metal oxide-coated silica flake pigment and the metal oxide-coated glass flake pigment are obtained by coating silica flake or glass flake with the same metal oxide as used in the above-mentioned metal oxide-coated alumina flake pigment. is there. The average particle size of these flake pigments is 3 to 60 μm, preferably 5 to 30 μm, and the thickness is 0.1 to 0.8 μm, preferably 0.2 to 0.4 μm.

The mass ratio of the metal oxide-coated alumina flake pigment / brilliant pigment in the glittering base coating composition used in the present invention is in the range of 90/10 to 10/90, preferably 70/30 to 10/90. It is. The above ratio is 90
If the ratio exceeds / 10, the three-dimensional glitter decreases, and
When the ratio is less than the above range, the glittering feeling may be insufficient.

Other brilliant pigments The above brilliant base coating composition has been used as a brilliant pigment in addition to the metal oxide-coated alumina flake pigment and the specific brilliant pigment described above, and has been used for paints. Can be contained. Examples of such a material include titanium metal flake, stainless steel flake, plate-like iron oxide, and phthalocyanine flake. These other brilliant pigments can be contained in any amount within a range that does not hinder the effects of the metal oxide-coated alumina flake pigment and the specified brilliant pigment.

Color Pigment The color clear coating composition used in the present invention contains a color pigment. Also, in the glitter base coating composition,
A coloring pigment can be contained as needed. Examples of such color pigments include those conventionally used for paints.Examples of organic pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, and quinophthalone pigments. And dioxazine-based pigments, quinacridone-based pigments, isoindolinone-based pigments, metal complex pigments, and the like. Examples of the inorganic pigments include yellow iron oxide, red iron oxide, titanium dioxide, and carbon black.

Coloring to be added to the color clear coating composition
The pigment is the hue H of the colored pigment in the Munsell display system.
_ThreeIs H₁-10 ≦ H_Three≤H₁+10, preferably H₁-5
≤H_Three≤H ₁Must be in the range of +5. Note that these
Is the specific glittering face for the Munsell hue circle 100.
Hue H₁With 0, counterclockwise +50, clockwise −50
It is a numerical value when expressed. Hue H_ThreeTo H₁-10 ≦ H_Three
≤H₁Metal oxide coating by limiting to the range of +10
Because the hue of alumina flake is emphasized,
The hue difference from the bright pigments stands out, and metal oxide coated aluminum
The naflake pigments are more raised and appear three-dimensional. I
Scarecrow, hue H_ThreeIs H₁-10 ≦ H_Three≤H₁From the range of +10
If it deviates, the color will become cloudy and the three-dimensional appearance will fade.

The content of the color pigment in the color clear paint is determined so as not to suppress the glitter of the metal oxide-coated alumina flake pigment in the glitter base coating film and the glitter of the specific glitter pigment. (Wavelength 4
00 to 700 nm) The transmittance is 3 μm when the dry film thickness is 30 μm.
It is necessary to adjust so as to be in the range of 0 to 90%.

On the other hand, regarding the addition of the coloring pigment to the glittering base coating composition, the addition amount and the kind of the pigment may be arbitrarily adjusted according to the hue as long as the effects of the metal oxide-coated alumina flake pigment and the glittering pigment are not hindered. Can be set. When the above-mentioned other glitter pigments and coloring pigments are used for the glitter base paint, the total content (PWC) of the pigment as a whole including the metal oxide-coated alumina flake pigment and the specific glitter pigment is less than 50%. Preferably, it is less than 30%. If it exceeds 50%, the appearance of the coating film deteriorates.

Other Components Other than the above components , the color clear coating composition and the glittering base coating composition used in the present invention mainly comprise polyamide wax or polyethylene oxide which is a lubricating dispersion of an aliphatic amide. Antisedimentation agent, a curing agent, an ultraviolet absorber, an antioxidant, a leveling agent, a surface conditioning agent such as silicon and organic polymers, a sagging agent, an extender pigment, a rust preventive pigment , Thickener, defoamer, lubricant, crosslinkable polymer particles (microgel)
Etc. can be appropriately added. The performance of paints and coatings can be improved by blending these additives at a ratio of 15 parts by mass or less based on 100 parts by mass of the vehicle (based on solid content).

The color clear coating composition and the glittering base coating composition used in the present invention comprise
Usually, it is 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. Examples of the organic solvent include those commonly used in the coatings field, for example, hydrocarbons such as toluene and xylene, acetone, ketones such as methyl ethyl ketone, ethyl acetate, cellosolve acetate, esters such as butyl cellosolve, There are alcohols such as i-propanol and n-butanol. When the use of an organic solvent is regulated from the environmental aspect, water is mainly used, but in this case, a suitable amount of a hydrophilic organic solvent such as the alcohol is contained to improve the dispersibility of the pigments. You can also.

The method for forming a glittering multi-layer coating film of the present invention comprises applying the glittering base coating composition on a base material to form a glittering coating film as a base coat layer. The topcoat layer is formed by applying at least one color clear coating as a topcoat layer on the glittering coating film.

The substrate is not particularly limited, and examples thereof include metals such as iron, aluminum, copper and alloys thereof, inorganic materials such as glass, cement and concrete;
Resins such as polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, and various FRP
And other plastic materials, wood, fiber materials (paper, cloth, etc.)
And natural or synthetic materials.

In the method for forming a glittering multilayer coating film of the present invention, the glittering base coating composition is applied to the above-mentioned substrate directly or via an undercoating film. In the case of parts, it is preferable to previously apply undercoating, intermediate coating, or the like by chemical conversion treatment, electrodeposition coating, or the like. Intermediate coating, in addition to the concealment of the base, imparting chipping resistance and ensuring adhesion with the top coat, if necessary, express a composite color with the top coat and are performed to enhance the design. The coating film is formed by using a gray color intermediate coating or a color intermediate coating.

In the method for forming a glittering multi-layer coating film of the present invention, a glittering base coating composition is first applied to the above-mentioned substrate as a base coat layer. In the case where the base material is a base coat coated with an undercoat, an intermediate coat, etc., the brilliancy is applied on the base coat by a wet-on-wet (W / W) method or a wet-on-dry (W / D) method. A base coating composition can be applied. 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 that has been baked and cured is applied.

The method of applying the above-mentioned glittering base coating composition on a substrate is not particularly limited, but a spray method, a roll coater method or the like is preferable, and it is also possible to apply a plurality of times. The dry film thickness of the base coat layer coated with the glittering base coating composition is preferably 5 to 50 μm, more preferably 10 to 30 μm per coat.

On the glittering base coating film layer thus formed, at least one color clear coating film is formed as a top coat layer. When the glittering base coating film contains a lot of glittering pigments, it is possible to improve the glitteriness of the surface by further applying one or more layers of a color clear paint or a clear paint containing no color pigment. it can. When a clear paint containing no color pigment is used in combination, there is no limitation on the order of applying the color clear coating film. For example, it may be a color clear coating and then a clear coating adjacent to the glittering base coating layer, or a clear coating and then a color clear coating adjacent to the glittering base coating layer.

The application of the color clear paint 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 above W / W method for the uncured or semi-cured base coat layer. When the clear paint is applied a plurality of times, all the clear paints may be applied and then baked at the same time, and it is not necessary to completely cure the color clear paints at the stage of applying the color clear paints first. Thus, using a color clear paint, W
/ W method, together with the glittering base coating layer and, if necessary,
It is baked at a temperature of up to 160 ° 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.

[0043]

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 4 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, the intermediate coating (“Olga S-90 Sealer Gray (N-
6) ", manufactured by Nippon Paint Co., Ltd.) was applied by air spraying 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.

On the other hand, in the preparation of the base material 1 as the base material for exhibiting the composite color of the base coat and the top coat, the intermediate coat was coated with “Olga S-90 Sealer Gray (N-4)”.
What was obtained in place of (Nippon Paint Co., Ltd.)
And

Preparation of glittering base 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 (trade name, “Uban 20SE”, manufactured by Mitsui Chemicals, Inc., solid content of 60% by mass) are blended at a solid content mass ratio of 80:20. The obtained vehicle was mixed with a metal oxide-coated alumina flake pigment, a brilliant pigment and, if necessary, carbon black in the types and proportions shown in Table 1. 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 an appropriate coating viscosity by using a stirrer to prepare a glittering base coating composition.

Preparation of Color Clear Paint Composition Acrylic / melamine resin clear paint 1 (trade name:
"Super Lac O-130 Clear", manufactured by Nippon Paint Co., Ltd., or 2 of a clear paint 2 containing a carboxyl group-containing polymer and an epoxy group-containing polymer ("Macflow O-520 Clear", manufactured by Nippon Paint Co., Ltd.)
Each kind was prepared, and a coloring pigment corresponding to the hue of the metal oxide-coated alumina flake pigment in the glittering base paint to be used was added to obtain a color clear coating composition.

The glitter base coating composition obtained above was applied to the surface of the substrate on which the glitter coating film was to be formed so that the dry film thickness was 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 coating, set for 3 minutes, apply color clear paint to dry film thickness of 35 μm, and apply at room temperature for 10 minutes.
Minutes and baked at a temperature of 140 ° C. for 30 minutes. The glitter and three-dimensional effect of the obtained coating film were evaluated by the following methods. Table 1 shows the results.

Evaluation method <Glittering feeling> The glittering feeling of the metal oxide-coated alumina flake pigment particles when the test plate was viewed almost from the front (highlighted area) was linked to the glittering particles when the viewing angle was moved. The movement was evaluated visually. 3: There is remarkable interlocking movement of glittering particles and glittering particles. 2 ... There is a little interlocking motion of glittering particles and glittering particles. 1. There is no interlocking motion of glittering particles and glittering particles. Feeling> Of the metal oxide-coated alumina flake pigments and glitter pigments in the coating film after the coating film formation, visually evaluate the phenomenon in which the hue of the metal oxide-coated alumina flake pigment is visually recognized as a three-dimensional appearance as if it were raised. did. 3: There is a noticeable 3D effect 2 ... There is a 3D effect 1 ... There is no 3D effect

[0050]

[Table 1]

The amount of each pigment compounded was a solid part by mass based on 100 parts by mass of the solid content of the paint. Kind of Alumina flake pigment coated with metal oxide: A1; Alumina flake pigment coated with gold-colored titanium oxide "Xirallic T60-20WIII Sunb
Eam Gold "(manufactured by Merck) A2; green coloring titanium oxide-coated alumina flake pigment" Xirallic T60-24WIII Steel "
lar Green "(manufactured by Merck Ltd.) B; a red-colored iron oxide-coated alumina flake pigment" Xi
rallic F60-51WIII Radiant
Red "(Merck)

Types of glitter pigments: B; Blue mica pigment coated with titanium oxide: "IRIODI"
N225WII "(manufactured by Merck) R1; iron oxide-coated red mica pigment:" IRIODIN "
504WII "(manufactured by Merck) R2; colored (red) aluminum flake pigment:" Friend Color F500RE "(manufactured by Showa Aluminum) G; titanium oxide-coated green mica pigment:" IRIOD "
IN235WII "(Merck)

Kinds of coloring pigments: A; (yellow color: isoindoline yellow) B; (green color: phthalocyanine green) C; (red color: perylene red) ΔHa is a metal oxide based on the hue of the bright pigment. Difference of alumina flake pigment coated with material. ΔHb is the hue difference of the coloring pigment based on the hue of the metal oxide-coated alumina flake pigment.

[0054]

The coated article formed by the method for forming a glittering multilayer coating film of the present invention is characterized by defining the hue difference between the metal oxide-coated alumina flake pigment and the glittering pigment in the glittering base paint. Thus, in addition to the glittering glitter due to the multi-directional reflection of the metal oxide-coated alumina flake pigment, a three-dimensional glitter can be exhibited. Further, by defining the hue difference between the color pigment in the color clear paint and the above-mentioned alumina flake pigment coated with the metal oxide, it is possible to form a coating film with a further enhanced three-dimensional appearance. Was. In addition, the coating film obtained by the present invention is tough, and exhibits a unique glittering feeling excellent in a three-dimensional appearance with transparency, so that it can be used in automobiles, motorcycles and other vehicles, vehicle outer panels, container outer surfaces, coil coating, home appliance industry, etc. It is preferably used in a painted product requiring glitter.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/29 C09D 5/29 201/00 201/00 F-term (Reference) 4D075 DC12 EC02 EC03 EC04 EC11 EC23 4J038 CD091 CG141 CH031 CH041 CH121 CJ031 CJ101 DA111 DB061 DD041 DD121 DF001 DG101 DG301 GA06 GA07 HA026 HA066 HA166 HA486 HA546 JA35 JB02 JB14 KA03 KA06 KA08 KA15 NA01 NA11 NA19 PA19 PB04 PB07 PB09

Claims (6)

[Claims] 1. A vehicle, a metal oxide-coated alumina flake pigment, and at least one selected from a colored mica pigment, an interference mica pigment, a colored aluminum pigment, a metal oxide-coated silica flake pigment, and a metal oxide-coated glass flake pigment. A brilliant base coating composition containing a brilliant pigment of the type described above, wherein the hue H ₁ in the Munsell display system of the metal oxide-coated alumina flake pigment is the hue H of the brilliant pigment relative to the Munsell hue circle 100. _{When 2 is set} to 0 and displayed counterclockwise +50 and clockwise -50, +2
A brilliant base coating composition having a hue range of 5 to +50 or -25 to -50 is applied to a substrate to form a brilliant base coating layer, and a vehicle and coloring are formed on the base coating layer. A color clear coating composition containing a pigment and a hue H in a Munsell display system of the color pigment.
_3, the hue H ₁ of the metal oxide coated alumina flake pigment and 0 to Munsell hue circle 100, the counterclockwise +5
0, clockwise -50, H ₁ -10 ≦ H ₃ ≦ H
_A method for forming a glittering multi-layer coating film, comprising applying a color clear coating composition having a hue range of ₁ + 10 to form a color clear coating layer. 2. A hue H ₁ in said metal oxide Munsell display system of the coated alumina flake pigments, + 33 to + 5
2. The method for forming a glittering multi-layer coating film according to claim 1, wherein the hue range is 0 or -33 to -50. 3. The glittering multilayer according to claim 1, wherein the hue H ₃ of the coloring pigment in the Munsell display system is in a hue range of H ₁ -5 ≦ H ₁ ≦ H ₂ +5. A method for forming a coating film. 4. The mass ratio of the metal oxide-coated alumina flake pigment to the glitter pigment is 90/10 to 10/90.
The method for forming a glittering multilayer coating film according to any one of claims 1 to 3, wherein 5. The glittering multi-layer coating film according to claim 1, wherein the vehicle of the color clear coating composition contains a carboxyl group-containing polymer and an epoxy group-containing polymer. Forming method. 6. A coated article, which is coated by the method for forming a glittering multilayer coating film according to any one of claims 1 to 5.