JP2002201425A - Gloss coating composition, method for forming coating film, and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gloss coating composition capable of obtaining a color feeling in the shade part, giving the color of similar shade in the highlight part and the shade part, and yellowish color in the middle part, and showing the design of giving two colors in three steps, and capable of forming a coating film giving gloss feeling of higher quality, a method for forming coating film, and a coated product. SOLUTION: This gloss coating composition is a coating composition containing s vehicle, colored gloss pigment (a), a mixture of minute particles of titanium dioxide and aluminum flakes (b), and a sintered compound oxide pigment (c), and the color of colored gloss pigment (a) and the color or the sintered compound oxide pigment (c) are not in similar shade, and both the color of the colored gloss pigment (a) and the color of the sintered compound oxide pigment (c) are in the range of -20 to -50 or +20 to +50 in Munsell hue circle display, where the color 10Y (yellow) is taken 0, and displayed counterclockwise to +50, and clockwise to -50, for Munsell hue circle 100.

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 containing a plurality of brilliant pigments is used, and a brilliant coating material for forming such a brilliant coating film is used. As such, there has been known a combination of interference mica and aluminum flake.

[0003] These coating films exhibit a dichroic design that exhibits different colors when viewed from almost directly in front of the direction of light reflection (highlight portion) and obliquely (shaded portion). However, the design that appears is that the color changes from the highlight area to the shade area.
It stays in color development. In contrast to such a design in which two colors are formed in two stages, a three-stage design in which a different color is formed in a middle portion between a highlight portion and a shade portion having a concealing property as a design having a higher quality feeling. It is desired to develop a design that produces two colors.

Further, a coating film containing the interference mica as a brightener generally has an insufficient concealing property. Therefore, a coating film having a further concealing property is required.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a colored portion in a shade portion, a highlight portion and a shade portion to produce a non-yellow similar color, and a shade portion and a high color portion. A yellowish color can be obtained in the middle of the light part, and a design that develops two colors in three stages can be developed.
An object of the present invention is to provide a glitter coating composition, a coating film forming method, and a coated article.

[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. A paint composition comprising a vehicle, (a) a colored glitter pigment, (b) a mixture of fine particle titanium dioxide and aluminum flake, and (c) a calcined composite oxide pigment, wherein the (a) colored glitter pigment is Is the same color as the hue of the calcined composite oxide pigment (c), the hue 10Y (yellow) in the Munsell hue circle display system is set to 0, and the counterclockwise +50 and clockwise with respect to the Munsell hue circle 100. -50
In the hue display of the display system indicated by the above, the glitter paint wherein the hue of the (a) colored glitter pigment and the hue of the (c) fired composite oxide pigment are in the range of -20 to -50 or +20 to +50. Composition. 2. In the above display system hue display, the glitter coating composition wherein the difference between the hue of the colored glitter pigment (a) and the hue of the composite oxide fired pigment (c) is less than 20. 3. In the hue display of the display system, the glitter paint wherein the hue of the colored glitter pigment (a) and the hue of the calcined composite oxide pigment (c) are in the range of -30 to -50 or +30 to +50. Composition. 4. (A) The above-mentioned glittering coating composition, wherein the coloring glittering pigment has a hiding property of 100 μm or less. 5. The mass ratio of (a) / (b) / (c) is 10 to 1
The glittering coating composition described above, wherein the composition is 00/10 to 100/100. 6. The above glittering coating composition, wherein the mass ratio between the fine particle titanium dioxide and the aluminum flake is 99/1 to 30/70. 7. The above (a) colored glitter pigment, (b) a mixture of fine particle titanium dioxide and aluminum flakes, and (c) the calcined composite oxide pigment are 5 to 50% as PWC.
The glittering coating composition described above. 8. The glitter coating composition according to the above, wherein the colored glitter pigment (a) is a colored aluminum flake pigment and / or a colored mica pigment. 9. A method for forming a coating film in which a base coat layer is formed on a substrate using the above-described glittering paint composition, and then a top coat layer is formed using a clear paint. 10. The above-described coating film forming method, wherein the clear coating contains a carboxyl group-containing polymer and an epoxy group-containing polymer. 11. A coated article to be coated by the above-mentioned coating film forming method. 12. A coated object in which the surface to be coated of the above-mentioned coated object has a curved surface.

[0007]

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 comprises a vehicle, (a) a colored glitter pigment, (b) a mixture of fine particle titanium dioxide and aluminum flake,
And (c) a coating composition containing a calcined composite oxide pigment.

A design that forms two colors in three stages In the present specification, a “ design that forms two colors in three stages” means that a highlight portion and a shade portion produce similar colors.
In the middle part between the highlight part and the shade part, it means a design that develops a yellowish color. This will be described with reference to FIG. 1 which is a conceptual diagram.

[0010] The coating material 1 has a coating film formed on a curved substrate to be coated such as an automobile door by using the above-mentioned glittering coating composition. In this coating film, the hue of the colored brilliant pigment appears in the highlight portion 2, and the hue of the composite oxide fired pigment develops in the shade portion 3. Here, the highlight portion is perpendicular to the light incident direction 5,
It refers to a portion viewed from a position substantially in front of the direction 6 in which light is reflected. On the other hand, in an intermediate portion 4 between the highlight portion 2 and the shade portion 3, a yellowish color, which is a composite color of the fine particle titanium dioxide and the aluminum flakes, is developed. At this time, the color developed in the highlight portion 2 and the shade portion 3 is not yellowish, and the highlight portion 2 and the shade portion 3 produce similar colors, so that the painted object 1 can be changed depending on the viewing angle. Highlight part → middle part → shade part and 3
It is possible to develop a two-color brilliant design at the stage. Since the painted object 1 is curved, the boundary of the highlight part 2 / intermediate part 4 / shade part 3 is not clearly distinguished in an actual coating film.
A design in which the color gradually changes over the / intermediate part 4 / shade part 3 is given.

As a first condition for expressing a design that forms two colors in these three stages, the hue of the (a) colored glittering pigment and the (c) hue of the calcined composite oxide pigment are as follows.
They have similar colors. In the case of non-similar colors, it is not possible to express a design that produces two colors in three stages.

Further, as a second condition, the hue 10Y (yellow) in the display system of the Munsell hue circle is set to 0, and the hue display of the display system displayed with +50 counterclockwise and −50 clockwise with respect to the Munsell hue 100. The hue of the (a) colored glittering pigment and the hue of the (c) fired composite oxide pigment are in the range of -20 to -50 or +20 to +50. If the ratio is out of this range, a design that develops two colors in three stages cannot be exhibited. Preferably, the hue of the colored glittering pigment (a) and the hue of the calcined composite oxide pigment (c) are -30 to -50 or +30 to +5.
It is in the range of 0.

The range of the similar colors is such that the difference between the hue of the colored glittering pigment (a) and the hue of the calcined composite oxide pigment (c) is 20 in the hue display in the Munsell hue circle display system. Is more preferably less than 5, more preferably less than 5. By satisfying these conditions, a design that develops two colors in three stages can be developed.

The hue of the colored brilliant pigment and the baked composite oxide pigment is the color development of the highlight portion.

(A) Colored glitter pigment As the colored glitter pigment (a), a colored aluminum flake pigment and / or a colored mica pigment are preferably used. Preferably, it is a colored aluminum flake pigment.

The above-mentioned colored aluminum flake pigment is an aluminum flake pigment obtained by coating a base aluminum flake with a colored pigment in the form of flakes. For example, the particle size range is 1 to 100 μm, preferably 1 to 70 μm.
A scaly one having an average particle diameter of 5 to 30 μm can be used. The colored aluminum flake pigment can obtain a desired hue by changing the type and amount (coating thickness) of the colored pigment to be coated.

On the other hand, the colored mica pigment is preferably a mica pigment in which the surface of natural muscovite or synthetic mica is coated with a colored pigment in the form of flakes. As such a colored mica pigment, the particle size range is 1 to 60 μm.
, Preferably 1 to 40 μm, and an average particle size of 15 to 25 μm.
m scale-like material can be used. The desired color can be obtained by adjusting the type and amount (coating thickness) of the colored pigment to be coated.

As the colored brilliant pigment, the colored aluminum flake pigment and the colored mica pigment can be used alone or in a mixture at an arbitrary mass ratio.

The hiding power of the colored glittering pigment is 10
It is preferably 0 μm or less. If it exceeds 100 μm, the resulting coating film cannot be provided with concealing properties. The concealing property means a minimum dry film thickness at which a coating film obtained from a paint containing 20% by mass of a colored glittering pigment based on the solid content of the paint cannot distinguish black and white of a black and white concealing paper.

(B) Fine particle titanium dioxide and aluminum
Mixture with flakes The mixture of the above-mentioned fine particle titanium dioxide and aluminum flakes develops a yellowish color at an intermediate portion between a highlight portion and a shade portion.

The fine particle titanium dioxide has an average particle diameter of:
Preferably it is 0.01 to 0.2 μm, more preferably 0.1 to 0.2 μm.
It is titanium dioxide of 02 to 0.1 μm. If the average particle size is less than 0.01 μm, there is a possibility that the coloring property is insufficient,
If it is 0.2 μm or more, there is a possibility that yellow color may not be produced when mixed with aluminum flake.

The above-mentioned aluminum flakes are obtained by converting aluminum, which is commonly used as a glitter material of metallic paint, into flakes and then treating them with a fatty acid or the like. Type or non-leafing type.
The average particle size is preferably 5 to 60 µm, more preferably 10 to 30 µm. When the average particle diameter is less than 5 μm, it is difficult to exhibit a glittering feeling, and when the average particle diameter is 60 μm or more, the appearance of the coating film may be poor. On the other hand, the thickness is 0.
It is 1 to 3 μm, preferably 0.2 to 1.5 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.
If it exceeds m, the coating film appearance may be degraded.

The mass ratio of the fine particle titanium dioxide to the aluminum flake in the above mixture is 99/1 to 30 /
70 is preferred. If it exceeds 99/1, the brilliant feeling is insufficient, and if it is less than 30/70, yellowish coloration may be insufficient. More preferably, it is 90/10 to 50/50.

(C) Fired Composite Oxide Pigment The fired composite oxide pigment (c) is a fired pigment composed of a composite of a metal oxide composed of two or more elements. Here, as the two or more kinds of elements, (1) Co, which expresses a color,
Ni, Fe, Mn, Cu, Cr, etc. are essential, and in addition to these, a color develops depending on conditions (2) Ti, Sb, As,
Bi and the like, and (3) Al, Si, Ca,
Mg, Ba, etc. are combined. By changing the mixing ratio, a desired calcined pigment can be obtained. These calcined pigments are in the form of a solid solution obtained by heat-treating a metal oxide composed of the above-mentioned elements and thermally diffusing, and are obtained by pulverizing coarse particles into a desired particle size after calcining. The average particle size is 0.
1 to 50 μm, more preferably 0.5 to 5 μm
m, more preferably 0.5 to 2 μm.

The relationship between the metal oxide component and the color development will be described below. Green type: TiO ₂ —CoO—NiO—ZnO, etc. Yellow type: TiO ₂ —BaO—NiO, TiO ₂ —Sb ₂ O ₃
-NiO like blue: CoO-Al ₂ O _3, etc. Brown color _{system: ZnO-Fe 2 O 3,} NiO-Fe 2 O 3 -
Al ₂ O _3, and the like _{blackish: CuO-Fe 2 O 3 -Mn} 2 O 3 , etc.

Examples of the above-mentioned fired composite oxide pigment include series such as "Dipoxide Color" (trade name) sold by Dainichi Seika Kogyo.

The above-mentioned fired composite oxide pigment has a lower tinting strength than ordinary coloring pigments, but when used in combination with the above-mentioned brilliant pigment, the color retention and strong color tint and shade at the shaded portion are improved. Is good, and a coating film exhibiting solid luster is obtained with high chroma even in the highlight portion, and a bright and vivid impression can be expressed as an appearance.

Ratio of pigment component In the glittering coating composition of the present invention, mass of (a) colored glittering pigment / (b) mixture of fine particle titanium dioxide and aluminum flake / (c) fired composite oxide pigment The ratio is preferably from 10 to 100/10 to 100/100. If the ratio is out of this range, there is a possibility that a design that develops two colors in three stages may not be exhibited. More preferably, it is 20-80 / 20-80 / 100.

The total content (PWC) of the above (a), (b) and (c) is preferably 5 to 30%. If it is less than 5%, it is difficult to develop a design that develops two colors in three stages,
If it exceeds 30%, the coating film appearance may be deteriorated. More preferably, it is 10 to 25%.

Other glitter pigments and coloring pigments can be contained. Examples of such other brilliant pigments include metal titanium flake, stainless flake, plate-like iron oxide, phthalocyanine flake, and hologram pigment. Color pigments include organic pigments and inorganic pigments.Examples of organic pigments include azo lake pigments, phthalocyanine pigments, indico pigments, berylen pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, and isoquinone pigments. Indolinone pigments, metal complex pigments and the like can be mentioned, and as inorganic pigments, for example, yellow iron oxide, red iron oxide, titanium dioxide, carbon black and the like can be mentioned.
Also, various extender pigments and the like can be used in combination. In addition, the total content (PWC) of all the pigments is preferably less than 55%, more preferably less than 30%. If it exceeds 55%, the appearance of the coating film deteriorates.

Vehicle The vehicle contained in the glitter coating composition is for dispersing the pigment and is composed of a resin for forming a coating film and, if necessary, a crosslinking agent.

Examples of the coating film forming resin 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. 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 Resin As the alkyd resin, the above polybasic acids and polyhydric alcohols are further added to fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), and natural resins (rosin, succinate, 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 resins 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 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-mentioned 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 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 insufficient. 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.

Other Components Other than the above components, the above-mentioned glittering coating composition may further comprise, in addition to the above-mentioned components, precipitated polyamide wax which is a lubricating dispersion of aliphatic amide and polyethylene wax which is a colloidal dispersion mainly composed of polyethylene oxide. Inhibitors, curing catalysts, UV absorbers,
Antioxidants, leveling agents, surface conditioners such as silicon and organic polymers, anti-sagging agents, thickeners, defoamers, lubricants, crosslinkable polymer particles (microgels), and the like 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 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, it may contain a suitable amount of hydrophilic organic solvent.

<Coating Film Forming Method> In the coating film forming method of the present invention, the brilliant coating composition is coated on a substrate to be coated, and the brilliant coating film forms two colors in three stages as a base coat layer. After forming the coating film, at least one clear coating is applied as a top coat layer on the glittering coating film thus obtained to form a top coat layer.

The substrate to be coated is not limited, and 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 natural or synthetic materials such as wood and fiber materials (paper, cloth, etc.). This substrate is 3
In order to effectively develop a design that develops two colors at the stage,
For example, it is preferable to have a curved surface like a car body or a door.

In the method for forming a coating film of the present invention, the above-mentioned brilliant coating composition is applied to the above-mentioned substrate directly or via an undercoating film.
It is preferable to previously apply undercoating by chemical conversion treatment, electrodeposition coating, intermediate 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 of the present invention, first, the above-mentioned brilliant coating composition is applied to the above-mentioned substrate as a base coat layer. Preferably, the glitter coating composition preferably covers the lower layer.

In the case where the above-mentioned base material is a base material coated with an undercoat, an intermediate coating or the like, a wet-on-wet (W / W) method or a wet-on-dry (W / D) 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 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 glitter coating composition is preferably 5 to 50 μm, more preferably 10 to 30 μm per coat.

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 method of forming a coating film of the present invention, those which are generally used for overcoating can be used. For example, acrylic resins, polyester resins, fluorine resins, 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 base coat when the difference in solubility between the base coat layer and the base coat layer is increased by acid rain resistance and the W / W method. It is preferably used from the viewpoint of not disturbing the orientation of the brightener in the layer. In addition, these clear coatings may include additives such as coloring pigments, extenders, modifiers, ultraviolet absorbers, leveling agents, dispersants, and defoaming agents as long as the transparency is not impaired. It is possible to mix.

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 Article> The coated article of the present invention is an article coated by the above-mentioned coating film forming method, and has the above-mentioned glittering coating film as a base coat layer formed on a substrate, and further has a coating thereon. At least one clear top coat layer is formed as the top coat layer. In the above-mentioned painted material, a colored portion is obtained in the shade portion, and the highlight portion and the shade portion are non-yellow and have similar colors.
Further, it exhibits a design in which two colors are formed in three stages such that a yellowish color is obtained in an intermediate portion between the shade portion and the highlight portion, and exhibits a more luxurious glitter. In particular, in a curved surface portion such as a car body or a door, a design that develops two colors in three stages is effectively exhibited. It is also possible to provide concealment.

[0053]

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.

Preparation of base materials of Examples 1 to 9 and Comparative Examples 1 to 5 A dull steel plate (length 300 mm, width 100 mm and thickness 0.8 mm) was 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 that the dry film thickness became 25 [mu] m. Next, after baking at 160 ° C. for 30 minutes, an intermediate coating (“Olga S-90 Sealer”, 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. An intermediate coating layer was formed and 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 (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. (A) colored brilliant pigment, (b) fine particle titanium dioxide, aluminum flake, (c) baked composite oxide pigment, and, if necessary, colored pigment in the type and proportion shown in Table 1 did. Then
The mixture was stirred and mixed with an organic solvent (mass ratio of toluene / xylene / ethyl acetate / butyl acetate = 70/15/10/5) by a stirrer so as to obtain an appropriate coating viscosity, thereby preparing 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 color change and the hiding power of the obtained coating film were evaluated by the following evaluation methods, and 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.) or a clear paint 2 containing a carboxyl group-containing polymer and an epoxy group-containing polymer ("" Mac Flow O-
520 Clear ", manufactured by Nippon Paint Co., Ltd.).

Evaluation method : Color change: When the obtained coating film was viewed obliquely (shade portion), and when the test plate was viewed obliquely from almost the front (highlight portion) obliquely (shade portion), It was visually evaluated whether or not a design that develops two colors in three stages of a highlight portion → intermediate portion → shade portion was developed. 3 ... A colored feeling is obtained in the shade portion, and the appearance of a design which produces two colors in three stages is remarkably exhibited. 2 ... A design in which a colored feeling is obtained in the shade portion and two colors are developed in three stages. The appearance of color is not obtained in the shade part, and the appearance of a design that develops two colors in three stages is not observed.

Hiding property: The state of see-through of the intermediate coating film in the obtained coating film was visually evaluated. 3: No see-through of the intermediate coating film is observed. 2 .: Transparency of the intermediate coating film is partially observed. 1 .: Transparency of the intermediate coating film is observed. Was determined by measuring the minimum dry film thickness when black-and-white concealment paper could not be discriminated using a paint containing a colored glittering pigment at 20% by mass based on the solid content of the paint.

[0059]

[Table 1]

As is clear from the results shown in Table 1, in this example, a coating film was formed by the coating film forming method of the present invention. A brilliant coating film exhibiting a color-developing design and having concealing properties was obtained. On the other hand, in the comparative example, it was not possible to obtain a brilliant coating film exhibiting a design of developing two colors in the above three stages.

[0061]

The glitter coating composition of the present invention contains (a) a colored glitter pigment, (b) a mixture of fine titanium dioxide and aluminum flakes, and (c) a calcined composite oxide pigment, and (A) a colored glittering pigment and (c)
By defining the hue relationship of the baked composite oxide pigment, a colored feeling can be obtained in the shade portion, and the highlight portion and the shade portion are non-yellow and have similar colors.
Further, it is possible to obtain a brilliant coating film exhibiting a design that develops two colors in three stages, such as a yellowish color being obtained in an intermediate portion between the shade portion and the highlight portion. Such a coating film expressing a design that develops two colors in three stages is:
Gives a more luxurious feel. Further, by selecting the kind of the colored glittering pigment to be used, it is possible to enhance the concealing property.

Since the coating film obtained by the present invention strongly exhibits the above-mentioned brilliant feeling, it has a unique brilliancy such as a vehicle outer plate of an automobile, a motorcycle or the like, these parts, a container outer surface, a coil coating, a home appliance industry and the like. It is preferably used in required coatings.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing the appearance of a design that produces two colors in three stages according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Painted object 2 Highlight part 3 Shade part 4 Intermediate part 5 Direction of light incidence 6 Direction of light reflection

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/06 C09D 201/06 201/08 201/08 F term (Reference) 4D075 CB04 CB07 CB11 CB36 DA06 DB02 DC12 EC02 EC04 EC10 EC11 EC23 EC54 4J038 CD101 CD121 CG141 DB061 DD041 DD121 DF011 DG111 DG121 DG131 DG221 DG271 DG281 GA03 GA06 GA09 HA026 HA066 HA296 HA546 JB28 JB31 JB34 JC38 KA08 KA12 KA15 PC10 PC07 PC10

Claims (12)

[Claims] 1. A vehicle, (a) a colored brilliant pigment, (b)
A coating composition containing a mixture of fine-particle titanium dioxide and aluminum flakes, and (c) a baked composite oxide pigment, wherein the (a) hue of the colored glittering pigment and the (c) baked composite oxide pigment The hue is a similar color, and the hue 10Y (yellow) in the Munsell hue display system is set to 0.
With respect to the Munsell hue circle 100, in the hue display of the display system indicated by +50 counterclockwise and −50 counterclockwise, the hue of the (a) colored glitter pigment and the hue of the (c) composite oxide fired pigment are -20 to -50 or +20 to +
A bright coating composition in the range of 50. 2. The glitter according to claim 1, wherein, in the hue display of the display system, the difference between the hue of the (a) colored glitter pigment and the hue of the (c) composite oxide fired pigment is less than 20. Paint composition. 3. The hue display of the display system, wherein the hue of the (a) colored glittering pigment and the hue of the (c) fired composite oxide pigment are -30 to -50 or +30 to +30.
The glitter coating composition according to claim 1, wherein the composition is in the range of 50. 4. The luminous pigment (a) having a hiding power of 10
The glittering coating composition according to any one of claims 1 to 3, which has a thickness of 0 µm or less. 5. The mass ratio of (a) / (b) / (c) is:
The glitter coating composition according to any one of claims 1 to 4, which is 10 to 100/10 to 100/100. 6. The glittering coating composition according to claim 1, wherein the mass ratio of the fine particle titanium dioxide to the aluminum flake is from 99/1 to 30/70. 7. The pigment (5) having a PWC of (a) a colored glittering pigment, (b) a mixture of fine particle titanium dioxide and aluminum flake, and (c) a baked composite oxide pigment.
The glittering coating composition according to any one of claims 1 to 6, which contains 0.1% by weight. 8. The glitter coating composition according to claim 1, wherein the colored glitter pigment (a) is a colored aluminum flake pigment and / or a colored mica pigment. 9. A coating film forming method comprising: forming a base coat layer on a substrate using the glitter coating composition according to claim 1; and forming a top coat layer using a clear paint. . 10. The method according to claim 9, wherein said clear coating material contains a carboxyl group-containing polymer and an epoxy group-containing polymer. 11. A coated article to be coated by the coating film forming method according to claim 9. 12. The coated article according to claim 11, wherein the surface to be coated of said coated article has a curved surface.