JPH11116861A - Bright coating composition, formation of bright coating film and bright coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bright coating composition containing a colored aluminum flake pigment and capable of imparting a strong bright appearance and an excellent appearance without generating a glittering appearance on a coating film, to provide a method for forming a bright coating film by coating the bright coating composition, and to provide a bright coating article on which the coating film is formed. SOLUTION: This bright coating composition contains a colored aluminum flake pigment having a 400 mesh sieve residue of <=0.01 wt.% and a water surface diffusion area value of 7,000-10,000 cm<2> /g. The colored aluminum flake pigment has a metal oxide coating layer formed by a chemical gas phase deposition method (CVD method). Aluminum flakes are heated a 170-250 deg.C for >=12 hr to remove organic impurities, and subsequently subjected to the formation of the metal oxide layers. This method for forming a bright coating layer comprises coating the surface of a substrate with the bright coating composition, further coating the coated substrate with a clear coating in an at least one layer before the coated bright coating composition is cured, and subsequently baking the coated coatings.

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 capable of forming a coating film having a strong luminosity and excellent appearance suitable for overcoating of automobiles and home appliances, and the brilliant coating composition. TECHNICAL FIELD The present invention relates to a method for forming a glitter coating film using a hydrophilic coating composition, and a glitter coating product on which such a coating film is formed.

[0002]

2. Description of the Related Art A glittering coating film formed by coating a glittering paint containing a glittering pigment has a flip-flop property and a high designability.
It is often used for painting automobiles. However, in recent years, the level of demand for high-class feeling and aesthetics has become high, and it is difficult to form a coating film satisfying such high requirements with the conventional glittering paint. For this reason, the practical application of various new glittering pigments and glittering coating compositions has been studied.

A colored aluminum flake pigment formed by forming a colored layer of a metal oxide or the like on aluminum flake is
Color variations and various interference colors can be obtained by changing the thickness of the coating film such as metal oxide, etc.
Conventionally, various manufacturing methods have been proposed. In addition, there has been proposed a technique for increasing the glitter of a formed coating film by using an interference mica pigment in combination.

For example, JP-A-5-70719 discloses a metallic paint containing a colored aluminum flake pigment and mica powder. This colored aluminum flake pigment is prepared by adding a thermally polymerized carboxylic acid in an organic solvent to an aluminum flake coated with a fatty acid such as oleic acid or stearic acid in order to prevent oxidation, and stirring the mixture by heating. And then a radically polymerizable unsaturated carboxylic acid is added to form a crosslinked resin layer on the surface. However, the aluminum flake pigment having such a configuration has insufficient flip-flop properties.

On the other hand, JP-A-6-145555 discloses a luster pigment based on an aluminum flake pigment obtained by removing organic impurities on the surface of the aluminum flake and coating it with a metal oxide. . This metal oxide-coated aluminum flake pigment is heated to 150 to 270 ° C. while fluidizing the aluminum flake with nitrogen to remove organic impurities from the surface, and then forms a metal oxide film such as iron oxide by a chemical vapor deposition method. It was done.

However, when a large amount of the above-mentioned metal oxide-coated aluminum flake pigment is incorporated into a resin for forming a coating film in order to increase the glitter of the coating film, the orientation and overlapping of the aluminum flakes may cause a problem in forming the coating film. A state in which aluminum flakes protrude from the coating film surface easily occurs. The aluminum flakes protruding from the surface of the coating film have a problem in that even if a clear coating is applied thereon, the appearance of the foreign particles gives a glimpse of a foreign substance (hereinafter referred to as a "glitter feeling"). For this reason, it was practically impossible to obtain a glittering coating film containing more than about 3% by weight of aluminum flake pigment without a flicker.

Accordingly, an object of the present invention is to solve the above-mentioned problems and to prevent the finished appearance of the coating film from having a flickering feeling.
A glitter coating composition containing a large amount of a colored aluminum flake pigment capable of imparting a strong glitter and an excellent appearance, a method of forming a coating film by applying the glitter coating composition, and such coating It is to provide a coating having a film.

[0008]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned object, the present inventors have sufficiently removed organic impurities such as fatty acids from the surface of aluminum flakes of aluminum flake pigment, and then carried out a chemical vapor deposition method. By forming a metal oxide layer by (CVD method) and further classifying,
Due to the uniform particle size distribution and excellent dispersibility, the vehicle
It is possible to obtain a colored aluminum flake pigment which does not cause a glittering coating to be formed on the glittering coating film formed even when added in an amount of more than 3 parts by weight with respect to 100 parts by weight (solid content basis). The present inventors have found that a glitter coating composition comprising the compound can form a glitter coating film having excellent glitter and appearance, and have reached the present invention.

That is, the glitter coating composition of the present invention is coated with a metal oxide layer formed by a chemical vapor deposition method, and has a 400 mesh sieve having a residue of 0.01% by weight or less of a colored aluminum flake pigment. It is characterized by containing.

In particular, the colored aluminum flake pigment to be added to the glittering coating composition of the present invention removes organic impurities such as fatty acids by heating at 170 to 250 ° C. for 12 hours or more before forming a metal oxide layer. Classification is preferably performed after the formation of the metal oxide layer.

Further, the method for forming a glitter coating film of the present invention is characterized in that at least one layer of a clear paint is applied while the glitter coating composition is not yet cured, and then baked together.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

[1] Glitter paint composition The glitter pigment in the glitter paint composition of the present invention contains a colored aluminum flake pigment as an essential component, and may further contain a mica pigment. In addition, the glitter coating composition contains components usually used in this type of coating, specifically, a film-forming resin, an organic solvent and / or water, and various additives such as a coloring pigment and an anti-settling agent. Can be blended.

[A] Bright pigment The bright pigment used in the present invention is mainly composed of a colored aluminum flake pigment, and may be mixed with a mica pigment as needed. (1) Colored aluminum flake pigment The colored aluminum flake pigment of the present invention is an aluminum flake having a metal oxide layer formed by a chemical vapor deposition method (CVD method) and having a sieve residue of 400 mesh of 0.01% by weight or less. 0.01% by weight of sieve residue of 400 mesh
If it is too high, a flicker will be produced.

The colored aluminum flake pigment preferably has a water surface diffusion area value of from 7000 to 10000 cm ² / g. The water surface diffusion area value is obtained by washing a colored aluminum flake pigment (usually stored in the form of a fatty acid paste) with acetone, drying a powder (W, unit: g) dispersed in isobutanol, and dropping the powder on the water surface. And diffused area (S,
It is the value of S / W obtained from the measured value of the unit: cm ² ). If the water surface diffusion area value is less than 7000 cm ² / g, it will not disperse sufficiently in the resin for forming a coating film, causing a flicker of the formed coating film.

The colored aluminum flake pigment has a thickness of
It is preferable that the average major axis be in the range of 0.1 to 2 μm and the average major axis be in the range of 1 to 25 μm. When the thickness is less than 0.1 μm, the mechanical strength is insufficient and the aluminum flakes are easily broken by the circulation, and when the thickness is more than 2 μm, the reflection of light is weakened and the glitter is reduced. Regarding the average major axis,
When the thickness is less than 1 μm, the glitter is insufficient, and
If it exceeds, projections and bumps are formed on the coating film surface. A more preferred average major axis is 5 to 20 μm.

[0016] Aluminum flakes are usually produced by ball milling in the presence of a fatty acid-based lubricant such as stearic acid. The colored aluminum flake pigment of the present invention is produced by (a) removing fatty acids from the surface of the aluminum flake, (b) forming a metal oxide layer by a CVD method, and (c) classifying.

(A) Step of removing fatty acid-based lubricant Before forming the metal oxide layer, aluminum flakes are heated in an atmosphere of nitrogen gas or nitrogen gas + air to remove organic impurities such as fatty acid-based lubricant. I do. Preferably, after the aluminum flakes are charged into the fluidized bed reactor, the aluminum flakes are heated to 170 to 250 ° C. while fluidizing the aluminum flakes by blowing nitrogen gas or nitrogen gas + air. The heating time is preferably at least 12 hours. Heating time 12
If the time is less than this, the residual amount of the fatty acid is large, and the adhesion of the metal oxide layer is weakened. In addition, the aluminum flakes are insufficiently deagglomerated and the particle size distribution is not uniform, which is not preferable. Note that the upper limit of the heating time is about 15 hours.

(B) Step of Forming Metal Oxide Layer When the fatty acid is completely removed from the aluminum flakes and deagglomerated, nitrogen gas saturated with a vaporized metal oxide precursor is kept in a fluidized state, Of oxygen or air and / or water vapor to form a metal oxide film. As the metal oxide precursor, Fe (C
O) ₅ , Mo (CO) ₆ , W (CO) _{6 and} other carbonyl compounds, Ti
Cl ₄ , SnCl ₄ , SiCl ₄ , chlorine compounds such as AlCl ₃ , Ti (O
Examples thereof include metal alkoxides such as R) ₄ and Zr (OR) ₄ , among which Fe (CO) ₅ is preferable. The carbonyl compound is hydrolyzed by oxygen and the chlorine compound and metal alkoxide are hydrolyzed by water vapor to form a metal oxide layer. Stop the reaction when the metal oxide layer reaches the desired thickness,
Reduce reactor temperature.

(C) Classification Step After cooling the obtained metal oxide-coated aluminum flakes, the metal flakes are classified until the residue of a 400-mesh sieve becomes 0.01% by weight or less. Since the classification method itself is known, its description is omitted.

(2) Mica pigment By mixing a mica pigment with a colored aluminum flake pigment, a pearl-like interference color can be obtained.
As the mica pigment, a pearl mica pigment obtained by coating a surface of natural mica or synthetic mica with a thin film of titanium dioxide, iron oxide, or a metal oxide such as chromium, cobalt, tin, and zirconium to impart an interference color effect is preferable. . The mica pigment has a particle size range of 0.5 to 60 μm, more preferably 0.5 to 60 μm.
It is preferably in the form of scaly particles having a mean particle size of from 5 to 25 µm.

(3) Blending amount of brilliant pigment When blending only a colored aluminum flake pigment as the brilliant pigment, the blending amount is preferably 3 parts by weight or more (based on solid content) based on 100 parts by weight of the vehicle. The upper limit of the amount of the colored aluminum flake pigment is about 20 parts by weight from a practical viewpoint. When the mica pigment is also blended, it is blended in such an amount that does not hinder the glitter of the colored aluminum flake pigment. The weight ratio of the colored aluminum flake pigment to the mica pigment (based on solid content) is 1/20 to 20/1.
Is preferable, and a ratio of 1/6 to 6/1 is more preferable.

[B] Vehicle The vehicle in which the colored aluminum flake pigment is dispersed is:
It comprises a coating film forming resin and, if necessary, a crosslinking agent. Examples of the resin for forming a coating film include an acrylic resin, a polyester resin, an alkyd resin, a fluororesin and the like, and an acrylic resin and a polyester resin are particularly preferable.

(1) Coating resin (a) Acrylic resin Acrylic resins include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate and N-methylolacrylamide. Hydroxyl-containing (meth) acrylate monomers, (meth) acrylic acid, crotonic acid, itaconic acid,
Ethylenically unsaturated monomers having a carboxyl group such as fumaric acid and maleic acid, and methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl acrylate, 2-ethylhexyl acrylate And at least one kind of alkyl (meth) acrylate monomer such as n-octyl acrylate, n-dodecyl acrylate, etc., can be obtained by polymerization by a usual method. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid. Further copolymerizable (meta)
Acrylonitrile, styrene, (meth) acrylamide, dimethylacrylamide, N, N-dimethylpropylacrylamide, N-butoxymethylacrylamide and the like may be blended. Number average molecular weight of acrylic resin is 1,800 ~
It is preferably 100,000, more preferably 5,000 to 20,000.

(B) Polyester resin The polyester resin is obtained by polycondensing (esterifying) a polyhydric alcohol and a polybasic acid or its anhydride.

The polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, glycerin, trimethylolethane, trimethylol Examples thereof include methylolpropane, pentaerythritol, and dipentaerythritol, and a combination of two or more of these polyhydric alcohols can be used.

Examples of polybasic acids or anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. Examples thereof include acid, maleic anhydride, fumaric acid, itaconic acid, and trimellitic anhydride, and these can be used in combination of two or more.

The number average molecular weight of the polyester resin is from 200 to
It is preferably 10,000, more preferably 300 to 6,000.

(2) Crosslinking Agent Examples of the crosslinking agent include amino resins such as melamine resins, and blocked polyisocyanate compounds. Further, a two-component polyurethane resin, a silicone resin or the like which can be cured by drying at room temperature can also be used.

(A) Amino resin As the amino resin, for example, a condensate obtained by reacting one or a mixture of two or more amino compounds such as melamine, urea, and benzoguanamine with formaldehyde, and the condensate may be methanol, butanol, or the like. And an alkyl etherified melamine resin reacted with a lower alcohol. The number average molecular weight of such an alkyl etherified melamine resin is preferably from 400 to 1,200.

In particular, an average of 0 to 1 per triazine ring
An amino resin having two imino groups is preferred, and an amino resin having an average of 0 to 0.2 imino groups is particularly preferred. The portion other than the imino group is bonded to an alkyl ether group or the like. The average number of imino groups per triazine ring was determined by the weight ratio of carbon, hydrogen and nitrogen determined by elemental analysis to NH / -NCH determined by ¹ H-NMR.
Calculated from the molar ratio of ₂ OR.

(B) Blocked polyisocyanate compound Examples of the blocked polyisocyanate compound include aliphatic polyfunctional isocyanates such as hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPD).
A) alicyclic polyfunctional isocyanates such as I), diphenylmethane-4,4'-diisocyanate (MDI) and hydrogenated MDI;
And the like, in which a functional group of a polyisocyanate compound is partially or completely blocked by a blocking agent.

(3) Blending Ratio The blending ratio of the resin for forming a coating film and the crosslinking agent is 90 to 50% by weight, preferably 85 to 60% by weight in terms of solid content.
% By weight, and the crosslinking agent is 10 to 50% by weight, preferably 15 to 50% by weight.
40% by weight. If the amount of the crosslinking agent is less than 10% by weight (the amount of the resin for forming a coating film exceeds 90% by weight), the crosslinking in the coating film is not sufficient. On the other hand, if the cross-linking agent exceeds 50% by weight (the resin for forming a coating film is less than 50% by weight), the storage stability of the coating composition is reduced and the curing speed is increased, so that the coating film appearance is deteriorated.

[C] Solvent Any solvent may be used as long as it can dissolve the vehicle.
It can be used as an organic solvent type, a non-aqueous dispersion type, an aqueous solution type or an aqueous dispersion type. However, since the use of an organic solvent is regulated from an environmental point of view, it is preferable to use an aqueous type. In the case of an aqueous system, an appropriate amount of a hydrophilic organic solvent may be contained.
Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate and butyl cellosolve, and alcohols.

[D] Other additives In addition to the above components, an antisettling agent, a coloring pigment, a curing catalyst, an ultraviolet absorber, an antioxidant, a surface conditioner such as silicone or an organic polymer, an anti-sagging agent, A tackifier, crosslinkable polymer particles (microgel), and the like can be appropriately added. By blending these additives at a ratio of 5 parts by weight or less based on 100 parts by weight of the vehicle (based on solid content), the performance of paints and coatings can be improved.

(1) Anti-settling agent As anti-settling agent, polyamide wax which is a swelling dispersion of aliphatic amide and polyethylene wax which is a colloidal dispersion mainly composed of polyethylene oxide are preferable. The compounding ratio of the anti-settling agent is 100 brilliant flake pigments.
The amount is preferably from 1 to 30 parts by weight, more preferably from 5 to 25 parts by weight, based on the weight of the solid content.

(2) Color pigments Color pigments include azo pigments, phthalocyanine pigments, indico pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and metal complexes. Organic pigments such as pigments, and inorganic pigments such as graphite, yellow iron oxide, red iron oxide, titanium dioxide and the like. The amount of the coloring pigment to be added can be arbitrarily set according to the hue as long as the coating film retains the glitter.

[2] Substrate The substrate (substrate) to which the glittering coating composition of the present invention is applied includes metals such as iron, aluminum, copper and alloys thereof, glass, cement, concrete and the like. Inorganic materials, resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyamide, acrylic resin, vinylidene chloride resin, polycarbonate, polyurethane, epoxy resin, and various plastic materials such as FRP, natural materials such as wood and fiber materials Materials and the like. The coating composition is applied to the substrate to be coated directly or via an undercoating film. In the case of coating the body of an automobile, it is preferable to apply a chemical conversion treatment, an electrodeposition coating, an intermediate coating, or the like in advance.

[3] Method for Forming Coating Film The glitter coating composition obtained by the above-described method is applied on a substrate, and at least one layer of clear coating material is coated on the glitter coating obtained.

(1) Brilliant coating film When using a substrate coated with an undercoat with an intermediate coating or the like, a wet-on-wet (W / W
The glittering coating composition of the present invention is applied by the W) method or the bake-on-wet (B / W) method. The W / W method is a method in which an undercoating film is formed and then dried by air drying or the like, and then applied in an uncured state or a semi-cured state.
This is a method of painting after baking a base coat. The coating method is not particularly limited, but a spray method, a roll coater method and the like are preferable. The dry thickness of the glittering coating film is preferably 5 to 50 μm, more preferably 10 to 30 μm.

(2) Clear coating film The clear coating material may be any of those commonly used for overcoating. The application of the clear paint on the coating film of the present invention can be performed by a wet-on-wet (W / W) method. When the clear paint is applied a plurality of times, the clear paint may be baked after the final clear coat is applied, and may be in a W / W, preheat or semi-cured state at the stage of forming the lower clear coat. Baking temperature after clear painting is 120
It may be up to 160 ° C. Dry film thickness of clear coating film is 10 ~ 80μm
Is preferable, and 20 to 50 μm is more preferable.

[0041]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Production Example 1 Production of Colored Aluminum Flake Pigment (a) As shown in FIG. 1, a cylindrical portion 1 having a conical lower end, a nozzle 2 for blowing nitrogen gas / air, a filling port 3 for aluminum flakes, A fluidized bed reactor having a nozzle 4 for injecting carbonyl iron (Fe (CO) ₅ ) / nitrogen gas, a filtration net 5 and an outlet 6 for the formed colored aluminum flake pigment was used. Aluminum flakes produced by ball milling in stearic acid (average particle size
15 μm) was charged into the fluidized bed reactor through the filling port 3 and heated to 200 ° C. for 15 hours while fluidizing with nitrogen gas to remove stearic acid and to deagglomerate aluminum flakes.

Next, iron pentacarbonyl iron (Fe
(CO) ₅ ) The nitrogen gas saturated in ₅ ) is sent from nozzle 4 and
An iron oxide film was formed on the aluminum flake at 0 ° C.
The obtained iron oxide-coated aluminum flake pigment was taken out from the outlet 6 and classified with a sieve of 400 mesh.

The colored aluminum flake pigment (a) thus obtained exhibited a gold color. The sieve residue of the 400 mesh is 0.005% by weight, and the water diffusion area is 90%.
00 cm ² / g.

Production Example 2 Production of Colored Aluminum Flake Pigment (b) (Comparative Example) The same procedure as in Production Example 1 was repeated except that the heating time of the aluminum flakes was changed to 7 hours. ) Was manufactured. The colored aluminum flake pigment (b) has a gold color, the sieve residue of 400 mesh is 0.24% by weight, and the water surface diffusion area is 6500 cm ^2.
/ G.

Examples 1 to 10 Preparation of substrate to be coated After dull steel plate (length 300 mm, width 100 mm and thickness 0.8 mm) is subjected to a chemical conversion treatment using a zinc phosphate treating agent (Surfdine SD2000, manufactured by Nippon Paint Co., Ltd.), An electrodeposition paint (Powertop U-50, manufactured by Nippon Paint Co., Ltd.) was applied by electrodeposition so that the dry film thickness was 25 μm. Then 160 ° C
After baking for 30 minutes, dry the middle coat (Olga S-90 Sealer Gray (N-6), Nippon Paint Co., Ltd.) to a dry film thickness of 40.
It was air-sprayed to a thickness of μm and baked at 140 ° C. for 30 minutes to form an intermediate coating film.

2. Preparation of glitter coating composition Acrylic resin (styrene / methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate /
Methacrylic acid copolymer, number average molecular weight about 20,000, hydroxyl value 45, acid value 15, solid content 50% by weight) and melamine resin (trade name: Uban 20SE, manufactured by Mitsui Toatsu Chemicals, Inc., solid content 60) % By weight) and the colored aluminum flake pigment (a) obtained in Production Example 1 in a ratio shown in Table 1 with respect to 100 parts by weight of a resin for forming a coating film obtained by blending the solid content weight ratio of 80:20. Was blended. Then, the mixture was stirred and mixed with an organic solvent (weight ratio of toluene / xylene / ethyl acetate / butyl acetate = 70/15/10/5) using a dissolver so as to obtain a coating-appropriate viscosity to prepare a glittering coating composition.

3. Formation and evaluation of brilliant coating film On the coated surface of the base material, the brilliant coating composition was dried to a film thickness of 15%.
It was coated to a thickness of μm. Coating is electrostatic coating machine (Auto R
EA, manufactured by Ransberg Gema Co., Ltd.), atomization pressure 2.8 kg / cm
² went. Atmosphere of booth during painting is temperature 25 ℃, humidity
It was kept at 75%. Set for 3 minutes after painting, apply acrylic / melamine resin clear paint (trade name: Super Lac O-130 Clear, manufactured by Nippon Paint Co., Ltd.) so that the dry film thickness becomes 35 μm, and set at room temperature for 10 minutes And baked at a temperature of 140 ° C. for 30 minutes. The glitter and appearance of the obtained coating film were evaluated according to the following criteria. Table 1 shows the results.

Glitter ◎: The colored glitter is very strong.・ ・ ・: Colored glitter is strong. Δ: Colored glitter is slightly recognized. ×: The colored glitter is weak.

Appearance of coating film ・ ・ ・: good, no flickering Δ: A slight flicker is recognized. X: There is a feeling of flickering and defective.

Comparative Examples 1 to 10 A glittering coating film was formed in the same manner as in Example 1 except that the colored aluminum flake pigment (b) obtained in Production Example 2 was blended in the ratio shown in Table 1, and then a clear coating was performed. A film was formed. The glitter and appearance of the obtained coating film were evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 11 A brilliant coating was conducted in the same manner as in Example 1 except that non-colored aluminum flake pigment (c) (trade name: Alpaste 7130NS, manufactured by Toyo Aluminum Co., Ltd.) was blended in the ratio shown in Table 1. A film was formed, followed by a clear coating. The glitter and appearance of the obtained coating film were evaluated in the same manner as in Example 1. Table 1 shows the results.

Table 1 Example 1 2 3 4 5 6 7 8 9 10 Bright coating aluminum flake pigment ⁽¹⁾ a 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 b----------c − − − − − − − − − − −Evaluation glitter of coating film △ △ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ Appearance ○ ○ ○ ○ ○ ○ ○ ○ △ △ Note (1) 100 parts by weight of coating resin And the unit: parts by weight. a: The colored aluminum flake pigment of Production Example 1. b: The colored aluminum flake pigment of Production Example 2. c: Alpaste 7130NS.

Table 1 (continued)Comparative example 1 2 3 4 5 6 7 8 9 Ten 11 Bright coating Aluminum flake pigment ⁽¹⁾  a − − − − − − − − − − − b 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 − c − − − − − − − − − − 5.0 Evaluation of coating film Brightness △ △ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ * Appearance ○ ○ △ × × × × × × × ○ Note (1), a to c: Same as above *: No coloring

As is clear from Table 1, the sieve residue of 400 mesh is more than 0.01% by weight and the water surface diffusion area is 8000 cm ^2.
/ G of a colored aluminum flake pigment (b) in an amount of 3% by weight or more when the glitter coating composition was applied, the glitter coating obtained had a flicker. (Comparative Examples 3 to 10). On the other hand, the sieve residue of 400 mesh is 0.01% by weight or less and the water surface diffusion area value is 7000
The coating film formed by the glittering coating composition of the present invention containing a colored aluminum flake pigment of 110,000 cm ² / g had good glitter and no flicker (Example 1).
~Ten).

Embodiments 11 to 14 Preparation of substrate to be coated After dull steel plate (length 300 mm, width 100 mm and thickness 0.8 mm) is subjected to a chemical conversion treatment using a zinc phosphate treating agent (Surfdine SD2000, manufactured by Nippon Paint Co., Ltd.), An electrodeposition paint (Powertop U-50, manufactured by Nippon Paint Co., Ltd.) was applied by electrodeposition so that the dry film thickness was 25 μm. Then 160 ° C
After baking for 30 minutes with
90 Sealer White (manufactured by Nippon Paint Co., Ltd.) was applied by air spraying so as to have a Munsell coating film brightness shown in Table 2 and baked at 140 ° C. for 30 minutes to form a colored undercoat film.

2. Preparation of glitter coating composition Acrylic resin (styrene / methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate /
Methacrylic acid copolymer, number average molecular weight about 20,000, hydroxyl value 45, acid value 15, solid content 50% by weight) and melamine resin (trade name: Uban 20SE, manufactured by Mitsui Toatsu Chemicals, Inc., solid content 60) % By weight) and 100 parts by weight of a resin for forming a coating film obtained by blending with a solid content weight ratio of 80:20 to the colored aluminum flake pigment (a) of Production Example 1 and the blue interference mica pigment.
(d) (Product name: Exterior Marlin Super Blue,
(Produced by Marl Co., Ltd.) at the ratio shown in Table 2. Then, the mixture is stirred with an organic solvent (toluene / xylene / ethyl acetate / butyl acetate = 70/15/10/5 by weight) with a dissolver so as to obtain a coating-appropriate viscosity to prepare a pearl metallic-based brilliant coating composition. did.

3. Formation and Evaluation of Glittering Coating Film The obtained glittering coating composition was applied to the colored base coating film surface so that the dry film thickness became 15 μm. The spraying was performed using an electrostatic coating machine (Auto REA, manufactured by Ransberg Gemma Co., Ltd.) with an atomization pressure of 2.
The test was performed at 8 kg / cm ² . The atmosphere of the booth during painting is temperature 25
C. and 75% humidity. Set for 3 minutes after painting, and clear acrylic / melamine resin clear paint (trade name:
Super Rack O-130 Clear, Nippon Paint Co., Ltd.
Is coated to a dry film thickness of 35 μm, and
And baked at a temperature of 140 ° C. for 30 minutes. The glitter and appearance of the obtained coating film were evaluated in the same manner as in Example 1. Table 2 shows the results.

Examples 15 and 16 The same procedures as in Example 11 were carried out except that gold interference mica pigment (e) (trade name: Iriodin 300 WII, manufactured by Merck Japan KK) was used instead of blue interference mica pigment (d). Similarly, a glitter coating film was formed, and then a clear coating film was formed.
The glitter and appearance of the obtained coating film were evaluated in the same manner as in Example 1. Table 2 shows the results.

Examples 17 and 18 A brilliant coating film was formed in the same manner as in Example 11 except that a substrate to be coated was used in which a colored base coating film was formed so that the Munsell hue was 4.5Y 6.7 / 1.5. Then, a clear coating film was formed. The glitter and appearance of the obtained coating film were evaluated in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 12 A glittering coating film was formed in the same manner as in Example 11 except that the colored aluminum flake pigment (b) was blended in the ratio shown in Table 2, and then a clear coating film was formed. The glitter and appearance of the obtained coating film were evaluated in the same manner as in Example 1. Table 2 shows the results
Shown in

Comparative Example 13 A glittering coating film was formed in the same manner as in Comparative Example 12 except that the gold interference mica pigment (e) was used instead of the blue interference mica pigment (d), and then a clear coating film was formed. . The glitter and appearance of the obtained coating film were evaluated in the same manner as in Example 1.
Table 2 shows the results.

Table 2 Example 11 12 13 14 15 16 Undercoat Munsell Brightness N8 N2.5 N8 N2.5 N8 N2.5 Brilliant coating film Brilliant pigment ⁽¹⁾ (a) Colored aluminum flake pigment a 0.28 0.28 0.17 2.33 0.28 2.22 b − − − − − − − (b) Mica pigment d 2.22 2.22 2.33 0.17 − − e − − − − 2.22 0.28 (b) / (b) ⁽²⁾ 1/8 1/8 1/14 14 / 1 1/8 8/1 Evaluation glitter of coating film ◎ ◎ ○ ◎ ◎ ◎ Appearance ○ ○ ○ ○ ○ ○ Note (1) Amount, unit: 100 parts by weight of resin for forming film. (2) Weight ratio of colored aluminum flake pigment / mica pigment. a: The colored aluminum flake pigment of Production Example 1. b: The colored aluminum flake pigment of Production Example 2. d: Blue interference mica pigment pigment. e: Gold interference mica pigment pigment.

[0064] Note (1), (2), a, b, d, e: Same as above. *: Munsell hue circle display, 4.5Y 6.7 / 1.5.

As is clear from Table 2, Examples 11 to 18 satisfying the conditions of the present invention can form a brilliant coating film having good luminosity and appearance, but the sieve residue of 400 mesh is 0.01% by weight. %, And Comparative Examples 12 and 13 in which the colored aluminum flake pigment (b) and the interference mica pigment having a water surface diffusion area of less than 7000 cm ² / g are blended, a coating film having a good appearance is not formed.

[0066]

As described in detail above, according to the present invention,
A glittering paint composition containing a colored aluminum flake pigment capable of imparting a strong glitter and an excellent appearance can be obtained without causing a flicker in the finished appearance of the coating film. Therefore, the glitter coating composition of the present invention,
It is suitable for use in automobiles and their parts, home appliances, and various fixtures and the like, which require a high-class feeling and aesthetics.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a fluidized bed reactor for producing a colored aluminum flake pigment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Cylindrical part 2 ... Nozzle which blows nitrogen gas / air 3 ... Filling port of aluminum flake 4 ... Nozzle for injection of metal oxide precursor / nitrogen gas 5 ... Filtration net 6 ... Colored aluminum flake pigment outlet

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09C 1/64 C09C 1/64

Claims (6)

[Claims] 1. A glitter comprising a colored aluminum flake pigment coated with a metal oxide layer formed by a chemical vapor deposition method and having a sieve residue of 400 mesh of 0.01% by weight or less. Paint composition. 2. The glittering coating composition according to claim 1, wherein the colored aluminum flake pigment is heated to 170 to 250 ° C. for 12 hours or more before forming the metal oxide layer to remove organic impurities. And a brilliant coating composition characterized by being classified after forming a metal oxide layer. 3. The glittering coating composition according to claim 1, wherein the colored aluminum flake pigment has a water diffusion area value of from 7000 to 10000 cm ² / g. . 4. The glitter coating composition according to claim 1, wherein the colored aluminum flake pigment and the mica pigment are contained in a weight ratio of 1/20 to 20/1. Brilliant coating composition. 5. A glittering coating composition according to any one of claims 1 to 4, which is applied to a surface to be coated of a substrate, and the glittering coating film obtained is obtained by curing at least one of the uncured films. A method for forming a glittering coating film, comprising applying a clear paint and baking together. 6. A brilliant coating product, which is applied by the brilliant coating film forming method according to claim 5.