JP2003113348A - Photoluminescent coating composition, method for forming coating film and multilayer coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoluminescent coating composition for forming a photoluminescent coating film exhibiting high chroma feeling at both of a highlight part which is the view of the squarely looked coating film, and a shade part which is the view of the obliquely looked coating film while keeping a metallic tone having dense feeling in a color metallic coating material, and further to provide a method for forming the coating film, and a multilayer coating film. SOLUTION: This photoluminescent coating composition contains a colored and deposited aluminum flake pigment, and a vehicle. The method for forming the coating film uses the photoluminescent coating composition for forming at least one layer in layers constituting the multiple layered coating film, and the multilayer coating film has at least one layer obtained by using the coating composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glitter coating composition, a method for forming a coating film, and a multilayer coating film obtained by this method.

[0002]

2. Description of the Related Art Japanese Patent Laid-Open Publication No. 11-80620 discloses a metallic paint capable of forming a coating film having an appropriate metallic surface gloss, and a metallic paint as a paint for exhibiting a design property on an automobile body. As a method for forming the laminated coating film described above, a method is described in which the metallic paint contains a bright pigment which is obtained by crushing a vapor-deposited metal film into metal pieces.

In the metallic paint using the glittering pigment, which is used as a metal piece by crushing the vapor-deposited metal film used in Japanese Patent Laid-Open No. 11-80620, a metallic tone having a dense feeling can be expressed. When a color metallic paint is used in combination with a coloring pigment, there is a problem that it is difficult to obtain a high-saturation feeling in both the highlight part when the coating film is viewed from the front and the shade part when the coating film is obliquely viewed.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is, in a color metallic paint, while maintaining a metallic tone having a dense feeling, the highlight portion of the coating film viewed from the front and the coating film being inclined. A glittering coating composition that forms a glittering coating film that exhibits a high-saturation feeling in both the shaded areas seen,
A coating film forming method and a multilayer coating film are provided.

[0005]

Means for Solving the Problems The present inventors have accomplished the present invention as a result of intensive studies in view of the above problems.

1. A glitter coating composition containing a colored vapor deposited aluminum flake pigment and a vehicle.

2. The amount of the color pigment attached to the colored vapor-deposited aluminum flake pigment is 20 to 50 with respect to 100 parts by mass of the vapor-deposited aluminum flake as the base material.
The glitter coating composition described above, which is 0 part by mass.

3. The average particle diameter (μm) of the vapor-deposited aluminum flakes that is the above-mentioned substrate is the X axis, and the average particle thickness (μ
m) in the XY orthogonal coordinate system with the Y axis as A (3.
5,0.01), B (6,0.01), C (60,0.
1), the above-mentioned glitter coating composition prepared in a range surrounded by a straight line connecting the points D (35, 0.1).

4. The range surrounded by the straight line connecting the above points is A (3.5,0.01), B (6,0.01), E
(30, 0.05), D (35, 0.1), the glitter coating composition.

5. The glitter coating composition, wherein the content of the colored vapor-deposited aluminum flake pigment is 0.1 to 50 parts by mass based on 100 parts by mass of the solid content of the vehicle.

6. In addition to the above colored vapor-deposited aluminum flake pigment, further selected from the group consisting of metal oxide-coated alumina flake pigment, metal oxide-coated silica flake pigment, graphite pigment, metal oxide-coated mica pigment, and plate-shaped iron oxide pigment. The above-mentioned glitter coating composition containing at least one pigment selected from the above.

7. A method for forming a coating film, wherein the glitter coating composition is used for forming at least one layer of the layers constituting the multilayer coating film.

8. On the base material, an undercoat coating film, an intermediate coating film,
A method for forming a multi-layer coating film in which a glitter coating film and a clear top coating film are sequentially formed, wherein the glitter coating film is formed from the above glitter coating composition.

9. The method for forming a coating film as described above, wherein the clear top coating film is formed from a coating material containing a carboxyl group-containing polymer and an epoxy group-containing polymer.

10. A multilayer coating film obtained by the above coating film forming method.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below.

[Glittering Paint Composition] The glittering paint composition of the present invention is a paint containing a colored vapor-deposited aluminum flake pigment (hereinafter also referred to as "colored vapor-deposited aluminum flake pigment") and a vehicle. The colored vapor-deposited aluminum flake pigment is a pigment obtained by shredding a vapor-deposited aluminum film into a flake-like base material, and various color pigments are attached to the base material by the method described below.

The above colored vapor-deposited aluminum flake pigment is produced by vapor-depositing an aluminum film on a base film, peeling off the base film, and then cutting the vapor-deposited aluminum film into flakes to obtain various colored pigments. Obtained by attaching.

The vapor-deposited aluminum flakes as a base material for the colored vapor-deposited aluminum flake pigment are obtained by cutting the vapor-deposited aluminum film into flakes. As the substrate, preferably, as shown in FIG. 1, the average particle size (μ
XY where m) is the X axis and the average particle thickness (μm) is the Y axis
In Cartesian coordinate system, A (3.5,0.01), B
(6, 0.01), C (60, 0.1), D (35,
0.1) is prepared in a range surrounded by a straight line connecting each point, so that by uniformly orienting in parallel in the glitter coating, it is possible to obtain a denseness without feeling the particle feeling of the aluminum flake pigment. It is possible to form a glittering coating film that satisfies a certain metallic gloss coating film. If the amount is out of the above range, a metallic metallic metallic design coating film having a dense aluminum flake particle conspicuity is not formed, and the glittering feeling of the present invention cannot be exhibited. More preferably, as shown in FIG.
(3.5, 0.01), B (6, 0.01), E (3
0, 0.05), D (35, 0.1) is a range surrounded by a straight line connecting the above points.

The above-mentioned colored vapor-deposited aluminum flake pigment has an average particle diameter (μm) as compared with aluminum flake pigments which have been conventionally used as luster pigments for automobiles.
The feature is that the aspect ratio, which is the ratio of / particle average thickness (μm), is high.

The average particle size is 50% of the particle size distribution measured by a laser diffraction type particle size distribution measuring device. The average particle thickness (μm) is a value obtained by the formula [4000 / water surface coverage (cm ² / g)], and the measuring method is, for example, “Aluminum Handbook” (published April 15, 1972). 9th edition, Japan Light Metals Association; Asakura Shoten), page 1243.

The aluminum flakes and the like used in the conventional metallic paint are obtained by crushing aluminum powder or aluminum foil with a ball mill or the like.
Since these aluminum flakes have a relatively large thickness and have irregularities on the surface, even if such aluminum flakes are oriented in a plane, the surface does not become flat and the aluminum flakes according to the present invention do not become flat. It is not possible to obtain a glittering coating film that satisfies the design coating film with a dense metallic luster that does not feel the graininess of the above.

For the vapor-deposited aluminum flakes as the above-mentioned substrate, for example, a plastic film of oriented polypropylene, crystalline polypropylene, polyethylene terephthalate or the like is used as a base film, a release agent is applied thereon, and aluminum vapor deposition is performed on the release agent. I do. After vapor deposition of aluminum, a top coat agent is applied, for example, on the vapor deposition surface in order to prevent oxidation of the vapor deposited aluminum. Examples of the release agent and the top coating agent include acrylic resin, vinyl resin, nitrocellulose, cellulose resin,
Resins such as polyamide resin, polyester resin, ethylene-vinyl acetate copolymer resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate copolymer resin and petroleum resin can be used.

The vapor-deposited aluminum film is peeled off from the base film, and is cut into flake-shaped aluminum, which is further classified to determine the average particle diameter (μm) on the X axis and the average particle thickness (μm). In the XY Cartesian coordinate system with Y as the Y axis, the specific range can be set. The flaky aluminum may have a release agent and a top coat agent attached thereto, but these are generally dissolved in a solvent used as a metallic paint.

The colored vapor-deposited aluminum flake pigment of the present invention uses the vapor-deposited aluminum flakes as a base material, and various color pigments are attached to the base material. As a method for attaching various color pigments, JP-A-1-315470, JP-A-9-40885, JP-A-9-124973, and JP-A-9-
The method described in 316357 etc. is used. For example, a method is preferred in which various color pigments are coated with a dispersant, and then the mixture is stirred and mixed with a base material in a non-polar solvent to be attached to the base material. Examples of the dispersant include benzoic acid, vinyl benzoate, salicylic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 3-amino-4-methylbenzoic acid, 3,4-diaminobenzoic acid, p- Aromatic carboxylic acids such as aminosalicylic acid, 1-naphthoic acid, cinnamic acid, aminocinnamic acid; ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1, 8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,8-diaminonaphthalene, 1,2-diaminocyclohexane, Stearyl propylene diamine, N-
Amino compounds such as β- (aminoethyl) -γ-aminopropyltrimethoxysilane and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane; aluminum or titanium chelate compounds and the like are used.

The color pigment deposited on the base aluminum flakes is fixed by coating it with a polymer polymerized by in-situ polymerization. Where in-si
Tu polymerization means polymerizing by polymerizing a polymerizable monomer in the step of producing a colored aluminum flake pigment, and specifically, a base aluminum flake to which a colored pigment is attached is dispersed in a solvent. A method may be exemplified in which a polymerizable monomer is added to the slurry, a polymerization initiator is added while stirring and mixing, and the mixture is polymerized to deposit the polymer on the surface of the base aluminum flake.

The polymer to be coated is, for example, synthesized from the following polymerizable monomers: acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, acrylic. Cyclohexyl acid, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-methoxyethyl acrylate, acrylic acid 2
-Diethylaminoethyl, butyl methacrylate, octyl methacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9
-Nonanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate,
Trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, ditrimethylolpropane tetraacrylate, styrene, α-methylstyrene, vinyltoluene,
Divinylbenzene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, maleic acid,
Crotonic acid, itaconic acid, cyclohexene vinyl monooxide, divinylbenzene monooxide.

The amount of the color pigment attached to the colored vapor-deposited aluminum flake pigment is preferably 20 with respect to 100 parts by mass of the vapor-deposited aluminum flake as the base material.
To 500 parts by mass. The amount of color pigment attached is 2
If the amount is less than 0 parts by mass, the high saturation may be deteriorated.
If it exceeds 0 parts by mass, the metallic feeling having a dense feeling may be deteriorated. It is more preferably 50 to 300 parts by mass.
Further, the resin component to be adhered is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the substrate. If the amount of the resin to be adhered is less than 20 parts by mass, the weather resistance may decrease, and if it exceeds 200 parts by mass, the finished appearance may deteriorate. More preferably, it is 30 to 100 parts by mass.
In the entire colored vapor-deposited aluminum flake pigment, the total of the colored pigment layer and the resin layer is preferably 0.03 to 0.5.
Adjust to μm. The total of the color pigment layer and the resin layer is 0.0
If it is less than 3 μm, the high chroma feeling and weather resistance may be deteriorated, and if it exceeds 0.5 μm, the metallic feeling having a dense feeling and the finished appearance may be deteriorated. More preferably, it is 0.03 to 0.3 μm.

The color pigment to be attached is preferably phthalocyanine blue, phthalocyanine green,
Examples include diketopyrrolopyrrole, quinacridone red, isoindolinone yellow, copper azomethine complex, perylene maroon, dioxazine violet, iron oxide, and indanthrene blue.

The content of the above colored vapor-deposited aluminum flake pigment is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the solid content of the vehicle. If the content of the colored vapor-deposited aluminum flake pigment is less than 0.1 part by mass, a glittering coating film satisfying a dense and highly metallic luster may not be obtained, and if it exceeds 50 parts by mass, the smoothness of the coating film may be improved. May not be obtained. More preferably 1 to
30 parts by mass.

On the other hand, the vehicle contained in the glitter coating composition of the present invention disperses the above colored vapor-deposited aluminum flake pigment, and is composed of a coating film forming resin and, if necessary, a crosslinking agent. .

Examples of the coating film forming resin constituting the vehicle include (a) acrylic resin, (b) polyester resin, (c) alkyd resin, (d) fluororesin,
(E) Epoxy resin, (f) Polyurethane resin, (g)
Examples thereof include polyether resins, and these can be used alone or in combination of two or more kinds. In particular,
Acrylic resins and polyester resins are preferably used.

Examples of the acrylic resin (a) include copolymers of acrylic monomers and other ethylenically unsaturated monomers. Acrylic monomers that can be used in the above copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl, t of acrylic acid or methacrylic acid.
-Butyl, 2-ethylhexyl, lauryl, phenyl,
Esterification products such as benzyl, 2-hydroxyethyl, 2-hydroxypropyl, ring-opening adducts of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with caprolactone, glycidyl acrylate or methacrylate, acrylamide, methacrylamide and N-methylol. Examples thereof include acrylamide and (meth) acrylic acid ester of polyhydric alcohol. Examples of the other ethylenically unsaturated monomers copolymerizable with these include styrene, α-methylstyrene, itaconic acid, maleic acid and vinyl acetate.

Examples of the polyester resin (b) include saturated polyester resins and unsaturated polyester resins, and examples thereof include a condensate obtained by heating and condensing a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid include saturated polybasic acid and unsaturated polybasic acid, and examples of the saturated polybasic acid include phthalic anhydride, terephthalic acid, succinic acid, and the like, and as unsaturated polybasic acid, Examples thereof include maleic acid, maleic anhydride, fumaric acid and the like.
Examples of polyhydric alcohols include dihydric alcohols and trihydric alcohols, and examples of dihydric alcohols include:
Examples thereof include ethylene glycol and diethylene glycol, and examples of the trihydric alcohol include glycerin and trimethylolpropane.

Examples of the alkyd resin (c) include polybasic acids and polyhydric alcohols, and fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), natural resins (rosin, amber, etc.), etc. The alkyd resin obtained by reacting with the denaturing agent to modify can be used.

The above-mentioned fluororesin (d) is any one of vinylidene fluoride resin, tetrafluoroethylene resin or a mixture thereof, a polymerizable compound containing fluoroolefin and hydroxy group, and other copolymerizable vinyl resins. Examples of the resin include various fluorine-based copolymers obtained by copolymerizing a compound monomer.

Examples of the epoxy resin (e) include resins obtained by the reaction of bisphenol and epichlorohydrin. Examples of the bisphenol include bisphenol A and F. Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001, and Epicoat 10.
04, Epicoat 1007, Epicoat 1009 (all are trade names, manufactured by Shell Chemical Co., Ltd.) and the like, and those obtained by chain extension of these with an appropriate chain extender can also be used.

Examples of the polyurethane resin (f) include resins having a urethane bond obtained by the reaction of various polyol components such as acrylic, polyester, polyether and polycarbonate with a polyisocyanate compound. As the polyisocyanate compound, 2,4-tolylene diisocyanate (2,4-
TDI), 2,6-tolylene diisocyanate (2,6
-TDI), and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (4,4'-MD
I), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), and mixtures thereof (MDI),
Naphthalene-1,5-diisocyanate (NDI),
3,3'-Dimethyl-4,4'-biphenylene diisocyanate (TODI), xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HDI), isophorone diisocyanate (I
PDI), hexamethylene diisocyanate (HD
I), hydrogenated xylylene diisocyanate (HXDI)
Etc. can be mentioned.

The above-mentioned polyether resin (g) is a polymer or copolymer having an ether bond, such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, or bisphenol. A polyether resin having at least two hydroxyl groups per molecule, such as a polyether derived from an aromatic polyhydroxy compound such as A or bisphenol F, can be mentioned. Further, the above polyether resin and succinic acid, adipic acid, sebacic acid,
Examples thereof include carboxyl group-containing polyether resins obtained by reacting polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid, or reactive derivatives such as acid anhydrides thereof.

The coating film-forming resin is classified into a curable type and a lacquer type, but a curable type is usually used. In the case of a curable type, it is used as a mixture with a cross-linking agent such as an amino resin, a (block) polyisocyanate compound, an amine type, a polyamide type, or a polyvalent carboxylic acid, and a curing reaction proceeds at heating or at room temperature. be able to. It is also possible to use a lacquer type coating film-forming resin having no curability and a curable type in combination.

When the vehicle contains a cross-linking agent, the proportion of the coating film-forming resin and the cross-linking agent is 90 to 50 mass% of the coating film-forming resin and 10 to 50 mass% of the cross-linking agent in terms of solid content. The coating film forming resin is preferably 85 to 60% by mass, and the crosslinking agent is 15 to 40% by mass. When the cross-linking agent is less than 10% by mass (when the coating film forming resin 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 (50% by mass of the coating film forming resin
If it is less than 1), the storage stability of the coating composition decreases and the curing rate increases, resulting in a poor coating film appearance.

The glitter coating composition of the present invention may contain other glitter pigments and coloring pigments in addition to the above colored vapor-deposited aluminum flake pigment.

Other bright pigments are preferably metal oxide-coated alumina flake pigments, metal oxide-coated silica flake pigments, graphite pigments, metal oxide-coated mica pigments, metal titanium flake pigments, stainless flake pigments, and plate-like pigments. At least one pigment selected from the group consisting of iron oxide pigments, metal-plated glass flake pigments, metal oxide-coated glass flake pigments, hologram pigments, and flake pigments composed of cholesteric liquid crystal polymers can be mentioned, more preferably metal oxides. At least one pigment selected from the group consisting of a substance-coated alumina flake pigment, a metal oxide-coated silica flake pigment, a graphite pigment, a metal oxide-coated mica pigment, and a plate-shaped iron oxide pigment.

Further, as a coloring pigment contained in the glitter coating composition, if necessary, a pigment which has been conventionally used for coating materials can be mentioned. As such a pigment, for example, an organic pigment is, for example, an azo lake pigment. , Phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments,
Isoindolinone-based pigments, metal complex pigments and the like,
Examples of inorganic pigments include yellow iron oxide, red iron oxide, titanium dioxide, and carbon black.

The glitter coating composition of the present invention comprises, in addition to the above components, a polyamide wax which is a lubricating dispersion of an aliphatic amide, a polyethylene wax which is a colloidal dispersion mainly composed of polyethylene oxide, an antisettling agent, Curing catalyst,
UV absorbers, antioxidants, leveling agents, surface modifiers such as silicones and organic polymers, anti-sagging agents, thickeners, defoamers, crosslinkable polymer particles (microgels), etc. are appropriately added and contained. be able to. These additives can improve the performance of a paint or a coating film, usually by blending at a ratio of, for example, 15 parts by mass or less with respect to 100 parts by mass of the vehicle (based on solid content).

The glitter coating composition of the present invention is usually provided in a form in which the above-mentioned components are dissolved or dispersed in a solvent. As the solvent, any solvent that dissolves or disperses the vehicle may be used, and an organic solvent and / or water may be used. Examples of the organic solvent include those commonly used in the field of coating materials. Examples thereof 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. Water is preferably used when the use of the organic solvent is regulated from the viewpoint of the environment. In this case, an appropriate amount of hydrophilic organic solvent may be contained.

[Coating Film Forming Method] The coating film forming method of the present invention is a method for forming a multilayer coating film on a substrate, and is used for forming at least one of the layers constituting the multilayer coating film. A method for forming a coating film using the glitter coating composition. Examples of the multilayer coating film include those in which an overcoating film is formed on the undercoating film by using the glitter coating composition, and those in which a clear coating film is formed on the overcoating film. it can. Further, the multilayer coating film comprises an undercoat coating film, an intermediate coating film, a glitter coating film, and a clear top coating film,
It is preferable that the glitter coating film is formed from the glitter coating composition.

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

In the coating film forming method of the present invention, the above-mentioned glitter coating composition is applied to the above substrate directly or through the undercoating film. However, when the substrate is an automobile body or parts, it is previously prepared. It is preferable to undercoat the above-mentioned base material by chemical conversion treatment, electrodeposition coating, spray coating, powder coating or the like.

When the glitter coating film is directly formed on the undercoat coating film on which the undercoat coating is applied without performing the intermediate coating, wet-on-wet (W / W) or wet-on-dry (W / W) D).

The W / W is a method of forming a lower layer coating film and then drying it by air drying or the like to form an upper layer coating film on the lower layer coating film in an uncured state or a semi-cured state. On the other hand, the W / D is a method of forming an upper coating film on a lower coating film obtained by baking and curing the lower coating film.

It is also possible to apply each coating several times. When the coating film is baked, it is baked at 80 to 160 ° C for a predetermined time. The dry film thickness of the glitter coating is 5
-30 μm is preferable, and more preferably 10-20 μm.
Is.

In the present invention, an intermediate coating film can be formed before the glitter coating film is formed on the above substrate. When the undercoating film is formed in the lower layer of the intermediate coating film, it is preferable to form the intermediate coating film by W / D with the undercoating film. The intermediate coating film may be formed by a solvent type paint, an aqueous paint or a powder type paint. The vehicle, pigment, and additives added as necessary for the paint used for forming the intermediate coating film may be those exemplified in the above-mentioned glitter coating composition.

The dry film thickness of the intermediate coating film is 20 to 10
0 μm is preferable, and if it is out of this range, the appearance of the coating film may deteriorate. More preferably, it is 30 to 50 μm.

Then, a glitter coating film is formed on the above intermediate coating film by using the glitter coating composition. This glitter coating film is preferably formed by the above W / D on the above intermediate coating film. The dry film thickness of the glitter coating film is 5 to 3
The thickness is preferably 0 μm, more preferably 10 to 20 μm.

Further, at least one clear top coat film is formed as a top coat layer on the glitter coating film. When the bright coating contains a large amount of bright pigment, two or more layers of clear coating can be applied to improve the smoothness of the surface. The above W / W is preferably used for forming the clear top coating film. When the clear paint is applied a plurality of times, the final clear paint may be applied and then baked at the same time, and the initial clear paint may not be completely cured. The dry film thickness of the clear top coating film is 20 to 20.
100 μm is preferable, and if it is out of this range, the appearance of the coating film may deteriorate. More preferably, it is 30 to 50 μm.

As the clear top coating film, a general clear coating can be used, and a so-called cloudy clear coating film imparting a semitransparent feeling may be used. Further, the clear top coating film may be formed from a solvent type paint, an aqueous paint or a powder type paint. As the solvent-based paint or the water-based paint, a one-pack paint may be used,
A two-pack type paint such as a two-pack type urethane resin may be used. By forming a clear top coat on the glitter coating, it is possible to improve gloss and prevent damage to the glitter pigment. As the clear coating, those generally used for top coating can be used, and a mixture of the above thermosetting resin and a crosslinking agent can be used. In particular, the coating containing the carboxyl group-containing polymer and the epoxy group-containing polymer described in JP-B-8-19315 has a glittering coating when applied to the glittering coating film as a measure against acid rain and W / W. It is preferably used from the viewpoint of not disturbing the orientation of the bright pigment in the film. In addition, these clear coatings may contain additives such as coloring pigments, extender pigments, modifiers, ultraviolet absorbers, leveling agents, dispersants, and defoaming agents, if necessary, within the range of not impairing their transparency. Can be included.

[Multilayer coating film] The multilayer coating film of the present invention is obtained by the above-mentioned coating film forming method, is formed on a substrate, and constitutes a multilayer coating film. At least one of the layers is a glitter coating film formed by using the glitter coating composition described above. Preferably, the multilayer coating film is formed from an undercoating film, an intermediate coating film, a glitter coating film, and a clear topcoating film.

[0059]

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 otherwise specified. The names of raw materials, paints, and equipment are trade names unless otherwise specified.

[Examples 1 to 14, Comparative Examples 1 and 2] [Preparation of base material] Dull steel plate (length 300 mm, width 100 m)
m and thickness 0.8 mm) with zinc phosphate treatment agent (trade name:
After chemical conversion treatment using "Surfdyne SD2000", manufactured by Nippon Paint Co., Ltd., a cationic electrodeposition coating (trade name:
"Power Top U-50" (manufactured by Nippon Paint Co., Ltd.) was electrodeposited to a dry film thickness of 25 μm. Then 1
After baking at 60 ° C. for 30 minutes, an intermediate coating (“Olga S-90 Sealer”, manufactured by Nippon Paint Co., Ltd.) was air-spray coated to a dry film thickness of 40 μm, and 140 ° C.
After baking for 30 minutes, an intermediate coating film was formed to obtain a base material.

[Preparation of glitter coating composition] Acrylic resin (copolymer of styrene / methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate / methacrylic acid, number average molecular weight of about 20,000, hydroxyl value of 4
5, acid value 15, solid content 50 mass%) and melamine resin (trade name: "Uban 20SE", manufactured by Mitsui Chemicals, Inc., solid content 60 mass%) are mixed at a solid content mass ratio of 80:20. To the obtained vehicle, the colored vapor-deposited aluminum flake pigment shown in Table 1 and, if necessary, other pigments were mixed in the proportions shown in Table 1. Then, the organic solvent (toluene / xylene / ethyl acetate / butyl acetate mass ratio = 70
/ 15/10/5) and the mixture was stirred and mixed by a stirrer so that the viscosity was suitable for coating, to prepare a glitter coating.

When the color pigment was phthalocyanine blue, 50 parts by weight of phthalocyanine blue was used with respect to 100 parts by weight of the vapor-deposited aluminum flakes. When the coloring pigment was diketopyrrolopyrrole red, 400 parts by mass of diketopyrrolopyrrole red was used with respect to 100 parts by mass of the vapor-deposited aluminum flakes.

In Comparative Example 1, non-colored evaporated aluminum flakes and color pigments were mixed with the vehicle.

[Clear paint] The following paints were used as the clear paint. A: Acrylic resin solvent-based clear coating (trade name: "Superlac O-130 clear", manufactured by Nippon Paint Co., Ltd.), B: Solvent-based clear coating composed of a blend of a carboxyl group-containing polymer and an epoxy group-containing polymer (trade name) :
"Macflow O-520 clear", manufactured by Nippon Paint Co., Ltd.).

[Formation of multi-layer coating film]
A glittering coating film was formed by coating the glittering coating composition shown in (1) to a dry film thickness of 20 μm. Then with W / W,
The clear top coating film was applied so that the dry film thickness was 50 μm to form a multilayer coating film. The baking conditions are 140 ° C,
It was 20 minutes. The following evaluation items of the obtained coating film were evaluated by the following evaluation methods. The results are shown in Table 1.

[Evaluation Method] Dense feeling: The glitter feeling when the test plate was viewed almost directly in front (highlight portion) was visually evaluated. 3 ... Does not feel the particle sensation of the colored vapor-deposited aluminum flake pigment, and has a remarkable metallic luster with a denseness. 2 ... Does not feel the particle sensation of the colored vapor-deposited aluminum flake pigment, and has a little dense metallic luster. … Colored vapor-deposited aluminum flake pigment particles are noticeable, and there is no dense metallic luster

Saturation: The visual saturation (good: little color turbidity) was evaluated when the test plate was viewed almost right above and obliquely (shaded portion). 4 ... No color turbidity and vivid color 3 ... Almost no color turbidity and vivid color 2 ... Slight color turbidity 1 ... color turbidity

[0068]

[Table 1]

As is clear from the results shown in Table 1, this example is a multi-layer coating film formed by the coating film forming method using the glitter coating composition of the present invention. A multi-layered coating that does not feel a graininess and maintains a dense metallic tone while exhibiting a high saturation feeling in both the highlight part when the coating film is viewed from the front and the shade part when the coating film is viewed obliquely. Was obtained.

On the other hand, in the comparative example, the multi-layer coating film obtained in the above-mentioned examples was not obtained.

[0071]

The glitter coating composition of the present invention contains a colored vapor-deposited aluminum flake pigment and a vehicle. Therefore, the multilayer coating film formed by this coating has a composition of aluminum flake pigment. It is possible to express a dense metallic tone without feeling graininess, and to develop a high-saturation feeling both in the highlight part when the coating film is viewed from the front and in the shade part when the coating film is obliquely viewed. .

Since the multi-layer coating film of the present invention exhibits the above-mentioned brilliance, it has a brilliance in vehicle outer panels such as automobiles and motorcycles, parts thereof, outer surfaces of various containers, coil coating, furniture, home appliance industry, communication industry and the like. Is preferably used in the field where is required.

[Brief description of drawings]

FIG. 1 Average particle size of aluminum flake pigment (μ
XY where m) is the X axis and the average particle thickness (μm) is the Y axis
It is explanatory drawing of a rectangular coordinate system.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09C 3/04 C09C 3/04 3/06 3/06 3/08 3/08 C09D 5/29 C09D 5 / 29 7/12 7/12 F-term (reference) 4J037 AA01 AA15 AA18 AA24 AA26 AA30 CA03 CA09 CB00 DD05 EE03 EE04 EE23 FF02 4J038 CB082 CD091 CG001 DB001 DD001 DD072 DD121 DF001 DG001 HA036 HA06 HA216 HA01 NA1517KA18 HA15 HA546 HA546 HA546 HA546 HA546 HA546

Claims (10)

[Claims] 1. A glittering coating composition containing a colored vapor deposited aluminum flake pigment and a vehicle. 2. The amount of the coloring pigment attached to the colored vapor-deposited aluminum flake pigment is 20 to 500 with respect to 100 parts by mass of the vapor-deposited aluminum flake as the base material.
The glitter coating composition according to claim 1, which is part by mass. 3. The average particle diameter (μm) of the vapor-deposited aluminum flakes as the base material is the X axis, and the average particle thickness (μm).
In the XY Cartesian coordinate system with the Y axis as A
0.01), B (6,0.01), C (60,0.
The glitter coating composition according to claim 1 or 2, which is prepared in a range surrounded by a straight line connecting points 1) and D (35, 0.1). 4. A range surrounded by a straight line connecting the points is
A (3.5, 0.01), B (6, 0.01), E (3
The bright coating composition according to any one of claims 1 to 3, wherein the bright coating composition is 0, 0.05) or D (35, 0.1). 5. The glitter property according to claim 1, wherein the content of the colored vapor-deposited aluminum flake pigment is 0.1 to 50 parts by mass with respect to 100 parts by mass of the solid content of the vehicle. Coating composition. 6. In addition to the colored vapor-deposited aluminum flake pigment, a metal oxide-coated alumina flake pigment, a metal oxide-coated silica flake pigment, a graphite pigment, a metal oxide-coated mica pigment, and a plate-shaped iron oxide pigment. The glitter coating composition according to claim 1, comprising at least one pigment selected from the group consisting of: 7. A coating film forming method using the glitter coating composition according to any one of claims 1 to 6 for forming at least one layer among layers constituting a multilayer coating film. 8. A method for forming a multilayer coating film in which an undercoat coating film, an intermediate coating film, a glitter coating film and a clear top coating film are sequentially formed on a substrate, wherein the glitter coating film is formed. , Claim 1
7. A method for forming a coating film, which is formed from the glitter coating composition according to any one of 1 to 6. 9. The method for forming a coating film according to claim 8, wherein the clear top coating film is formed from a coating material containing a carboxyl group-containing polymer and an epoxy group-containing polymer. 10. A multilayer coating film obtained by the coating film forming method according to claim 7.