JP2001232283A - Brilliant film forming method and coated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant film forming method for improving the saturation and demonstrating the brilliant feeding provided with stereoscopic feeling. SOLUTION: In the brilliant film forming method for forming the brilliant base film containing a brilliant pigment of coloring properties and a coloring pigment on a base and then forming the color clear film containing the coloring pigment, (a) the hue H2 of the Munsel system of the color of the brilliant base film is in the hue range of +25 to +50 or -25 to -50 when the hue H1 of the Munsell system of the color of the coloring pigment in the brilliant base film to the Munsell color cycle 100 is set at 0 and displayed by the left hand +50 and right hand -50 and (b) the hue H3 of the Munsell system of the color pigment in the color clear film is H2-10<=H3<=H2+10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In a field where high design is required such as an automobile body, it is necessary to form a composite coating of a coating film using a brilliant paint containing a brilliant material and a color clear coating film. Are known. As such a technique, Japanese Patent Publication No. 2642798 discloses a multilayer coating film comprising a metallic base coating film containing a coloring pigment and a metallic powder, and a color clear coating film containing a coloring pigment. The light transmittance of the clear coating film is 400 to
In the wavelength range of 700 nm, the average transmittance when measuring the transmittance of a film having a thickness of 30 μm is 30% to 90%.
% And the brightness of the metallic base coating film is
It is disclosed that the L value is 30 or less.

[0003] However, the glittering multi-layer coating film formed in this way is intended to reduce the variation of the color tone with respect to the variation in the film thickness of the color clear coating film. It does not lead to the expression of brilliant feeling having a three-dimensional effect.

[0004]

Accordingly, an object of the present invention is to provide a composite coating film comprising a color clear coating film and a glittering base coating film containing a glittering pigment having coloring properties and a coloring pigment. It is an object of the present invention to provide a method for forming a glittering coating film capable of improving the luster and exhibiting a glittering feeling with a three-dimensional effect, and a coated article coated by this method.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, have reached the present invention. 1. After forming a glittering pigment having coloring properties and a glittering base coating film containing a coloring pigment on a substrate, a glittering coating film forming method for forming a color clear coating film containing a coloring pigment comprises: The hue H ₂ of the brilliant pigment having the above-mentioned coloring property is the hue H ₁ in the Munsell display system of the color pigment color in the brilliant base coating film with respect to the Munsell hue circle 100.
Is 0, the hue range is +25 to +50, or -25 to -50 when displayed in a counterclockwise direction of +50 and a clockwise direction of -50, and (b) a color pigment color in the color clear coating film. The hue H ₃ in the Munsell display system is H ₂ −
A method for forming a glittering coating film, wherein 10 ≦ H ₃ ≦ H ₂ +10. 2. (C) Saturation C _B in the Munsell display system of a composite coating film of the glittering base coating film and the color clear coating film having a chroma C _B of 3 or more in the Munsell display system of the glittering base coating film. the relationship between C _B and _T is, C _T / C _B ≧
The above method for forming a glittering coating film, which is 1.2. 3. Said chroma C _B in glittering base coating film Munsell display system of the above glistening coating forming method is 3-8. 4. The brilliant pigment having the above coloring property is an interference mica pigment, a colored mica pigment, a colored aluminum flake pigment,
The above method for forming a glittering coating film, which is at least one of a metal oxide-coated alumina flake pigment, a metal oxide-coated glass flake pigment, and a metal oxide-coated silica flake pigment. 5. The above glittering coating film forming method, wherein the color clear coating film contains a carboxyl group-containing polymer and an epoxy group-containing polymer. 6. A coated article coated by the above glittering coating film forming method.

[0006]

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

A method for forming a glittering coating film according to the present invention comprises forming a glittering pigment having coloring properties and a glittering base coating film containing the coloring pigment on a substrate, and then coloring the coloring pigment. In the glittering coating film forming method for forming a color clear coating film containing (a) the color pigment color in the glittering base coating film, wherein the hue H ₂ of the glittering pigment having the above-mentioned coloring property is in relation to the Munsell hue circle 100. of the hue H ₁ and 0 in the Munsell display system, it left around +50,
When displayed in a clockwise direction of −50, the hue range is +25 to +50 or −25 to −50, and (b) the hue H ₃ in the Munsell display system of the color pigment color in the color clear coating film is , H ₂ −10 ≦ H ₃ ≦ H ₂ +10. Hue of H ₂ bright pigment having the coloring refers to interference colors when forming a coating film.

In the above condition (a), the hue H ₂ of the brilliant pigment having the above-mentioned coloring properties is defined as 0, the hue H ₁ of the color pigment in the brilliant base coating film is 0, the counterclockwise direction is +50, and the clockwise direction is −
When displayed at 50, +25 to +50, or -25 to
By providing a hue range of −50, a three-dimensional glitter is exhibited in a composite coating film of the color clear coating film and a glittering pigment having coloring properties and a glittering base coating film containing a coloring pigment. Can be. More preferred hue H ₂ is the hue H ₁ and 0, the counterclockwise +50, clockwise -50
+35 to +50, or -35 to -5
0 hue range.

Further hue H ₃ in Munsell display system color pigment colors in the color clear coating film is the above condition (b), by an _{H 2 -10 ≦ H 3 ≦ H} 2 +10, the color clear In a composite coating film of a coating film and a glittering pigment having coloring properties and a glittering base coating film containing a coloring pigment, the saturation can be improved. Range of the hue H ₃ is _{H 1 + 10~H 1 ~H 1 -10} . This range means that the hue H ₁ of the color pigment in the glittering base coating film and the hue H ₃ of the coloring pigment color in the color clear coating film are the same hue in terms of hue. This is a condition for improvement. If the ratio is out of the range, the saturation cannot be improved.

In order to further improve the chroma of the multi-layer coating film, it is preferable that the condition (c) is such that the luster base coating film has a chroma C _B of 3 or more in the Munsell display system and the luster base coating film has relationship between the chroma C _T and the C _B in the Munsell display system of composite coating film of the film and the color clear coating color, a C _T / C _B ≧ 1.2. If the value is outside the range of the condition (c), the saturation may not be improved. Further, more preferably chroma C _B in the Munsell display system of the glittering base coating film is 3-8.

The above hue can be adjusted by changing the types and amounts of various coloring pigments contained in the glittering base coating film and the color clear coating film.
On the other hand, to adjust the saturations C _T and C _B , the type and amount of the color pigment in the glittering base coating film and the color pigment in the color clear coating film are changed so as to satisfy the above condition (c). It can be done by doing.

The above hue and saturation can be measured using an SM color computer (manufactured by Suga Test Instruments Co., Ltd.). Further, the hue H ₁ of the color pigment in the glittering base coating film and the hue H ₃ of the color pigment color in the color clear coating film are, when a single pigment is used, the hue of the pigment when formed into a coating film. Hue, and in the case of a plurality of pigments, means a mixed hue when formed into a coating film. The above-mentioned saturations C _T and C _B , and hues H ₁ , H ₂ and H ₃ all represent the saturation or hue exhibited when the coating film is formed. The hue of the brilliant pigment pigment having coloring properties described below is a hue obtained by a coating film when formed on a black underlayer, and in the case of interference mica pigments, refers to interference colors, such as colored mica or colored aluminum flakes. In the case of non-interfering color mica such as pigment, it refers to the hue of the pigment itself.

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

In the method for forming a glittering coating film of the present invention,
The glitter base coat is formed directly on or through the base coat on the base material, but when the painted product coated by the glitter coat forming method of the present invention is an automobile body and parts, a chemical conversion treatment is performed in advance. It is preferable to perform electrodeposition coating and, if necessary, undercoating with an intermediate coating or the like. In the present specification, the substrate refers to the above-described substrate or a substrate on which the above-described treatment or undercoating has been performed.

[0015] When the base material is a base-coated material, a wet-on-wet (W
/ W) method or the wet-on-dry (W / D) method can form the glittering base coating film. With the above W / W method, after a base coat is applied, it is dried by air drying or the like,
The W / D method is a method of coating a base film that has been baked and cured, while the uncoated state or semi-cured state is applied to the base film.

The glittering base paint used for forming the glittering base coating film is obtained by dispersing a glittering pigment having coloring properties and a coloring pigment in a vehicle.

As the above-mentioned brilliant pigment having coloring properties, preferably, interference mica pigment, colored mica pigment, colored aluminum flake pigment, metal oxide-coated alumina flake pigment, metal oxide-coated glass flake pigment, metal oxide-coated Examples include at least one pigment of silica flake pigment, metal-plated glass flake, graphite, stainless flake, plate-like iron oxide, phthalocyanine flake, and hologram pigment. More preferably, at least one pigment of interference mica pigment, colored mica pigment, colored aluminum flake pigment, metal oxide coated alumina flake pigment, metal oxide coated glass flake pigment, metal oxide coated silica flake pigment is exemplified. . A glitter pigment other than the above pigments, for example, an aluminum flake pigment or white mica can be used in combination within a range that does not impair the glitter of these pigmented glitter pigments.

The content of the above-mentioned brilliant pigment having coloring properties (P
WC) is preferably from 0.1 to 30% by mass, and if it is less than 0.1% by mass, glitter may be insufficient, and 30% by mass.
If it exceeds, the coating film appearance may not be obtained. Preferably, it is 0.1 to 20% by mass.

Further, as the coloring pigment used in the glittering base paint, there can be mentioned those which have been conventionally used for paints. As such, as organic pigments, for example, azo lake pigments, phthalocyanine pigments, indico pigments, berylen pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments And inorganic pigments such as, for example, graphite, yellow iron oxide, red iron oxide, titanium dioxide, and carbon black. The addition amounts of the glitter pigment and the coloring pigment are set in accordance with the development of the hue and saturation satisfying the above conditions (a) and (b). When a glittering pigment and a coloring pigment are used in the glittering base paint, the total content (PWC) of the pigment as a whole is preferably less than 50%, and more preferably less than 30%.
Less than is more preferable. If it exceeds 50%, the appearance of the coating film deteriorates. Also, various extender pigments and the like can be used in combination.

The vehicle contained in the glittering base paint comprises 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)
A polyether resin is mentioned, and in particular, an acrylic resin and a polyester resin are preferably used from the viewpoint of weather resistance. 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 and a curable type together.

The acrylic resin (a) includes a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Acrylic monomers that can be used in the above copolymerization include acrylic acid or methacrylic acid methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-hydroxy Esterified compounds such as ethyl and 2-hydroxypropyl, ring-opened adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide and N-
Methylol acrylamide, polyhydric alcohol (meth)
There are acrylic esters and the like. Other ethylenically unsaturated monomers copolymerizable therewith include styrene, α-methylstyrene, itaconic acid, maleic acid, vinyl acetate and the like.

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

As the alkyd resin (c), in addition to the above polybasic acids and polyhydric alcohols, fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), natural resins (rosin, amber, etc.), etc. An alkyd resin obtained by reacting the above-mentioned denaturing agent can be used.

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

Examples of the epoxy resin (e) include resins obtained by the reaction of bisphenol and epichlorohydrin. Examples of the bisphenol include bisphenols A and F. Examples of the bisphenol type epoxy resin include, for example, Epicoat 828, Epicoat 1001, Epicoat 100
4, Epicoat 1007, Epicoat 1009 (all manufactured by Shell Chemical Co., Ltd.), and those obtained by chain-extending these with an appropriate chain extender can also be used.

As the polyurethane resin (f), there can be mentioned a resin 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-TD
I), 2,6-tolylene diisocyanate (2,6-T
DI), 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, xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HD
I), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (HXDI) and the like.

The polyether resin (g) is a polymer or copolymer having an ether bond, and is a polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene 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 polyether resin and succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, polyvalent carboxylic acids such as trimellitic acid, or a reactive derivative such as an acid anhydride thereof. Carboxyl group-containing polyether resin obtained by the above method.

When the above-mentioned vehicle contains a crosslinking agent, the ratio of the resin for forming a coating film to the crosslinking agent is 90 to 50% by mass, and the content of the crosslinking agent is 10 to 50% by mass in terms of solid content. Preferably, the coating film forming resin is 85 to 60% by mass, and the crosslinking agent is 15 to 40% by mass. 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 may not be sufficient. On the other hand, if the cross-linking agent exceeds 50% by mass (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. There is.

In addition to the above-mentioned components, the above-mentioned brilliant base coating material includes a polyamide wax as a lubricating dispersion of an aliphatic amide, a polyethylene wax as a colloidal dispersion mainly composed of polyethylene oxide, a curing catalyst, an ultraviolet absorber,
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 above-mentioned glittering base paint is usually provided in a form in which the above-mentioned constituents are 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 ethyl ketone, esters such as ethyl acetate, butyl acetate, cellosolve acetate and butyl cellosolve, and alcohols. When the use of an organic solvent is regulated from the viewpoint of the environment, it is preferable to use water. In this case, an appropriate amount of a hydrophilic organic solvent may be contained.

The method for forming the above-mentioned glittering base coating film 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 thickness of the glittering base coating film is preferably from 5 to 50 μm, more preferably from 10 to 30 μm per coat.

In the glittering coating film forming method of the present invention, a color clear coating film further containing a coloring pigment is formed on the glittering base coating film thus formed. By forming at least one layer of the color clear coating film, the relationship between the hue H ₃ of the color pigment color in the color clear coating film and the hue H ₁ of the color pigment color in the glittering base coating film, By satisfying the above condition (b), the saturation of the multilayer coating film can be improved. Further, under the above condition (a), the hue H ₁ of the color pigment color in the glittering base coating film.
And the hue H ₂ of the brilliant pigment having the coloring property, the hue H ₃ of the color pigment in the color clear coating film is obtained.
Can also serve as the hue of H ₂ bright pigment color and non-similar colors having the coloring, express brilliance sense of depth.

In the above condition (c), the saturation C of the composite coating film of the glittering base coating film and the color clear coating film is defined.
_T is, by satisfying the C _T / C _B ≧ 1.2 relative to the chroma C _B of the glittering base coating film can be a multilayer coating film having a more excellent color saturation to form .

The color clear coating used for forming the color clear coating film contains a coloring pigment and a vehicle. The coloring pigment is blended in such an amount that the transparency is not impaired. As the coloring pigment used here, the coloring pigment used for the glittering base paint can be used.
As a vehicle contained in the above color clear paint,
An acrylic resin, a polyester resin, a fluororesin, an epoxy resin, a polyurethane resin, a polyether resin and at least one resin for forming a coating film selected from these modified resins and the above-mentioned crosslinking agent used in the glittering base paint. Although a mixture of these can be used,
When the clear coating containing a carboxyl group-containing polymer and an epoxy group-containing polymer described in JP-A No. 9315 is used to prevent acid rain and to increase the difference in solubility between the glittering base coating film and the W / W method, the It is preferably used from the viewpoint of not disturbing the orientation of the glittering pigment in the glittering base coating film. If necessary, additives such as extenders, modifiers, ultraviolet absorbers, leveling agents, dispersants, defoamers and the like can be blended as long as the transparency is not impaired.

The method of forming the color clear coating film is not particularly limited, but a spray method, a roll coater method and the like are preferred. The dry film thickness of the color clear coating film is 1
20 to 50 μm is preferable per coat, and 25 to 40 μm
m is more preferred.

In the present invention, the formation of the color clear coating film is carried out on the glittering base coating film. This formation may be performed after or before the glittering base coating film is cured. Before curing, the bright base coating film and the color clear coating film are cured simultaneously. When the color clear coating film is applied a plurality of times, the color clear coating film may be baked simultaneously after the final color clear coating film is applied, or may be baked for each layer. The color clear coating film thus formed has 12
It is baked at a temperature of 0 to 160 ° C. for a predetermined time to obtain a glittering coating film. In order to protect the coating film, a clear coating film containing no coloring pigment may be formed on the color clear coating film.

Coated product A coated product obtained by the coating film forming method of the present invention is obtained by coating a base material with a brilliant base coating film by the above-described brilliant coating film forming method.
Next, a color clear coating film was formed. The color pigment color hue H ₁ , the color pigment color hue H ₂ , and the color pigment color hue H ₃ in the color clear coating film in the glitter base coating film are determined by the above conditions (a) and (b). By satisfying (3), a multi-layer coating film exhibiting a three-dimensional glitter is formed. Further, under the above condition (c), the saturation C _B in the Munsell display system of the glittering base coating film is 3 or more, and the saturation C _T of the composite coating film of the glittering base coating film and the color clear coating film is: C _T / C _B ≧ relative to the chroma C _B of the glittering base coating film
By satisfying 1.2, a multilayer coating film having more excellent chroma is formed.

[0038]

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.

[0039] Examples 1-7, prepared dull steel plate of Comparative Example 1-2 substrate (length 300 mm, width 100mm and thickness 0.8mm) the zinc phosphate treatment agent ( "Surf Dyne SD2
000 "(manufactured by Nippon Paint Co., Ltd.), and then a cationic electrodeposition paint (" Power Top U-50 ", manufactured by Nippon Paint Co., Ltd.) was electrodeposited so as to have a dry film thickness of 25 [mu] m. Then, after baking at 160 ° C. for 30 minutes, an intermediate coating (“Olga S-90 Sealer Gray”,
(Nippon Paint Co., Ltd.) was applied by air spray coating so as to have a dry film thickness of 40 μm, and baked at 140 ° C. for 30 minutes to form an intermediate coating film, which was used as a substrate.

Preparation of glittering base paint Acrylic resin (styrene / methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate /
Methacrylic acid copolymer, number average molecular weight about 20,000,
A hydroxyl value of 45, an acid value of 15, and a solid content of 50% by mass) and a melamine resin ("Uban 20SE", manufactured by Mitsui Chemicals, Inc., solid content of 60% by mass) are blended at a solid content mass ratio of 80:20 to obtain. Glitter pigments and coloring pigments having coloring properties shown below were blended in the amounts shown in Table 1 (PWC) with the obtained vehicle. Subsequently, an organic solvent (mass ratio of toluene / xylene / ethyl acetate / butyl acetate = 70/15/10/5)
At the same time, the mixture was stirred and mixed by a stirrer so as to have a proper coating viscosity to prepare a glittering coating composition.

Bright pigment: Bright pigment A (interference mica: interference color green, "Iriodin 235WII", manufactured by Merck), bright pigment B (colored mica: red, "Iriodin 5")
04WII ”, manufactured by Merck Co., Ltd., glitter pigment C (colored aluminum flake pigment: blue,“ Friend Color F500BL ”, manufactured by Showa Aluminum Co., Ltd.), glitter pigment D (metal oxide-coated alumina flake pigment:
Interference color gold, "Xirallic T60-20W
III Sunbeam Gold ", manufactured by Merck & Co., Ltd., brilliant pigment E (metal oxide-coated glass flake pigment: green," EXTERIA MERLIN FIREM "
IST GREEN ”, manufactured by Engelhard)

Color pigment: Color pigment A (green color: phthalocyanine green) Color pigment B (red color: perylene red) Color pigment C (blue color: phthalocyanine blue) Color pigment D (yellow color: isoindoline yellow) Color pigment E (Black color: carbon black)

Preparation of Color Clear Coating Color clear coating was acrylic / melamine resin clear coating 1 (“Super Lac O-130 Clear”,
Nippon Paint Co., Ltd.) or a clear coating material 2 containing a carboxyl group-containing polymer and an epoxy group-containing polymer ("Macflow O-520 Clear", manufactured by Nippon Paint Co., Ltd.) in the amount shown in Table 1 ( PWC). Next, the organic solvent (toluene / xylene / ethyl acetate / butyl acetate mass ratio = 70/15/10 //
The mixture was stirred and mixed so as to have an appropriate coating viscosity according to 5) to prepare a color clear coating.

[0044]Formation of coating film The light shown in Table 1 was applied to the surface of the substrate on which the intermediate coating film was formed.
Apply bright base paint so that dry film thickness becomes 15μm
did. Coating is electrostatic coating machine ("Auto REA", AB
B Industry Co., Ltd.), atomization pressure 2.8kg / c
m^TwoI went in. Set for 3 minutes after painting, then
The color clear paint shown in No. 1 was dried to a thickness of 50 μm.
And set at room temperature for 10 minutes.
Bake at a temperature of 0 ° C. for 30 minutes. Kara for evaluation
-Use a clear coating film that does not contain coloring pigments in the clear coating film.
Created for each glitter base coating, and the meaning of the obtained coating
The following evaluation of the three-dimensional effect as the designability 1 and the design improvement 2 as the designability 2
The results were shown in Table 1. The coloring property
Hue H of glittering pigments having_TwoTo the Munsell hue circle 10
Munsell table of coloring pigment color in glittering base coating film for 0
Hue H in the indicator system₁0, counterclockwise +50, clockwise
The above-mentioned brilliant base coating film is represented by X when represented by -50
Hue H of Colored Pigment Color₁Of the above brilliant pigment
Hue H_TwoX and the color
Hue H of the color pigment in the rear coating film _ThreeThe light above
Hue H of bright pigment_TwoIs shown in Table 1 as Y
Was. In addition, C of the above glittering base coating film_B, The brilliant base
Saturation C of composite paint film consisting of
_TAre shown in Table 1.

Evaluation Method Designability 1 (Improvement of Saturation): The effect of improving the saturation of the formed multi-layer coating film as compared with a multi-layer coating film having a clear coating film containing no coloring pigment as a top coat was evaluated. It was evaluated visually. 3: Significantly improved saturation 2: Saturation improved 1: Saturation not observed Appearance 2 (three-dimensional appearance): Formed multi-layer coating film, top coated with clear coating film containing no coloring pigment The three-dimensional effect was visually evaluated as compared with the multi-layer coating film. 3: Three-dimensional effect is noticeable. 2: Three-dimensional effect. 1: No three-dimensional effect.

[0046]

[Table 1]

As is clear from the results shown in Table 1, in Examples 1 to 7, coatings were formed by the method for forming a glittering coating film of the present invention. Since the hue and saturation of the above satisfy the above conditions (a) and (b), the effect of improving the saturation of the multilayer coating film was obtained. On the other hand, in Comparative Examples 1 and 2, the conditions (a) and (b)
Was not satisfied, so that the effect of improving the saturation was not recognized.

[0048]

The method for forming a glittering coating film of the present invention comprises the steps of: providing a substrate with a hue H ₁ of a color pigment in the glittering base coating film, a hue H _{2 of} the glittering pigment, and a color clear coating film on the substrate; By satisfying the above conditions (a) and (b) with the hue H ₃ of the color pigment color in the inside, the composite coating film of the glittering base coating film and the color clear coating film has improved saturation and three-dimensional appearance. It became possible to express a brilliant feeling.

Further, the above condition (c): the chroma C _B of the glitter base coating in the Munsell display system is 3 or more, and the chroma C of the composite coating of the glitter base coating and the color clear coating. _T is, by satisfying the C _T / C _B ≧ 1.2 relative to the chroma C _B of the glittering base coating film, further composite coating film with glittering base coating film and the color clear coating Color saturation can be improved.

Since the coating film obtained by the present invention exhibits the above-mentioned brilliant design, it is required to have a brilliant and patterned pattern such as a vehicle outer plate of a car or a motorcycle, a container outer surface, a coil coating, a home appliance industry, etc. Is preferably used.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) B05D 7/24 303 B05D 7/24 303B B32B 7/02 103 B32B 7/02 103 C09D 5/29 C09D 5/29 163 / 00 163/00 201/00 201/00 F term (reference) 4D075 AE03 CB01 CB13 DC12 EA43 EC02 EC03 EC04 EC10 EC11 EC23 4F100 AA19B AA19H AA20B AA20H AB03A AB10B AB10H AC05B AC05H AG00B AG00H AK25B AK25C AK36A AK25B AK25C AK36A BA10C BA13 CA13B CC00B CC00C DE02B DE02H GB16 GB31 GB32 GB48 HB00C JL10C JN01C JN21B JN28 JN30 YY00B 4J038 CC061 CC081 CD111 CD121 CF071 CG061 CG141 CG171 CH031 CH041 CH121 GA1 DD01 DB06 DB01 DB06 HA446 HA486 HA546 KA08 KA15 KA21

Claims (6)

[Claims] 1. A method for forming a glittering coating film, comprising: forming a glittering pigment having coloring properties and a glittering base coating film containing a coloring pigment on a substrate, and then forming a color clear coating film containing the coloring pigment. In (a), the hue H ₂ of the brilliant pigment having coloring properties is such that the hue H ₁ in the Munsell display system of the color pigment color in the brilliant base coating film is 0 with respect to the Munsell hue circle 100, and the counterclockwise direction is +50. The hue range of +25 to +50, or -25 to -50 when displayed with clockwise rotation of -50, and (b) the hue H in the Munsell display system of the color pigment color in the color clear coating film
₃ is a method for forming a glittering coating film in which H ₂ −10 ≦ H ₃ ≦ H ₂ +10. (C) Munsell display of a composite coating film of the glittering base coating film and the color clear coating film color having a chroma C _B of 3 or more in the Munsell display system of the glittering base coating film. relationship between the C _B and chroma C _T in the system is, C _T
2. The method of claim 1, wherein / C _B ≧ 1.2. Wherein the chroma C _B in the Munsell display system of the bright base coating film, glistening coating forming method according to claim 1 or 2 wherein the 3 to 8. 4. The brilliant pigment having coloring properties includes interference mica pigment, colored mica pigment, colored aluminum flake pigment, metal oxide-coated alumina flake pigment, metal oxide-coated glass flake pigment, metal oxide-coated silica flake. 4. A pigment according to claim 1, which is at least one pigment.
The method for forming a glittering coating film according to any one of the preceding claims. 5. The method according to claim 1, wherein the clear top coating contains a carboxyl group-containing polymer and an epoxy group-containing polymer. 6. A coated article coated by the glittering coating film forming method according to any one of claims 1 to 5.