JP5421028B2 - Coating method - Google Patents

Description

  The present invention relates to a coating film forming method capable of forming a coating film with high whiteness, excellent density, lightness change from highlight (near specular reflection light) to shade (oblique direction), and calmness. It is.

  The purpose of applying the paint is to protect the material and impart aesthetics. In industrial products, the appearance (color) is important in order to increase the product power. The paint colors of industrial products demanded by consumers are various, but in recent years, especially in the fields of automobile outer panels, home appliances, etc., white paint colors have become clean and popular. In particular, the white pearl color, whose appearance changes slightly depending on the viewing angle, is attracting attention as a color that combines cleanliness and luxury.

  A white pearl color coating film is obtained by applying a metallic base paint containing scaly glittering pigment on a white color base paint film, and further applying a top clear paint to form a multilayer paint film. be able to. Brightness is expressed by the scaly glittering pigment blended in the metallic base paint.

  Conventionally, silver-type or interference-type pearl pigments in which a transparent scale-like substrate is coated with titanium dioxide have been used as scale-like glitter pigments to be blended in the metallic base paint. When an interference type pearl pigment is used, an interference color appears in the highlight and a complementary color appears in the shade, so that the paint color may change depending on the observation angle.

  When a silver type pearl pigment is used, there is no change in color tone depending on the observation angle as described above, but turbidity may occur due to scattering of the pearl pigment in the shade.

  Patent Document 1 relates to a coating composition for forming a coating film excellent in design properties and a coating film forming method, and in a multilayer coating film formed by coating a color base coating material, an interference color coating material, and a clear coating material, The interference color paint is a paint containing two or more kinds of interference color pigments, and when the interference color pigment divides the hue circle into 100 and displays it in the clockwise direction +50 and the counterclockwise direction −50, one of them When the hue of the interference color pigment is 0, the paint composition is such that at least one color of the remaining interference color pigment falls within the range of +40 to +50 and −40 to −50. A method for forming a multilayer coating film is described. According to this method, a mild coating color with little change in color tone depending on the observation angle can be obtained. However, when two or three kinds of interference color pigments having different interference colors are used in combination, a particle feeling is developed and a dense feeling is insufficient. There was a problem to do.

JP-A-8-218009

  An object of the present invention is to provide a coating film forming method capable of forming a coating film with high whiteness, excellent denseness, a gradual change in brightness from highlight (near specular reflection light) to shade (oblique direction), and calmness. Is to provide.

The present invention
1. Light interference with different interference colors in which the base color is a color base coating film with a lightness L * in the range of 75 to 90 in the L * a * b * color system, and a translucent scaly base material is coated with titanium dioxide. Coating method obtained by sequentially forming a metallic base coating film containing four types of functional pigments and a top clear coating film,
2. The hue angle h of the interference color L * c * h color system in the highlight of the four types of light interference pigments is in the range of 12 ° to 22 °, 86 ° to 96 °, 144 ° to 154 °, respectively. , 26
Item 2. The method for forming a coating film according to Item 1, which is within a range of 3 ° to 273 °.
3. The coating film forming method according to Item 1 or 2, wherein the total amount of the light-interfering pigment is within the range of 4 to 20 parts by mass as the solid content with respect to 100 parts by mass of the resin solid content of the metallic base coating film,
4). 4. The coating film forming method according to any one of 1 to 3, wherein the light interference pigment is a titanium oxide-coated alumina flake pigment obtained by coating scaly aluminum oxide with titanium dioxide.

  The method for forming a coating film according to the present invention is capable of forming a coating film with high whiteness, excellent density, and lightness change from highlight (near specular reflection light) to shade (diagonal direction) and calmness. In particular, it is useful in fields where a high-grade appearance is required, such as automobile outer panels and home appliances.

  In the coating film forming method of the present invention, the base material is a metal such as iron, zinc or aluminum, an alloy of these metals, a molded product plated or vapor-deposited with these metals, and glass, plastic or foam. A material such as a molded product by the body can be listed. A treated material obtained by subjecting these materials to a degreasing treatment or a surface treatment can also be used as a base material. Furthermore, a coating film forming material in which an undercoat coating film or an intermediate coating film is formed on the above substrate can be used as the substrate. Of these, a film-forming material is particularly preferable.

  The above-mentioned undercoat film is used to conceal the surface of the material, impart anticorrosion and rustproofness to the material, and further improve the adhesion between the intermediate coat film and topcoat film described later and the material. It is formed and can be obtained by applying and curing an undercoat. The type of the undercoat paint is not particularly limited, and examples thereof include an electrodeposition paint and a solvent-type primer.

  The intermediate coating film is formed to conceal the surface of the material or the undercoating film, or to impart adhesion or chipping resistance. It can be obtained by applying and curing a paint. Here, the undercoat coating film may be dry-cured or uncured. The type of the intermediate coating is not particularly limited, and known ones can be used. For example, an organic solvent-based or water-based intermediate coating containing a thermosetting resin composition and a color pigment can be preferably used.

  In the method for forming a coating film according to the present invention, when a substrate on which an intermediate coating film is formed is used as a substrate, the lightness L * in the L * a * b * color system of the intermediate coating film is 70 or more. It is preferable from the point of the whiteness of a multilayer coating film. The L * a * b * color system is a color system defined by the International Lighting Commission in 1976 and adopted in JIS Z 8729, and L * is a numerical value representing lightness. Specifically, the lightness of the intermediate coating film is a spectroscopic light received at an angle of 45 degrees from specular reflection light using MA-68II (trade name, manufactured by x-Rite, multi-angle spectrophotometer). It is defined as a numerical value obtained by calculation based on the reflectance.

  In the method of the present invention, in the case of using a base coating film and / or an intermediate coating film formed as a base material, the base coating film and / or the intermediate coating film is heated and described later after crosslinking and curing. Although the color base coating film can be formed, the color base coating film can also be formed in a state where the undercoating film and / or the intermediate coating film is uncured, and the method of the present invention also includes this case. .

  In the coating film forming method of the present invention, a color base coating film having a lightness L * in the range of 75 to 90 in the L * a * b * color system is formed on the substrate.

  The color base coating film can be formed by applying a color base paint containing a titanium oxide pigment on a base material, followed by drying and curing.

  Titanium oxide pigments are widely used as white pigments because of their high refractive index, and there are rutile and anatase types depending on the crystal form, and any of these may be used in the present invention. From the point of view, the rutile type can be used. Moreover, you may use what processed the surface with inorganic compounds, such as a silica, a zirconium, and aluminum, for the purpose of improving a dispersibility and a weather resistance. From the viewpoint of the hiding power of the color base coating film, it is preferable to use those having a primary particle diameter in the range of 100 to 400 nm, and more preferably in the range of 200 to 300 nm.

  The content of the titanium oxide pigment in the color base paint is preferably 30 to 150 parts by weight, particularly preferably 100 parts by weight of resin solids, which is a vehicle-forming component described later, from the viewpoint of concealability, finish, and brightness. Is 50-90 mass parts.

  In addition to the titanium oxide pigment, a color pigment can be blended in the color base paint for the purpose of finely adjusting the hue and brightness of the multilayer coating film. The color pigment is not particularly limited, and specific examples thereof include transparent iron oxide pigments, composite metal oxide pigments such as titanium yellow, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, and perylenes. Pigments, perinone pigments, benzimidazolone pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, selenium pigments, indigo pigments Or any one of carbon black pigments or the like can be used in combination.

  In the present invention, when a color pigment other than a titanium oxide pigment is blended in the color base paint, the content is 100 masses of resin solid content in the case of an organic pigment or a carbon black pigment from the point of brightness of the multilayer coating film. It is preferably 0.1% by mass or less based on parts, and in the case of an inorganic pigment, it is preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.05 to 3 parts by mass. It is preferable to be within.

  The color base paint can usually contain a resin component as a vehicle. Specifically, the resin component includes a base resin such as an acrylic resin, a polyester resin, an alkyd resin, or a urethane resin having a crosslinkable functional group such as a hydroxyl group, and a melamine resin, a urea resin, or a polyisocyanate as necessary. A combination of a crosslinking agent such as a compound (including a block body) is used, and these are used by being dissolved or dispersed in a solvent such as an organic solvent and / or water.

  Furthermore, for color base paints, various additives such as solvents such as water or organic solvents, pigment dispersants, anti-settling agents, curing catalysts, antifoaming agents, antioxidants, UV absorbers, and extender pigments as necessary. Etc. can be appropriately blended.

  The color base coating film of the present invention can be formed by applying the color base paint by a method such as electrostatic coating, air spray, airless spray, and drying and curing. The thickness of the color base coating film is preferably in the range of 10 to 45 μm based on the cured coating film from the point of hiding the substrate and the smoothness of the coating film, more preferably in the range of 15 to 35 μm. It is. The color base paint of the present invention can usually be crosslinked and cured at a temperature of about 70 to about 150 ° C.

  In the present invention, a light interference pigment obtained by coating a translucent scaly substrate with titanium dioxide on a cured coating film obtained by applying a color base paint and drying and curing, or on an uncured coating film surface. A metallic base coating film is formed by painting a metallic base coating containing four types.

  Specific examples of the translucent scaly substrate include mica, artificial mica, and alumina flakes. Among these substrates coated with titanium dioxide, four types whose interference color is controlled by the thickness of the coating layer of titanium dioxide are used. As the light interference pigment in which four kinds of translucent scaly substrates used are coated with titanium dioxide, the hue angle h in the L * c * h color system of the interference color is red: 12 ° to 22 °, respectively. Within the range, yellow (gold): within the range of 86 ° to 96 °, green: within the range of 144 ° to 154 °, blue: within the range of 263 ° to 273 ° obtained by coating From the point of the whiteness of the coating film obtained, it is preferable.

  In the present specification, the interference color of the light interference pigment obtained by coating a translucent scaly substrate with titanium dioxide is 75 parts by mass of a hydroxyl group-containing acrylic resin (hydroxyl value 100, number average molecular weight 20000) and 25 parts by mass of melamine resin. 15 parts by mass of the light-interfering pigment per 100 parts by mass of the resin component consisting of the above, mixed by stirring, diluted with solvent to an appropriate viscosity for coating, and an organic solvent having a solid content of about 25% The paint obtained by preparing the mold paint is air spray-coated on a coating plate on which a black (N-2) coating film has been formed in advance so as to have a film thickness of 18 μm as a cured coating film, and then at room temperature for 15 minutes. Leave it on, and then apply a clear paint (Lugabe Kukuriya, manufactured by Kansai Paint, trade name, acrylic resin / amino resin type, organic solvent type) on the uncured coating surface as a cured coating film so that the air is 35 μm. Spray coating MA-68II manufactured by X-Rite Co., Ltd. (commercial product) was further allowed to stand at room temperature for 15 minutes and then heated and dried at 140 ° C. for 30 minutes using a hot air dryer. And a colorimetric value measured based on the spectral reflectance received at 15 ° with respect to the specularly reflected light. The L * C * h color system is a color system designed based on the L * a * b * color system specified by the International Commission on Illumination in 1976 and adopted in JIS Z 8729. H represents a hue angle, and is an angle moved counterclockwise with the red axis as 0 ° in the chromaticity diagram.

  In the present invention, from the point of denseness of the multilayer coating film, a titanium oxide-coated alumina flake in which scaly aluminum oxide is coated with titanium dioxide as a light-interfering pigment in which a translucent scaly substrate is coated with titanium dioxide. Preference is given to using pigments.

  The scaly aluminum oxide pigment coated with titanium dioxide is a scaly glittering pigment coated with titanium dioxide using scaly aluminum oxide as a base material, and is described in JP-A-9-77512.

  In the present invention, as a light interference pigment in which a translucent scaly substrate is coated with titanium dioxide, four types having different interference colors as described above are used so that the ratio of each light interference pigment becomes equal. use. Therefore, the additive color mixture of the interference colors of the respective light interference pigments is white. Therefore, the whiteness of the coating film is increased, and a coating film having a finer texture can be obtained. Furthermore, there is little turbidity in the shade (oblique direction), and there is an effect that a light-weight coating from the highlight to the shade is gradual and a soft texture can be obtained.

  In the method of the present invention, the blending amounts of the four types of optical interference pigments in the metallic paint are based on 100 parts by mass of the solid content of the resin composition to be described later in terms of the whiteness and denseness of the resulting coating film. It is preferably in the range of 0.5 to 40 parts by mass, more preferably in the range of 2 to 20 parts by mass, and particularly preferably in the range of 6 to 15 parts by mass. Further, the blending amount of each of the four types of pigments is preferably in the range of 20 to 30% by mass with respect to the total amount of the four types of light-interfering pigments, more preferably from the point of not exhibiting a chromatic color with highlights. Is in the range of 23 mass% to 27 mass%, particularly preferably in the range of 24 mass% to 26 mass%.

  In the present invention, the scale-like glitter pigment obtained by coating a translucent scale-like base material with titanium dioxide has a mean particle size in the range of 5 to 45 μm. From the viewpoint of the finish and the denseness, the particle size is preferably in the range of 7 to 30 μm, particularly preferably in the range of 8 to 25 μm. It is preferable to use a thickness in the range of 0.05 to 1.5 μm. The particle diameter and thickness here mean numerical values obtained by observing the light interference pigment with an optical microscope or an electron microscope.

  The metallic base paint of the present invention can contain a resin component as a vehicle in addition to the light interference pigment in which a translucent scaly substrate is coated with titanium dioxide. The resin component is preferably a thermosetting resin composition. Specifically, for example, a base resin such as an acrylic resin, a polyester resin, an alkyd resin, or a urethane resin having a crosslinkable functional group such as a hydroxyl group, and a melamine resin. , Urea resins, polyisocyanate compounds (including block bodies) and the like are also used in combination, and these can be used by dissolving or dispersing them in a solvent such as an organic solvent and / or water.

  Furthermore, for metallic base paints, solvents such as water or organic solvents, rheology control agents, pigment dispersants, antisettling agents, curing catalysts, antifoaming agents, surface conditioners, antioxidants, UV absorbers are used as necessary. Various additives such as additives, extender pigments and the like can be appropriately blended.

  In the coating film forming method of the present invention, the metallic base coating can be applied by a method such as electrostatic spray coating, air spraying, airless spraying, and the film thickness is 0.5 to 30 μm based on the cured coating film. Is preferably in the range of 5 to 25 μm, particularly preferably in the range of 7 to 18 μm.

  When spraying a metallic base paint, the solid content is usually 15 to 50% by weight, preferably 20 to 40% by weight, and the viscosity at 20 ° C. is 15 to 20 seconds / Ford cup. It is preferable to adjust so as to be # 3. The metallic base coating itself can be crosslinked and cured, usually at a temperature of about 70 to about 150 ° C.

  In the coating film forming method of the present invention, the metallic base coating can be applied by a method such as electrostatic spray coating, air spraying, airless spraying, and the film thickness is 0.5 to 30 μm based on the cured coating film. Is preferably in the range of 5 to 25 μm, particularly preferably in the range of 7 to 18 μm.

  In the coating film forming method of the present invention, one or more top clear paints are further applied on the paint film obtained by applying the metallic base paint to form a top clear paint film.

  In the method of the present invention, a top clear paint described later can be applied on the coating film on which the metallic base paint has been applied and cured, but the coating film in an uncured state without being heated and cured after the metallic base paint has been applied. Top clear paint can be applied on top.

  As the top clear coating material of the present invention, conventionally known ones can be used without limitation. For example, a liquid or powdery coating composition containing a base resin and a crosslinking agent can be applied. Examples of the base resin include acrylic resin, polyester resin, alkyd resin, fluororesin, urethane resin, and silicon-containing resin containing a crosslinkable functional group such as a hydroxyl group, a carboxyl group, a silanol group, and an epoxy group. It is done. As a crosslinking agent, a melamine resin capable of reacting with the functional group of the base resin, urea resin, polyisocyanate compound, block polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, Examples thereof include alkoxysilane group-containing compounds or resins. Moreover, additives, such as solvents, such as water and an organic solvent, a curing catalyst, an antifoamer, and a ultraviolet absorber, can be suitably mix | blended as needed.

  As the top clear paint in the present invention, a color clear paint containing a color pigment and / or a dye can be used as long as transparency is not impaired. As the color pigments and dyes, those known in the art for inks and paints can be used alone or in combination of two or more. The addition amount may be appropriately determined, but is preferably 30 parts by mass or less, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the vehicle-forming resin composition in the top clear coating. Within range.

  In the present invention, when two or more layers of the top clear paint are applied, the color clear paint can be applied to the first layer.

  The top clear coating in the present invention can be applied by a method such as electrostatic coating, air spray, airless spray, and the film thickness is preferably in the range of 5 to 40 μm based on the cured coating film.

  In the present invention, when the top clear paint is applied without heating and curing the color base paint and / or the metallic base paint, these paints can be simultaneously heated and cured after the top clear paint is applied. The top clear coating film itself can be crosslinked and cured at a temperature of about 70 to about 150 ° C.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to only these examples. “Part” and “%” are based on mass.
(Production Example 1) Production of hydroxyl group-containing acrylic resin 40 parts of ethylene glycol monoethyl ether acetate was charged into a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, stirred and mixed, and the temperature was raised to 135 ° C. Warm up. Subsequently, the following monomer / polymerization initiator mixture was dropped into a reaction vessel maintained at the same temperature over 3 hours, and aging was performed for 1 hour after the completion of the dropping. Thereafter, a mixture of 10 parts of ethylene glycol monoethyl ether acetate and 0.6 parts of 2,2′-azobis (2-methylpropionitrile) was dropped into the reaction vessel over 1 hour and 30 minutes maintained at the same temperature. Aged for another 2 hours. Next, ethylene glycol monoethyl ether acetate was distilled off under reduced pressure to obtain a hydroxyl group-containing acrylic resin having a hydroxyl value of 54 mgKOH / g, a number average molecular weight of 50,000 and a resin solid content of 65% by mass. Here, the number average molecular weight means that measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
Monomer / polymerization initiator mixture:
From 38 parts of methyl methacrylate, 17 parts of ethyl acrylate, 17 parts of n-butyl acrylate, 7 parts of hydroxyethyl methacrylate, 20 parts of lauryl methacrylate and 1 part of acrylic acid and 2 parts of 2,2′-azobis (2-methylpropionitrile) Mixture.
(Production Example 2) Production of acrylic resin emulsion Thermometer, thermostat, stirrer, reflux condenser and reactor equipped with 130 parts by mass of deionized water, Aqualon KH-10 (trade name, surfactant, No. 1) 0.52 parts by mass) (manufactured by Ichi Kogyo Seiyaku Co., Ltd.) was charged, stirred and mixed in a nitrogen stream, and heated to 80 ° C. Next, 1% of the total amount of the following monomer emulsion (1) and 5.3 parts by mass of 6% ammonium persulfate aqueous solution were introduced into the reaction vessel and maintained at 80 ° C. for 15 minutes. Then, the remaining monomer emulsion (1) was dripped in the reaction container hold | maintained at the same temperature over 3 hours, and it age | cure | ripened for 1 hour after completion | finish of dripping. Thereafter, the following monomer emulsion (2) was dropped into the reaction vessel over 1 hour and aged for 1 hour, and then cooled to 30 ° C. while gradually adding 40 parts by mass of a 5% dimethylethanolamine aqueous solution to the reaction vessel. , While filtering through a 100 mesh nylon cloth, discharging with an average particle size of 100 nm (submicron particle size distribution measuring device “COULTER N4 type” (manufactured by Beckman Coulter), diluted with deionized water and measured at 20 ° C. An acrylic resin emulsion having a solid content concentration of 30% was obtained. The obtained acrylic resin had an acid value of 33 mgKOH / g and a hydroxyl value of 25 mgKOH / g.

  Monomer emulsion (1): 42 parts by weight of deionized water, 0.72 parts by weight of Aqualon KH-10, 2.1 parts by weight of methylenebisacrylamide, 2.8 parts by weight of styrene, 16.1 parts by weight of methyl methacrylate, ethyl acrylate Monomer emulsion (1) obtained by mixing and stirring 28 parts by mass and 21 parts by mass of n-butyl acrylate.

Monomer emulsion (2): 18 parts by weight of deionized water, 0.31 parts by weight of Aqualon KH-10, 0.03 parts by weight of ammonium persulfate, 5.1 parts by weight of methacrylic acid, 5.1 parts by weight of 2-hydroxyethyl acrylate Monomer emulsion (2) obtained by mixing and stirring 3 parts by mass of styrene, 6 parts by mass of methyl methacrylate, 1.8 parts by mass of ethyl acrylate and 9 parts by mass of n-butyl acrylate.
(Production Example 3) Polyester resin production Thermometer, thermostat, stirrer, reflux condenser and reaction vessel equipped with water separator, trimethylolpropane 109 parts by mass, 1,6-hexanediol 141 parts by mass, hexahydro anhydride 126 parts by mass of phthalic acid and 120 parts by mass of adipic acid were charged, and the temperature until reaching 160 ° C. to 230 ° C. was increased to 3 hours, and then a condensation reaction was performed at 230 ° C. for 4 hours. Thereafter, the temperature of the obtained condensation reaction product was lowered to 170 ° C., and 38.3 parts by weight of trimellitic anhydride was further added to add a carboxyl group, and the mixture was reacted at 170 ° C. for 30 minutes. Dilution with ethyl-1-hexanol gave a polyester resin solution with a solid content of 70%. The obtained polyester resin had an acid value of 46 mgKOH / g, a hydroxyl value of 150 mgKOH / g, and a weight average molecular weight of 6,400. Here, the weight average molecular weight means that measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
(Production Example 4) Production of white titanium oxide dispersion 1 In a 225 ml mayonnaise bottle, 15.4 parts of the hydroxyl group-containing acrylic resin obtained in Production Example 1, 20 parts of ethylene glycol monoethyl ether acetate, JR-903 (trade name) , White titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.), and after stirring and mixing, 130 parts of 1.5 mm diameter glass beads were further introduced and sealed, and DASH2000-K Disperser (trade name, manufactured by LAU, Dispersion for 60 minutes. After the dispersion, 100-mesh wire mesh filtration was performed to remove the glass beads to obtain a white titanium oxide dispersion 1 having a solid content of 70.3% by mass and a mass ratio of pigment solid content to resin solid content of 5/1.
(Production Example 5) Production of white titanium oxide dispersion 2 In a 225 ml mayonnaise bottle, 14.3 parts of the polyester resin obtained in Production Example 3, 20 parts of deionized water, and 0.8 part of 2- (dimethylamino) ethanol , JR-903 (trade name, white titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) was added, and after stirring and mixing, 130 parts of 1.5 mm diameter glass beads were added and sealed, and DASH2000-K Disperser (product) Name, manufactured by LAU, shake type paint conditioner) for 60 minutes. After the dispersion, 100-mesh wire mesh filtration was performed to remove the glass beads to obtain a white titanium oxide dispersion 2 having a solid content of 70.3% by mass and a mass ratio of pigment solid content to resin solid content of 5/1.
(Production Example 6) Preparation of carbon black pigment dispersion In a 225 ml mayonnaise bottle, 40.8 parts of the hydroxyl group-containing acrylic resin obtained in Production Example 1, 32.8 parts of ethylene glycol monoethyl ether acetate, MONARCH 1300 (trade name) , Carbon black pigment, manufactured by Cabot Corporation), and after stirring and mixing, 130 parts of 1.5 mm-diameter zirconia beads were added and sealed, and DASH2000-K Disperser (trade name, manufactured by LAU, Using a shaking paint conditioner) for 60 minutes. After the dispersion, 100-mesh wire mesh filtration was performed to remove zirconia beads to obtain a carbon black pigment dispersion having a solid content of 40.3% by mass and a mass ratio of pigment solid content to resin solid content of 1/5.
(Production Examples 7 to 13) Preparation of scale-like glitter pigment liquids 1 to 7
100 parts of ethylene glycol monobutyl ether was put into a stainless steel beaker, and then, Extractor Lumina RED (trade name, titanium dioxide-coated mica pigment, red interference, manufactured by BASF Corp.), Expert Lumina GOLD (trade name, titanium dioxide-coated mica pigment, Yellow interference, manufactured by BASF), Exterior Lumina GREEN (trade name, titanium dioxide-coated mica pigment, green interference, manufactured by BASF), and Luminer BLUE (trade name, titanium dioxide-coated mica pigment, blue interference, manufactured by BASF) 25 parts of each were added and mixed by stirring to obtain a scaly glittering pigment liquid 1 in which the total amount of scaly glittering pigments was about 50% by mass, and the ratio to the total amount of each scaly glittering pigment was 25% by mass. . Further, in the same manner as in Production Example 7, scale-like glitter pigment liquids 2 to 7 were obtained so that the ratio of the scale-like glitter pigment was the ratio shown in Table 1.

(Measurement of interference color of scaly glitter pigment)
The highlight color of the scaly glittering pigment used in the examples and comparative examples and the color of the colored pigment were measured in the following manner, and the results are shown in Table 1.

  The highlight color of the scaly glittering pigment is a resin component comprising 75 parts of the hydroxyl group-containing acrylic resin obtained in Production Example 1 and 25 parts of Uban 28-60 (trade name, butyl etherified melamine resin, manufactured by Mitsui Chemicals). Based on 100 parts by mass of the resin solid content with respect to 100 parts (solid content), the scaly glittering pigment is blended so as to be 15 parts by mass as a solid content, and a dedicated thinner so that the viscosity is appropriate for coating Dilute with stirring and mix. Using a doctor blade, the obtained coating material is applied on a coated plate on which a black (N-2) coating film has been formed in advance so as to have a cured coating film thickness of 20 μm. After leaving at room temperature for 3 minutes, the coating film obtained by drying for 30 minutes in an atmosphere of 80 ° C. using a hot-air drying oven was subjected to MA-68II (trade name, manufactured by x-Rite, multi-angle spectroscopy). Using a photometer, MA-68II (trade name, multi-angle spectrophotometer) manufactured by X-Rite was used to obtain a spectral reflectance that was received at 15 ° with respect to specular reflection light. The hue angle h in the L * C * h color system measured based on this was shown.

(Production Examples 14 to 22) Preparation of Color Base Paints 1 and 2 and Metallic Base Paints 1 to 7 75 parts of a hydroxyl group-containing acrylic resin obtained in Production Example 1, Uban 28-60 (trade name, butyl etherified melamine resin, Mitsui Chemicals) The hydroxyl group-containing acrylic resin, Euban 28-60, and pigment dispersion so that the ratio of the colored pigment and scaly glittering pigment is as shown in Table 2 per 100 parts (solid content) of 25 parts of resin component The body and scale-like glitter pigment liquid were mixed and stirred, and diluted to an appropriate viscosity for coating to prepare color base paints 1 and 2 and metallic base paints 1 to 7 having a solid content of about 25%.

(Production Examples 23 and 24) Preparation of Color Base Paint 3 and Metallic Base Paint 8 100 parts of acrylic resin emulsion obtained in Production Example 2, 50 parts of polyester resin solution obtained in Production Example 3 Cymel 325 (trade name, Nippon Cytec (Industry, melamine resin, solid content 80%) 37.5 parts and the white titanium oxide dispersion 2 obtained in Production Example 5, the scaly glitter pigment liquid is colored pigments and scaly glitter pigments are shown in Table 2. In addition, Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener), 2- (dimethylamino) ethanol and deionized water are mixed so that the ratio shown in FIG. In addition, Ford Cup No. at pH 8.0, paint solids 25%, 20 ° C. A color base paint 3 and a metallic base paint 8 having a viscosity of 40 according to 4 were prepared.

(Measurement of lightness L * of the paint film obtained by applying the color base paint)
After applying the above color base paints 1 to 3 as a cured coating film to a smooth tin plate using an air spray so as to have a thickness of 30 μm, it is allowed to stand at room temperature for 15 minutes, and then heated to 140 ° C. using a hot air dryer. The coating film cured and dried by heating for 30 minutes in an atmosphere was received at 45 ° with respect to specular reflection light using MA-68II (trade name, manufactured by x-Rite, multi-angle spectrophotometer). The lightness L * in the L * a * b * color system measured based on the spectral reflectance is shown in Table 2.

Examples 1-5, Comparative Examples 1-3
(Creation of test plate)
Cationic electrodeposition paint “ELECRON 9400HB” (trade name: manufactured by Kansai Paint Co., Ltd., epoxy resin polyamine-based cation resin) on steel plate (JISG3141, size 400 × 300 × 0.8 mm) subjected to adjustment degreasing and zinc phosphate treatment (Using a block polyisocyanate compound as a curing agent) is electrodeposited so as to have a film thickness of 20 μm based on the cured coating film, and heated at 170 ° C. for 20 minutes to be crosslinked and cured to be electrodeposited. A membrane was obtained.

On the obtained electrodeposited surface, an intermediate coating “Lugerbake Intermediate Coating Gray N-7” (trade name: manufactured by Kansai Paint Co., Ltd., polyester resin / melamine resin type, organic solvent type) is used as an air spray. Based on the cured coating film, it was applied to a film thickness of 30 μm, heated at 140 ° C. for 30 minutes to be crosslinked and cured, and a coated plate on which an intermediate coating film was formed was used as a substrate.
In the process shown in Table 4 on the base material prepared in the coating (1), a color base paint and a metallic base paint were applied in the following manner, and a top clear paint was further applied to prepare a test plate.

Using a REA gun, color base paint was applied as a cured coating film to a thickness of 30 μm under conditions of a boot temperature of 25 ° C. and a humidity of 75%, and allowed to stand at room temperature for 15 minutes, and then the metallic base paint was applied. Under the conditions of a boot temperature of 25 ° C. and a humidity of 75%, a cured coating film was applied so as to have a thickness of 15 μm, and then a top clear paint (Lugabe Kukuriya, manufactured by Kansai Paint, (Product name, acrylic resin / amino resin type, organic solvent type) using a mini-bell type rotary electrostatic coating machine, so that it becomes 30 μm as a cured coating film under conditions of a boot temperature of 25 ° C. and a humidity of 75%. Painted. After coating, the sample was allowed to stand at room temperature for 15 minutes, and then heated in a hot-air circulating drying oven at 140 ° C. for 30 minutes to simultaneously dry and cure the multilayer coating film to obtain a test plate.
(Evaluation of design properties)
The design properties of the test plate were evaluated in the following manner, and the results are shown in Table 3.

(1) Designability evaluation by visual inspection Visual: Engineers and designers who have been engaged in the paint design of automobile exterior paint for 3 years or more by illuminating the created coated plate with an artificial sun lamp (Ceric, color temperature 6500K) Observation was made by changing the angle with respect to the illumination of the test plate. 1) Dense feeling of highlight (near specular reflection light), 2) Turbidity of shade (oblique direction), 3) Overall whiteness was evaluated according to the following criteria. .
1) Dense feeling of highlights (near specular reflection light)
5: An excellent dense feeling is shown.
4: A feeling of denseness is large.
3: There is a dense feeling.
2: There is little denseness.
1: There is no dense feeling.
2) Turbidity of shade (oblique direction)
5: There is no cloudiness of shade.
4: There is almost no cloudiness of a shade.
3: Shade is less turbid.
2: Shade is cloudy.
1: Shade turbidity is remarkable.
3) Overall whiteness 5: Excellent overall whiteness.
4: Overall whiteness is good.
3: White as a whole.
2: The overall whiteness is small.
1: There is no overall whiteness.
(2) Whiteness Using MA-68II (trade name) manufactured by X-Rite, spectral reflectance was measured at a light receiving angle of 45 ° with respect to specularly reflected light. The Yxy value in the degree field of view was calculated, and the whiteness (JIS Z8715) is shown in Table 3.

  The coating film forming method of the present invention can be applied to various industrial products, particularly to the outer plate of an automobile body.

Claims (4)

Light interference with different interference colors in which the base color is a color base coating film with a lightness L * in the range of 75 to 90 in the L * a * b * color system, and a translucent scaly base material is coated with titanium dioxide. A coating film forming method obtained by sequentially forming a metallic base coating film containing four types of functional pigments and a top clear coating film. The hue angle h of the interference color L * c * h color system in the highlights of the four types of light interference pigments is in the range of 12 ° to 22 °, 86 ° to 96 °, 144 ° to 154 °, 263, respectively. °
The method for forming a coating film according to claim 1, which is in a range of ˜273 °. The coating film forming method according to claim 1 or 2, wherein the total amount of the light-interfering pigment is in the range of 4 to 20 parts by mass as the solid content with respect to 100 parts by mass of the resin solid content of the metallic base coating film. The coating film forming method according to any one of claims 1 to 3, wherein the light interference pigment is a titanium oxide-coated alumina flake pigment obtained by coating scaly aluminum oxide with titanium dioxide.