JP5580145B2 - Coating composition, coating film forming method and coating film using the same - Google Patents

Description

The present invention forms a coating film that dramatically changes from a bright chromatic coating film to an achromatic coating film when the incident angle of light is changed with respect to the normal of the coating film surface. It is related with the coating composition which can be performed.

Conventionally, when a paint containing a glittering material having an angle-dependent interference effect is used, the interference hue of specular reflection light obtained by changing the observation angle of the formed coating film from the face angle to the glazing angle The change was only from a chromatic color to a chromatic color with a different hue, and the effect of changing to a chromatic color at the face angle and achromatic color at the glazing angle was not obtained.

  For example, as a dichroic paint composition that enables a calm dichroism that exhibits different colors depending on the viewing angle, (1) a vehicle, (2) a metal oxide-coated silica flake pigment, and if necessary ( 3) A dichroic coating composition containing a glitter pigment and / or a colored pigment is known (see Patent Document 1). In the case of this invention, by including a “metal oxide-coated silica flake pigment” and a “brilliant pigment and / or colored pigment”, the coated film after coating is viewed from about 90 degrees and about 15 degrees. The problem is to obtain different colors when viewed from above. However, it is not shown that the “metal oxide-coated silica flake pigment” and the “brilliant pigment and / or colored pigment” have a complementary color relationship, and are achromatic when viewed from about 15 degrees. Absent. From this, this invention was different from the novel design which this inventor aimed at.

  Further, as a glittering paint composition capable of expressing a three-color design depending on the angle at which the coating film is viewed, a clear coating composition containing a vehicle and two or more interference glittering pigments, One of the interference bright pigments is (a) an interference bright pigment having an average particle size of 5 to 10 μm, and the other is (b) an interference bright pigment having an average particle size of 10 to 30 μm and (a). (C) {average particle diameter of interference bright pigment of (b) -average particle diameter of interference bright pigment of (a) = 10 to 25 μm} A glittering coating composition having a relationship of (2) is known (see Patent Document 2). In the case of the present invention, by setting the hue difference between the two kinds of interference bright pigments to a specific range, it is possible to obtain a trichromatic coating film that gives a colored feeling in the shade portion and expresses a trichromatic design. It describes what you can do. However, the trichromatic coating changes from chromatic to chromatic even if the hue changes, and when changing from face angle to glazing angle, the color of the coating changes from chromatic to achromatic. It was different from the novel design aimed by the inventor of this application.

In addition, a synergistic effect of colored glitter pigments with high color gamut selectivity and other glitter pigments to obtain a coating film that exhibits a sense of depth with little white blur in the shade area and a high saturation feeling in the highlight area. (A) a first glitter pigment in which the entire surface of the flaky substrate is substantially covered with a layer in which a color pigment is dispersed in a matrix mainly composed of silicon oxide, b) a second bright pigment composed of a bright pigment different from the first bright pigment, and (c) a bright paint composition containing a vehicle, the first bright pigment and the second bright pigment Is known, and the pigment content (PWC) is 1 to 30% (see Patent Document 3). In the case of the present invention, by adding two kinds of glitter pigments, the shade portion (the state in which the coating film is viewed obliquely) has a deep feeling without white blur and the highlight portion (the coating film is viewed from directly above). It is an object of the present invention to form a coating film exhibiting a high saturation feeling in the state of the above. However, the interference color of the first bright pigment and the interference color of the second bright pigment are not shown to have a complementary relationship, and are not achromatic at the glazing angle. From this, this invention was different from the novel design which this inventor aimed at.

In addition, the use of titanium dioxide-coated silica flakes to suppress the phenomenon that the bottom color becomes white (discoloration) when seen from the shade position, which occurs in coating films containing interference mica pigments, is a laminated pearl coating with excellent transparency. As a method for obtaining a film, a step of forming a mica base coating film on a substrate on which an undercoat coating film and an intermediate coating film are formed; a step of forming a clear coating film on the substrate without curing the mica base coating film; And a step of curing the mica base coating and the clear coating by heating, wherein the mica base coating for forming the mica base coating comprises titanium dioxide coated silica flakes, A laminated composition comprising a pigment mass content (PWC) in the range of 1 to 18%, and the lightness of the laminated pearl coating is 0 to 30 in terms of L value. Method of forming the Le coating is known (see Patent Document 4). In the case of the present invention, “titanium dioxide-coated silica flake” is used as a “mica-based coating film”, and when viewed from the shade position, the bottom color becomes white (colorless), and the transparency is improved. The object is to obtain an excellent laminated pearl coating film. That is, it is disclosed that silica flakes are used so as not to become an achromatic color at a glazing angle. In addition, in the present invention, although there is a suggestion of the combined use with other bright pigments, it is not shown to have a complementary color relationship with the titanium dioxide-coated silica flake pigment, and the glazing angle is achromatic. Absent. From this, this invention was different from the novel design which this inventor aimed at.

In addition, a high-saturation feeling can be obtained in the shade part, the color difference between the interference colors in the highlight part and the shade part is emphasized, and a multi-colored design can be expressed, and a coating film that obtains a more luxurious feeling of glitter. A paint composition containing a vehicle, an interference bright pigment, and a composite oxide fired pigment as the bright paint composition that can be formed, wherein the interference color hue of the interference bright pigment is a hue of 0 in the Munsell display system. And the interference color hue H of the composite oxide calcined pigment is in the hue range of +30 to +50 or -30 to -50 when displayed in the counterclockwise direction +50 and clockwise direction -50 with respect to the Munsell hue ring 100. A glittering paint composition is known (see Patent Document 5). However, in the case of the present invention, by adding a color pigment to the interference bright pigment, the coating film to be formed has a high chroma feeling at the shade portion and becomes achromatic at the glazing angle aimed by the present inventor. It was different from the new design.

  Further, as a designable metallic paint utilizing the complementary color relationship of pigment, (B) 0.1 to 15 parts by weight of metallic powder, (C) phthalocyanine-based, perylene-based, First colored pigment 0.1 to 0.1 μm in primary particle size selected from danstron, azomethine, benzimidazolone, quinacridone, anthraquinone, diketopyrrolopyrrole and dioxazine 10 parts by weight and (D) a second colored pigment having a primary particle size of 0.1 to 2 μm selected from diketopyrrolopyrrole, quinacridone, pyrazolone, naphthol AS, iron oxide and double metal oxides A coating composition containing 0.5 to 50 parts by weight, the primary particle size of the pigment (C) is relatively smaller than that of the pigment (D), and the pigment (C) and the pigment (D) have a complementary color relationship. Known (See Patent Document 6). However, the coating film formed from this coating composition was not able to obtain the effect of having a chromatic color at the face angle and an achromatic color at the glazing angle.

JP 2000-086943 A JP 2003-073620 A JP 2005-126467 A JP 2001-327915 A JP 2002-121494 A JP 9-235492 A

Raimund Schmid et.al “European Coatings Journal” (7-8) P 702-705 (1997)

As described above, conventionally, coating compositions that are capable of forming a coating film having angle dependency and high chroma due to a synergistic effect by the combination of glitter pigments have been known. By continuously changing the face angle from the face angle to the glazing angle, it is possible to form a coating film in which the hue changes continuously, and the face angle is chromatic and the glazing angle is achromatic. A paint composition that can be obtained has not been obtained.
In the present invention, the hue is continuously changed by changing the observation angle of the coating film from the face angle to the glazing angle, and the face angle is chromatic and the glazing angle is achromatic. It aims at providing the coating composition which can form a film | membrane, the coating-film formation method using the coating composition, and the coating film obtained by it.

As a result of intensive studies to solve the above problems, the present inventors have (A) a metal oxide-coated silica flake that is a glitter material having an angle-dependent interference effect and (B) an angle-dependent interference. Incorporating metal oxide-coated mica and / or metal oxide-coated alumina flakes, which are bright materials having no effect, at a specific ratio, the interference color of component (A) and the interference of component (B) in the glazing angle of the coating film The inventors have found that the above-mentioned problems can be solved by making colors complementary to each other, and have completed the present invention.

That is, the present invention includes (A) a metal oxide-coated silica flake that is a glitter material having an angle-dependent interference effect, and (B) a metal oxide-coated mica that is a glitter material that does not have an angle-dependent interference effect. And / or the content ratio ((A) / (B)) of the (A) component to the (B) component of the metal oxide-coated alumina flakes is 1 / 1.3 to 1/6 in terms of solid content mass ratio. A coating composition contained in a proportion, wherein the interference color of the component (A) and the interference color of the component (B) in the glazing angle of the coating film obtained by coating the coating composition are those of the Munsell color system When the interference color of the component (A) is set to hue 0 in the Munsell display system for the hue ring 100, and the hue is displayed as +50 counterclockwise and −50 clockwise, the interference color of component (B) Is +40 to +50 or -40 to -50 A saturation color (C value) in a variable angle spectrocolorimeter at a glazing angle of a coating film obtained by applying the coating composition, which is in a complementary color relationship within a phase range, is 20 or less, and an observation angle When the face angle is changed from the face angle to the glazing angle, the measured color of the coating film has the highest saturation, which is measured in the vicinity of the regular reflection angle within the range of 10 to 70 degrees. the lowest difference between the saturation coating composition characterized in that 15 or more (here, the face angle, the incident angle of the light source is in the range of 0 degrees or et 25 °, incident angle acceptance angle The glazing angle refers to the observation angle in which the incident angle is in the range of 50 to 70 degrees, and the light receiving angle is in the vicinity of the regular reflection of the incident angle). provide.
In the coating composition, the interference color of the component (A) and the interference color of the component (B) at the glazing angle of the coating film are different from the hue ring 100 of the Munsell color system ( A) The interference color of the component is set to hue 0 in the Munsell display system, and when this is displayed with counterclockwise +50 and clockwise rotation −50, the interference color of component (B) is +42.5 to +50, Alternatively, a coating composition having a complementary color relationship in the hue range of −42.5 to −50 is provided.
In the coating composition, the metal oxide-coated mica of the component (B) is coated with a metal oxide selected from metal oxides of titanium dioxide, iron oxide, chromium, cobalt, tin, or zirconium. The metal oxide-coated mica, wherein the metal oxide-coated alumina flake of the component (B) is a metal oxide-coated alumina flake coated with a metal oxide selected from titanium dioxide and iron oxide I will provide a.

The present invention also provides (A) a metal oxide-coated silica flake that is a glitter material having an angle-dependent interference effect, and (B) a metal oxide-coated mica that is a glitter material that does not have an angle-dependent interference effect. And / or the content ratio ((A) / (B)) of the (A) component to the (B) component of the metal oxide-coated alumina flakes is 1 / 1.3 to 1/6 in terms of solid content mass ratio. In the method of forming a coating film by coating a coating composition containing a proportion, the interference color of component (A) and the interference of component (B) in the glazing angle of the coating film obtained by coating the coating composition When the color is set to the Munsell color system hue ring 100, the interference color of the component (A) is set to 0 in the Munsell display system, and when this color is displayed with counterclockwise +50 and clockwise -50, (B) interference color components, + 40 ~ + 50, or Is - by complementary colors in the color range of 40 to-50, the saturation in the variable angle spectrophotometer at a grazing angle of coating film obtained by coating the coating composition (C value) When the observation angle is changed from the face angle to the glazing angle, the measured incident angle of the color of the coating film is measured in the vicinity of the regular reflection angle within the range of 10 degrees to 70 degrees. A coating film forming method characterized in that a coating film having a difference between the highest saturation and the lowest saturation of 15 or more is formed (here, the face angle is the incident angle of the light source is 0) in the range of time or al 25 degrees refers to the acceptance angle that the mirror reflection vicinity of viewing angle of the incident angle, the grazing angle is in the range of incidence angle of 70 degrees from 50 degrees, the light receiving angle of incidence It refers to the observation angle near the regular reflection of the corner.) To.
Further, in the coating film forming method according to the present invention, the interference color of the component (A) and the interference color of the component (B) in the glazing angle of the coating film are in the Munsell color system hue ring 100. When the interference color of the component (A) is set to hue 0 in the Munsell display system, and when this is displayed with counterclockwise +50 and clockwise rotation −50, the interference color of the component (B) is +42.5 to +50. Or a method for forming a coating film having a complementary color relationship in a hue range of −42.5 to −50.
The present invention provides the coating film forming method, wherein the metal oxide-coated mica of the component (B) is a metal oxide selected from metal oxides of titanium dioxide, iron oxide, chromium, cobalt, tin, or zirconium. Coated metal oxide-coated mica, wherein the (B) component metal oxide-coated alumina flake is a metal oxide-coated alumina flake coated with a metal oxide selected from titanium dioxide and iron oxide A forming method is provided.

Further, the present invention provides a coating film characterized in that the coating composition is applied as a base coat paint to form a base coat paint film, and a clear paint is applied on the base coat paint film to form a clear paint film. A forming method is provided.
In the present invention, the first base coat paint is applied to form a first base coat paint film, and the paint composition is applied as a second base coat paint on the first base coat paint. There is provided a coating film forming method characterized in that a film is formed and a clear coating film is formed by applying a clear coating on the second base coat coating film.
Moreover, this invention provides the coating film obtained by the said coating-film formation method.

In the coating composition of the present invention, the hue changes continuously by continuously changing the observation angle of the coating film from the face angle to the glazing angle, and the face angle is chromatic and the glazing angle is A coating film having an excellent design property of becoming an achromatic color can be formed.

FIG. 1 is an explanatory diagram showing a face angle and a glazing angle. FIG. 2 is an explanatory diagram showing an “ab chromaticity diagram” of an example of the present invention and a comparative example. FIG. 3 shows the hue ring of the Munsell color system.

First, definitions of terms used in the present invention will be described.
The regular reflection angle refers to an angle when regular reflection is performed at an angle symmetrical to the incident light with respect to the normal line of the measurement coating film.
The complementary color relationship refers to a hue having a relative relationship in the hue ring of the Munsell color system.
More specifically, when the interference color of the component (A) is set to hue 0 in the Munsell display system with respect to the hue circle 100, and when this hue is displayed as counterclockwise +50 and clockwise -50, interference color of B) component, + 40 ~ + 50, or - 40 to-50 to be in the color range of complementary relationship. FIG. 3 shows the Munsell color system hue circle.

Further, the metal oxide-coated silica flake which is a glitter material having an angle-dependent interference effect of the component (A) used in the present invention, and a metal which is a glitter material having no angle-dependent interference effect of the component (B). For the single hue of oxide-coated mica, metal oxide-coated alumina flakes, etc., select the closest color chart by comparison with “Standard Color Chart (JIS Z8721 compliant, Japanese Standards Association 1981)”. The hue (Munsell notation) was used.

Face angle refers to an observation angle in which the incident angle is in the range of 0 to about 25 degrees, and the light receiving angle is in the vicinity of the regular reflection of the incident angle (the range of the regular reflection angle ± 10 degrees). Means an observation angle having an incident angle in the range of about 50 to 70 degrees and a light receiving angle in the vicinity of regular reflection of the incident angle (range of regular reflection ± 10 degrees). For ease of understanding, these are shown in FIG. In addition, (a) is a normal line of the coating film surface. In FIG. 1, the angle between the incident light beam and the normal line is the incident angle, and the angle between the reflected light (light receiving) line and the normal line is the reflection angle. In the left view of FIG. 1, in the range of 0 degrees or al 25 degree incidence angle, the reflection angle is near regular reflection angle of incidence (the range of the specular reflection angle ± 10 °), the viewing angle in this case Become a face angle. In the right diagram of FIG. 1, since the incident angle is in the range of 50 to 70 degrees and the reflection angle is in the vicinity of the regular reflection of the incident angle (the range of the regular reflection angle ± 10 degrees), the observation angle in this case is gray. Become a ging angle.
The face angle and the glazing angle are described in Raimund Schmid et al., “European Coating Journal, July-August 1997, pages 702-705” (see Non-Patent Document 1).

The saturation of the interference color means a saturation value measured at a light receiving angle near the regular reflection of the incident angle in the variable angle spectrocolorimeter.
Having an angle-dependent interference effect means that the hue at the light receiving angle in the vicinity of each regular reflection angle with respect to a plurality of incident angles is different with respect to the coating film.
For example, in the case of metal oxide-coated mica, there is an interference effect, but there is no change in hue due to the difference in incident angle, and red mica is a hue measured on the light receiving surface near each regular reflection at any incident angle. Is magenta, and green mica is not a bright material having an angle-dependent interference effect because the hue measured on the light-receiving surface in the vicinity of each regular reflection is green at any incident angle.

Saturation changes from a chromatic color to an achromatic color. When the incident angle is 0 to 25 degrees in the color measurement of the coating film by the variable angle spectrophotometer, the saturation measured in the vicinity of the regular reflection angle is Although the highest saturation (in the case of C value, the higher the value, the higher the saturation is), the saturation measured in the vicinity of the regular reflection angle is low when the incident angle is 50 to 70 degrees. Saturation (C value is 20 or less), and the difference between the highest saturation and the lowest saturation measured in the vicinity of the regular reflection angle when the measured incident angle is in the range of 10 to 70 degrees. It means 15 or more. When the C value exceeds 20, it is not an achromatic color but a chromatic color, and the present invention is characterized in that the C value of the coating film at the glazing angle is an achromatic color of 20 or less.

The variable angle spectrocolorimeter used in the present invention is “Variable angle high speed spectrophotometer GSP-2 type (variable angle spectrocolorimetric system GCMS-4)” manufactured by Murakami Color Research Laboratory Co., Ltd.
Further, the continuous change in hue is that the incident angle and the reflection angle are “10 degrees and 0 degrees”, “15 degrees and 5 degrees”, and “20 degrees and 10 degrees with respect to the normal line of the coating surface. ”,“ 25 degrees and 15 degrees ”,“ 30 degrees and 20 degrees ”,“ 35 degrees and 25 degrees ”,“ 40 degrees and 30 degrees ”,“ 45 degrees and 35 degrees ”,“ 50 degrees and 40 degrees ”, (A, b) 13 of “ab chromaticity diagram” measured in the conditions of “55 degrees and 45 degrees”, “60 degrees and 50 degrees”, “65 degrees and 55 degrees”, and “70 degrees and 60 degrees”. When the values are plotted on the ab coordinate axis, 13 colorimetric values on the coordinates continuously change so as to draw an arc.

Hereinafter, the present invention will be described in detail.
The bright material having an angle-dependent interference effect which is the component (A) used in the paint composition of the present invention is a plurality of coating films formed from the paint composition comprising the glitter material and the film-forming resin. The material in which the hue in the light reception angle in the vicinity of each regular reflection angle with respect to the incident angle is different. Specifically, metal oxide-coated silica flakes are applicable.

Examples of the metal oxide-coated silica flake include those disclosed in JP-A-2000-086943 (Patent Document 1), and specific examples thereof include, for example, iron oxide (iron monoxide or trioxide). (Diiron) or silicon dioxide flakes coated with titanium dioxide.
Examples of commercially available iron oxide-coated silica flakes and titanium dioxide-coated silica flakes include the product name “Color Stream” series manufactured by Merck.
Metal oxide-coated silica flakes may be used singly or in combination of two or more.

In the present invention, examples of the (B) component metal oxide-coated mica and metal oxide-coated alumina flake include those used as a glittering material for glittering paints.
Examples of the metal oxide-coated mica include those in which a metal oxide coating is formed on the surface of flaky mica particles, and titanium dioxide, iron oxide and other chromium, cobalt, tin on the surface of natural muscovite and synthetic mica. And an interference mica pigment coated with a thin film of a metal oxide such as zirconium.
Examples of the metal oxide-coated alumina flake include flaky aluminum oxide (Al ₂ O ₃ ) coated with a metal oxide having a high refractive index, such as titanium dioxide and iron oxide. For example, the product name “Silary” manufactured by Merck & Co., Inc. may be mentioned.
(B) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The present invention is characterized in that when the observation angle is continuously changed from the face angle to the glazing angle, the hue changes continuously, and the face angle is chromatic and the glazing angle is achromatic. However, as an essential requirement, the interference color at the glazing angle of the component (A) and the interference color at the glazing angle of the component (B) have a complementary color relationship.

Particularly preferably, the variable angle high-speed spectrophotometer when the incident angle of the coating film obtained by coating the coating composition containing the component (A) and the component (B) in a certain ratio is 50 to 70 degrees. The C value of the measured saturation is preferably 20 or less, more preferably 15 or less. In addition, in order to change from a chromatic color at the face angle to an achromatic color at the glazing angle, the vicinity of the regular reflection angle is the highest saturation when the incident angle is 0 to 25 degrees, and It is preferable that the difference between the highest value and the lowest value of the C value of saturation measured by the variable-angle high-speed spectrophotometer within the range of the measurement incident angle of 10 degrees to 70 degrees is 15 or more. More preferably, the difference between the highest value and the lowest value of the C value of saturation measured by the variable-angle high-speed spectrophotometer within the range of the measurement incident angle of 10 degrees to 70 degrees is 30 or more. is there.

As described above, the regular reflection angle refers to an angle when regular reflection is performed at an angle symmetrical to the incident light with respect to the normal line of the measurement coating film, and the complementary color relationship is relative to the hue ring of the Munsell color system. It is a hue that has a relationship to. More specifically, when the interference color of the component (A) is set to hue 0 in the Munsell display system with respect to the hue circle 100, and when this hue is displayed as counterclockwise +50 and clockwise -50, interference color of B) component, + 40 ~ + 50, or - 40 to-50 to be in the color range of complementary relationship.
(A) with respect to the interference color of the hue components, the interference color of the (B) component, + 40 ~ + 50 or - if it is not the hue range of 40 to-50, the chromatic saturation to achromatic There is no change.

The content ratio ((A) / (B)) of the component (A) to the component (B) in the coating composition of the present invention is 1 / 1.3 to 1/6 in terms of solid content mass ratio, preferably 1 /1.4 to 1/5, more preferably 1 / 1.5 to 1 / 4.5.
When the content ratio of the component (A) is greater than 1 / 1.3 with respect to the component (B) or less than 1/6 of the component (B), the observation angle is changed from the face angle to the glazing angle. By continuously changing the hue, the hue is continuously changed, and the effect that the face angle is chromatic and the glazing angle is achromatic is not observed.

Further, the total content of the component (A) and the component (B) is preferably 0.5 to 40% by mass, more preferably 1.0 to 30% by mass, and particularly preferably 2.0% in the total solid content of the paint. -25% by mass.
When the total content of the component (A) and the component (B) is less than 0.5% by mass in the total solid content of the paint, the observation angle is continuously changed from the face angle to the glazing angle. Hue changes, and the effect of a chromatic color at the face angle and an achromatic color at the glazing angle is reduced. When it exceeds 40 mass%, the external appearance property of a coating film will fall.

As the coating film-forming resin used in the coating composition of the present invention, resins that are usually used as coating-film forming resins for coatings can be used without limitation. Specific examples thereof include one kind or a combination of two or more kinds such as acrylic resin, polyester resin, alkyd resin, polyolefin resin, chlorinated polyolefin resin, fluororesin, and silicon resin.

The coating composition of the present invention may be a single type or a non-crosslinked lacquer type coating composition containing two or more types of coating-forming resins, or the single type or two or more types of coating compositions. The film-forming resin can be combined with a cross-linking resin composed of one kind or a combination of two or more kinds such as an amino resin, a (block) polyisocyanate compound, and an epoxy compound, for example, to obtain a cross-linking curable coating composition. .

In the coating composition of the present invention, other color pigments and various additives can be blended as necessary. As color pigments, those conventionally used for paints are used. For example, organic pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments. Pigments, quinacridone pigments and the like can be mentioned, and inorganic irons include yellow iron oxide, bengara, titanium dioxide, carbon black and the like. In addition, it is preferable not to mix | blend an aluminum flake pigment with the coating composition of this invention.
Additives include UV absorbers such as benzotriazole and oxalic acid anilide, antioxidants such as benzophenol, leveling agents such as silicone, viscosity control agents such as wax and organic bentonite, curing catalysts, etc. Is mentioned.

The coating composition of the present invention can be used by dissolving in an organic solvent. As the organic solvent, aromatic hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, ether solvents and the like can be used.
The coating of the coating composition of the present invention is usually used in usual coating methods, for example, spray coating methods such as air spray, electrostatic air spray, airless spray, roll coater, flow coater, dipping type coating machine, etc. Examples thereof include a coating method using a coating machine, or a coating method using a brush, a bar coater, an applicator and the like. Of these, the spray coating method is preferred.

The base material to which the coating composition of the present invention is applied includes metals, iron, aluminum, magnesium or alloys containing these alloys, molded articles of inorganic materials such as glass and concrete, polyethylene, polypropylene, and ethylene-vinyl acetate. Copolymer, polyamide, polyacryl, polyester, vinyl chloride resin, vinylidene chloride resin, polycarbonate, polyurethane, acrylonitrile-butadiene-styrene copolymer resin moldings, plastic material moldings such as FRP, wood, For example, paper. In addition, it is arbitrary to apply an electrodeposition coating material or an intermediate coating material to these substrates in advance.

The coating composition of the present invention is suitable for use as a base coat in automobile applications and industrial applications. Therefore, a method of forming a coating film by a two-coat one-bake or two-coat two-bake coating method in which a base material is coated with the coating composition of the present invention as a base coat and then a clear coating is applied, or the coating composition of the present invention As a base coat, a first base coat paint is applied, and then the coating composition of the present invention is applied as a second base coat, and then a clear paint is applied. 3 coat 1 bake 3 coat 2 bake 3 coat 3 bake paint A method for forming a coating film by a method is used.
In particular, by using a white or light-colored base coat or a deep-colored base coat for the first base coat, the brightness of the coating film consisting of three layers can be adjusted, and the design variation can be expanded. Can do.

A well-known thing can be used for the clear coat in the coating-film formation method using the coating composition of this invention.
In addition, as the first base coat in the coating film forming method using the coating composition of the present invention, those known as a colored base coat or a color base coat are usually used, for example, disclosed in JP-A-2007-216220. And the like.

In the coating film forming method using the coating composition of the present invention, when the first base coat is used, the dry coating thickness is preferably 2 to 40 μm, more preferably 5 to 30 μm. Moreover, 1-30 micrometers is preferable, as for the dry coating film thickness of the coating composition of this invention, More preferably, it is 3-25 micrometers, Most preferably, it is 5-20 micrometers. Further, the dry coating thickness of the clear coating is preferably 10 to 70 μm, more preferably 20 to 50 μm.
If the dry coating thickness of the coating composition of the present invention is less than 1 μm, the base may not be concealed.

In the coating film forming method of the present invention, the clear coat paint is applied on the base coat film to form a clear coat film layer, and the clear coat film layer is baked and cured. The baking temperature may be appropriately selected in the range of usually 120 to 180 ° C., and the baking time may be appropriately selected in the range of usually 10 to 60 minutes.
In the case of three coats consisting of the first base coat, the second base coat of the present invention, and the clear coat, each base coat is applied without being baked, and is applied by wet-on-wet. The 1-bake method is preferable from the viewpoint of energy saving.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not restrict | limited at all by these Examples.

<Production Example 1>
Preparation of base coat coating composition B-1 In a beaker, (A) a titanium dioxide-coated silica flake (trade name “Colorstream” T20-, manufactured by Merck & Co., Inc.) as a glittering material having an angle-dependent interference effect. "02WNT", Hue at glazing angle: Red color, 2.3 parts by mass, and (B) Metal oxide-coated mica (Merck, trade name "Iriodin 235WNT", Hue at glazing angle: Blue-green color) 4.8 parts by mass of color stream T20-02WNT and a complementary color relationship in the glazing angle), 10 parts by mass of mixed organic solvent (mass ratio of toluene / xylene / butyl acetate / butanol = 30/40/20/10) Mix and wet, then in another container, acrylic resin varnish BASF Coatings Japan Co., Ltd., trade name “LB-7800”, heating residue 50% by mass, hydroxyl value 46 mgKOH / g, acid value 7 mgKOH / g, number average molecular weight 20,000) 120 parts by mass and butylated melamine 50 parts by mass of resin varnish (Mitsui Chemicals Co., Ltd., trade name “Uban 20SE”, heating residue 60% by mass) and 30 parts by mass of the above mixed solvent are mixed and stirred, and wet in the mixed varnish solution. The mixture of (A) and (B) was gradually added with stirring, and the mixture was sufficiently stirred to be uniform to obtain a base coating composition B-1.

<Production Example 6>
Preparation of base coat coating composition B-6 In a dispersion container, 30 parts by mass of acrylic resin varnish “LB-7800” and 3.1 parts by mass of carbon black (trade name “Pigment Black FW200” manufactured by Degussa) A carbon black coating composition was prepared by dispersing 25 parts by mass of xylene with a sand mill until the particle size became 10 μm or less.

(A) Titanium dioxide-coated silica flake (Merck, product name “Colorstream T20-02WNT”, hue at glazing angle: red color) 3.3 parts by mass and (B) metal oxide-coated mica (manufactured by Merck & Co., trade name “Iriodin 235WNT”, hue at glazing angle: blue-green system color, color stream T20-02WNT and complementary color relationship at face angle 7 parts by mass) is mixed with 10 parts by mass of a mixed organic solvent (mass ratio of toluene / xylene / butyl acetate / butanol = 30/40/20/10) and then wetted. 120 parts by mass of resin varnish “LB-7800” and butylated melamine 50 parts by mass of the resin varnish “Uban 20SE” and 30 parts by mass of the mixed solvent were mixed and stirred, and the wet mixture of (A) and (B) was gradually added to the mixed varnish solution while stirring. Stir well. Next, the total amount of the carbon black coating composition was added, and the mixture was sufficiently stirred so as to obtain a base coating composition B-6.

<Production Example 13>
Preparation of base coat paint composition B-13
In a dispersion container, acrylic resin varnish acrylic resin varnish “LB-7800” 30 parts by mass, coloring pigment (manufactured by DIC Corporation, “Fastgen Green 2YK”, green organic pigment) 2.2 parts by mass and xylene 25 parts by mass Were dispersed with a sand mill until the particle size became 10 μm or less to prepare a color pigment coating composition.

In a beaker, (A) Titanium dioxide-coated silica flakes (trade name “Colorstream T20-02WNT” as a bright material having an angle-dependent interference effect, hue at glazing angle: red color) 7.5 parts by mass is wetted with 10 parts by mass of a mixed organic solvent (toluene / xylene / butyl acetate / butanol mass ratio = 30/40/20/10), and then placed in a separate container in an acrylic resin varnish “ LB-7800 "120 parts by mass, butylated melamine resin varnish" Uban 20SE "50 parts by mass and 30 parts by mass of the above mixed solvent were mixed and stirred, and the wet (A) was stirred into the mixed varnish solution. Slowly added and stirred well.
Next, the entire amount of the above-described color pigment coating composition was added, and the mixture was sufficiently stirred so as to obtain a base coating composition B-13.

<Production Examples 2-5, 7-12 and 14>
Preparation of Base Coat Coating Compositions B-2 to 5, 7 to 12 and 14 Using the raw materials shown in Tables 1 and 2 in the same manner as in Production Example 1, base coat coating compositions B-2 to B-5, B-7 to 12 and B-14 were obtained.

In addition, (A)-(C) component of the raw material in Table 1 and Table 2 is demonstrated in detail below.
(A1) Color stream T20-02WNT: manufactured by Merck & Co., Inc., titanium dioxide-coated silica flake, hue at glazing angle 7.5RP (red color).
(A2) Color stream T20-01WNT: manufactured by Merck Ltd., titanium dioxide-coated silica flakes, hue 10GY (green system color) at glazing angle.
(A3) Color stream T20-03WNT: manufactured by Merck Ltd., titanium dioxide-coated silica flake, hue 10R (orange color) at a glazing angle.

(B1) Iriodin 235WNT: manufactured by Merck Co., Ltd., metal oxide coated mica, hue at glazing angle 7.5G (blue-green system color), color stream T20-02WNT, T20-03WNT and complementary colors (in hue ring 100) On the other hand, when the interference color of the color stream T20-02WNT is set to hue 0 in the Munsell display system, the interference color of Iriodin 235WNT is clockwise when the hue is displayed as +50 counterclockwise and -50 clockwise. 50.)

(B2) Iriodin 215WNT: manufactured by Merck, metal oxide-coated mica, hue at glazing angle is 2.5R (red color), color stream T20-01WNT and complementary color relationship at glazing angle (in hue ring 100) On the other hand, when the interference color of the color stream T20-01WNT is set to hue 0 in the Munsell display system, the interference color of Iriodin Ultra 215WNT is counterclockwise when displayed at +50 counterclockwise and -50 clockwise. However, it is not complementary to the color stream T20-02WNT (for the hue ring 100, the interference color of the color stream T20-02WNT is set to hue 0 in the Munsell display system. When it is displayed as around +50 or around -50 Interference color of gin 215WNT is, is right around -5.0).

(B3) Lumina Turquoise T303D: manufactured by BASF, metal oxide-coated alumina flakes, hue at glazing angle is 7.5BG (blue color), color stream T20-03WNT and complementary color relationship at glazing angle (Hue ring) When the interference color of color stream T20-03WNT is set to hue 0 in the Munsell display system with respect to 100, and this hue is displayed with counterclockwise +50 and clockwise rotation −50, the interference color of Lumina Turquoise T303D is It is -47.5 clockwise.)

(B4) Silical T60-24WNT: manufactured by Merck Co., Ltd., metal oxide-coated alumina flake, hue at glazing angle is 7.5G (green color), color stream T20-02WNT and complementary color relationship at glazing angle Certain (when the interference color of the color stream T20-02WNT is set to hue 0 in the Munsell display system with respect to the hue circle 100, and when the hue is displayed with a counterclockwise rotation of +50 and a clockwise rotation of -50, it is silly. (The interference color of T60-24WNT is -50 clockwise.)

(B5) Iriodin 223 WNT: manufactured by Merck Ltd., metal oxide-coated mica, hue at glazing angle is 7.5P (purple system color), color stream T20-01WNT and complementary color relationship at glazing angle (in hue ring 100) On the other hand, when the interference color of the color stream T20-01WNT is set to hue 0 in the Munsell display system, the interference color of Iriodin 223WNT is clockwise when the hue is displayed as +50 counterclockwise and -50 clockwise. 47.5.)

(B6) CFS Marine Fine Blue 6303V: manufactured by BASF, metal oxide-coated mica, hue at glazing angle is 7.5 PB (blue system color), complementary to color stream T20-01WNT at glazing angle (hue) When the interference color of the color stream T20-01WNT is set to hue 0 in the Munsell display system with respect to the ring 100, and this hue is displayed with a counterclockwise rotation of +50 and a clockwise rotation of −50, Extramarlin CFS Fine Blue 6303V The interference color is -37.5 clockwise.)
(C1) Pigment Black FW200: manufactured by Degussa, carbon black pigment (C2) Fastgen Green 2YK: manufactured by DIC Corporation, green organic pigment

<Examples 1-7, Comparative Examples 1-7>
Preparation of test specimen for evaluation in 2C1B coating system
Cationic electrodeposition paint (BASF Coatings Japan Co., Ltd., trade name “Aqua No. 4200”) was electrodeposited on a zinc phosphate-treated mild steel plate to a dry film thickness of 20 μm and baked at 175 ° C. for 25 minutes. Further, an intermediate coating (BASF Coatings Japan Co., Ltd., trade name “Aqua GX Sealer”) was applied by air spraying to a dry film thickness of 30 μm and baked at 140 ° C. for 30 minutes. Next, as the base coat paint, the above base coat paint composition B-1 is diluted with the above mixed organic solvent so as to have a spray coating viscosity of 12 to 13 seconds (20 ° C., Ford Cup # 4), and then dried. After air spraying to a thickness of 15 μm and setting at room temperature for 10 minutes, an acrylic / melamine resin-based clear paint (BASF Coatings Japan Co., Ltd., trade name “Bellcoat No. 6200 Clear”) is used as an aromatic oil. Air diluted to a coating thickness (Ford Cup # 4, 25 seconds at 20 ° C.) diluted with naphtha (trade name “Solvesso 100” manufactured by Esso Corporation) to a dry film thickness of 30 μm by a wet-on-wet method. A test piece was prepared by spray coating and baking at 140 ° C. for 30 minutes.
In the case of Examples 2 to 7 and Comparative Examples 1 to 7, test pieces were similarly prepared.

<Evaluation method of test plate>
The saturation (C value) of the coating film on the obtained test plate was measured using a “variable angle high-speed spectrophotometer GSP-2 type (variable angle spectrophotometric system GCMS-4)” manufactured by Murakami Color Research Laboratory Co., Ltd. Then, the incident angle from the light source and the light receiving angle were respectively changed and measured, and the results are summarized in Tables 3 to 4.
(1) Saturation increase value A value obtained by subtracting the C value at an incident angle of 70 degrees from the C value at an incident angle of 10 degrees. Shows how much saturation increases by changing from glazing angle to face angle. The larger the value in the positive direction, the greater the increase in saturation from glazing angle to face angle. When is negative, it indicates that the saturation is lowered by changing the glazing angle to the face angle.

(2) Saturation change width The saturation change width is the highest saturation and the lowest saturation of the saturation values measured with the variable-angle high-speed spectrophotometer within the range of the incident angle of measurement from 10 degrees to 70 degrees. The saturation change width was evaluated as “◯” when the saturation change width was 15 or more, and “X” when less than 15.
(3) Visual evaluation of effect from chromatic color to achromatic color The hue changes continuously by changing the observation angle from the face angle to the glazing angle, and the face angle is chromatic and the glazing angle is Visual evaluation was carried out step by step from ◎, ○, Δ, and × from a remarkable achromatic effect to a case where the effect could not be confirmed.

A: The color when the coating film is observed from the face angle is chromatic, and the saturation from the face angle when the observation angle is changed to the glazing angle is remarkably large.
○: The color when the coating film is observed from the face angle is chromatic, and the saturation reduction from the face angle when the observation angle is changed to the glazing angle can be clearly confirmed visually.
(Triangle | delta): The color when a coating film is observed from a face angle is a chromatic color, and it is possible to visually confirm the saturation reduction from a face angle when changing an observation angle to a glazing angle.
×: When the coating film is observed from the face angle, the color is chromatic, or even if the color is achromatic, the saturation from the face angle when the observation angle is changed to the glazing angle is visually observed. I can't confirm.

(4) Achromatic evaluation of glazing angle The case where the C value at an incident angle of 50 to 70 degrees was 20 or less was evaluated as “◯”, and the case where it exceeded 20 was evaluated as “X”.
(5) Finished appearance: The finished film was visually evaluated for the presence or absence of sharpness.
○: Vivid image △: Poor visual quality ×: Exquisite gloss

In order to compare and explain the “ab chromaticity diagram” and “saturation” color measurement results of Example 5 and Comparative Example 7 of the present invention, those results are shown in FIG. In FIG. 2, ▲ is Example 5 and ■ is Comparative Example 7.

Comparative Example 1 is a case where the ratio of the component (A) to the component (B) is outside the scope of the claims (the component B is less than the lower limit value), and from chromatic to achromatic at an incident angle of 30 to 50 degrees. However, at a glazing angle exceeding an incident angle of 50 degrees, the color returned to chromatic.
In Comparative Example 2, the ratio of the component (A) to the component (B) was outside the scope of the claims (the component B was greater than the upper limit value), and the color was chromatic at all angles.
Comparative Example 3 is a case where the component (A) and the component (B) are not complementary in the glazing angle, and are achromatic at the face angle and chromatic at the glazing angle. Showed a change in color.

Comparative Example 4 does not contain the component (A), and the component (B) uses two types of mica having a complementary color relationship in the Munsell color system with a glazing angle of 7.5G and 2.5R. And it was achromatic at all angles.
Comparative Example 5 does not contain the component (A), and the component (B) is a mica and metal oxide-coated alumina flake having a complementary color relationship in the Munsell color system of 2.5R and 7.5G in terms of glazing angles. When using, it was achromatic at all angles.
Comparative Example 6 is a case where the component (A) of red coloration and a green organic pigment are used at a glazing angle, and changes from a chromatic color to an achromatic color at an incident angle of 45 to 55 degrees, but exceeds an incident angle of 55 degrees. The glazing angle has returned to chromatic.

Comparative Example 7 is a trace of Example 13 of Patent Document 2 in the background art (a titanium dioxide-coated silica flake pigment that develops red color in a highlight portion). The pigment “Color Stream T20-01WNT” of (A2) used in Comparative Example 7 had a red color at the highlight (face angle) and a green color at the glazing angle. In Comparative Example 7, a complementary color relationship at the glazing angle was recognized between (A2) and (B6), but the C value was 30 or more at all angles, and chromatic colors at all angles. Met.

In FIG. 2, the saturation can be considered as a distance from the measured value to the origin (0 point). The smaller the numerical value, the achromatic color, and the larger the numerical value, the brighter chromatic color. In the case of the example shown in FIG. 2, both the example 5 and the comparative example 7 are considered on the basis of the numerical value when the incident angle is 0 degree, and on the “ab chromaticity diagram” in the counterclockwise direction as the incident angle is increased. Is moving. In the case of Example 5, as the incident angle increases, the color changes from a chromatic color to an achromatic color. In the case of Comparative Example 7, it is always shown that the color is chromatic regardless of the incident angle.

Claims (9)

(A) A metal oxide-coated silica flake that is a glitter material having an angle-dependent interference effect, and (B) a metal oxide-coated mica and / or metal oxide that is a glitter material having no angle-dependent interference effect . A coating composition containing the coated alumina flakes in a ratio in which the content ratio of the component (A) to the component (B) ((A) / (B)) is 1 / 1.3 to 1/6 in terms of solid content mass ratio. The interference color of the component (A) and the interference color of the component (B) in the glazing angle of the coating film obtained by applying the coating composition are compared with the hue ring 100 of the Munsell color system. the interference color of the (a) component and the hue 0 in the Munsell display system, for this color, left around +50, when projected on the right around -50, the interference color of the (B) component + 40 ~ + 50 Or complementary colors in the hue range of -40 to -50 In the coating film obtained by applying the coating composition, the chroma (C value) in the variable angle spectrocolorimeter at the glazing angle of the coating film is 20 or less, and the observation angle is glazed from the face angle. When the angle of incidence is changed to the angle, the measured incident angle of the coating film is between the highest saturation and the lowest saturation measured in the vicinity of the regular reflection angle within the range of 10 to 70 degrees. difference coating composition characterized in that 15 or more (here, the face angle, the incident angle of the light source is in the range of 0 degrees or et 25 °, the light receiving angle is near regular reflection angle of incidence It refers to the observation angle, and the glazing angle refers to an observation angle in which the incident angle is in the range of 50 to 70 degrees and the light receiving angle is in the vicinity of the regular reflection of the incident angle). The interference color of the component (A) and the interference color of the component (B) at the glazing angle of the coating film are different from the hue ring 100 of the Munsell color system. When this is set to 0 and the counterclockwise +50 and clockwise -50 are displayed for this hue, the interference color of component (B) falls within the hue range of +42.5 to +50 or -42.5 to -50. The coating composition according to claim 1, which has a complementary color relationship. The metal oxide-coated mica as the component (B) is a metal oxide-coated mica coated with a metal oxide selected from metal oxides of titanium dioxide, iron oxide, chromium, cobalt, tin, or zirconium, The coating composition according to claim 1 or 2, wherein the metal oxide-coated alumina flake as component B) is a metal oxide-coated alumina flake coated with a metal oxide selected from titanium dioxide and iron oxide. (A) A metal oxide-coated silica flake that is a glitter material having an angle-dependent interference effect, and (B) a metal oxide-coated mica and / or metal oxide that is a glitter material having no angle-dependent interference effect . A coating composition containing the coated alumina flakes in a ratio in which the content ratio of the component (A) to the component (B) ((A) / (B)) is 1 / 1.3 to 1/6 in terms of solid content mass ratio. In the method for forming a coating film by coating an object, the interference color of the component (A) and the interference color of the component (B) in the glazing angle of the coating film obtained by coating the coating composition are expressed in the Munsell color system. For the hue ring 100, the interference color of the (A) component is set to hue 0 in the Munsell display system, and when this hue is displayed with counterclockwise +50 and clockwise -50, the interference of the (B) component Color is +40 to +50 or -40 to -5 By setting the complementary color relationship within the hue range of 0, the saturation (C value) in the variable angle spectrocolorimeter at the glazing angle of the coating film obtained by applying the coating composition was 20 or less. When the observation angle is changed from the face angle to the glazing angle, the measured incident angle of the color of the coating film is the maximum of the saturation measured in the vicinity of the regular reflection angle within the range of 10 degrees to 70 degrees. in the coating film-forming method (wherein a difference between the lowest saturation and high color saturation and forming a coating film is 15 or more, the face angle, the incident angle of the light source is 0 ° or et 25 ° in the range of, refers to the acceptance angle that the mirror reflection vicinity of viewing angle of the incident angle, the grazing angle is in the range of incidence angle of 70 degrees from 50 degrees, the specular reflection near the incident angle acceptance angle Refers to the observation angle. The interference color of the component (A) and the interference color of the component (B) at the glazing angle of the coating film are different from the hue ring 100 of the Munsell color system. When this is set to 0 and the counterclockwise +50 and clockwise -50 are displayed for this hue, the interference color of component (B) falls within the hue range of +42.5 to +50 or -42.5 to -50. The coating film forming method according to claim 4, which has a complementary color relationship. The metal oxide-coated mica as the component (B) is a metal oxide-coated mica coated with a metal oxide selected from metal oxides of titanium dioxide, iron oxide, chromium, cobalt, tin, or zirconium, The coating film forming method according to claim 4 or 5, wherein the metal oxide-coated alumina flake as component B) is a metal oxide-coated alumina flake coated with a metal oxide selected from titanium dioxide and iron oxide. A coating composition comprising: coating a coating composition according to claim 1 as a base coat paint to form a base coat paint film; and applying the clear paint on the base coat paint film to form a clear paint film. Method. A first base coat paint is applied to form a first base coat paint film, and the second base coat paint is applied on the first base coat paint as a second base coat paint. And forming a clear coat film by applying a clear paint on the second base coat film. The coating film obtained by the coating-film formation method in any one of Claims 4-8 .

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