MULTILAYER COATING FILM AND COATED ARTICLE

Abstract

The flip-flop properties and the metallic impression are enhanced in a metallic coating. The coating includes a colored base layer formed directly or indirectly on a surface of a coating target, and a bright material-containing layer containing flaked bright materials and a colorant and layered on the colored base layer. With respect to the bright material-containing layer in a state without the colorant, Y(10?) of the XYZ color system is set to be 50 or more and 850 or less, and Y(20?) is set to be equal to k?Y(10?), where k is in a range of 0.2?k?0.6 and is determined according to the Y(10?). The colorant concentration of the bright material-containing layer is determined according to k.

Claims

1. A multilayer coating film comprising: a colored base layer containing a colorant and formed directly or indirectly on a surface of a coating target, and a bright material-containing layer containing flaked bright materials and a colorant and layered on the colored base layer, wherein
a following equation is employed: Y(20?)=k?Y(10?), where k is a coefficient, Y represents a Y value according to an XYZ color system, which is calibrated by a standard white plate, of the bright material-containing layer in a state without the colorant, Y(10?) represents a Y value of reflected light measured at a receiving angle (an angle toward a light source from a specular reflection angle) of 10?, and Y(20?) represents a Y value of reflected light measured at the receiving angle of 20?, and a colorant concentration C of the bright material-containing layer is expressed in percent by mass, and the Y(10?), the coefficient k, and the colorant concentration C are three variables, and satisfy, when x-, y-, and z-coordinate axes of a three-dimensional orthogonal coordinate space represent the three variables, that coordinates (Y(10?), k, C) are in a range defined by a octahedron consisting of eight planes expressed by equations A to H, shown below, in which the planes expressed by the equations C and F form an inwardly protruding ridge and the planes expressed by the equations D and G form an outwardly protruding ridge.
3000y?120z+3000=0Equation A:
3000y?120z=0Equation B:
5x?3750y?2000=0Equation C:
5x?3750y+1000=0Equation D:
15000y?9000=0Equation E:
5x?1250y?3000=0Equation F:
5x?1250y=0Equation G:
15000y?3000=0Equation H:

2. The multilayer coating film of claim 1, wherein the bright material is an aluminum flake with a thickness of 25 nm or more and 200 nm or less.

3. The multilayer coating film of claim 2, wherein the aluminum flake is oriented at an angle of 3 degrees or less with respect to a surface of the bright material-containing layer.

4. The multilayer coating film of claim 1, wherein the colorants of the colored base layer and the bright material-containing layer are deep in color.

5-8. (canceled)

9. The multilayer coating film of claim 2, wherein the colorants of the colored base layer and the bright material-containing layer are deep in color.

10. The multilayer coating film of claim 3, wherein the colorants of the colored base layer and the bright material-containing layer are deep in color.

11. The multilayer coating film of claim 4, wherein the colorants of the colored base layer and the bright material-containing layer are in similar colors.

12. The multilayer coating film of claim 9, wherein the colorants of the colored base layer and the bright material-containing layer are in similar colors.

13. The multilayer coating film of claim 10, wherein the colorants of the colored base layer and the bright material-containing layer are in similar colors.

14. The multilayer coating film of claim 11, wherein the colorants of the colored base layer and the bright material-containing layer are in a blackish color.

15. The multilayer coating film of claim 12, wherein the colorants of the colored base layer and the bright material-containing layer are in a blackish color.

16. The multilayer coating film of claim 13, wherein the colorants of the colored base layer and the bright material-containing layer are in a blackish color.

17. The multilayer coating film of claim 1, wherein a transparent clear layer is layered directly on the bright material-containing layer.

18. The multilayer coating film of claim 2, wherein a transparent clear layer is layered directly on the bright material-containing layer.

19. The multilayer coating film of claim 3, wherein a transparent clear layer is layered directly on the bright material-containing layer.

20. The multilayer coating film of claim 4, wherein a transparent clear layer is layered directly on the bright material-containing layer.

21. The multilayer coating film of claim 11, wherein a transparent clear layer is layered directly on the bright material-containing layer.

22. The multilayer coating film of claim 14, wherein a transparent clear layer is layered directly on the bright material-containing layer.

23. A coated object including the multilayer coating film of claim 1.

24. A coated object including the multilayer coating film of claim 2.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] FIG. 1 is a diagram schematically illustrating a cross-sectional view of a multilayer coating film.

[0041] FIG. 2 is a diagram schematically illustrating a cross-sectional view of a known multilayer coating film to show how light is scattered by bright materials and is diffused on a base layer.

[0042] FIG. 3 is a diagram schematically illustrating a cross-sectional view of the multilayer coating film according to the present invention in which scattered light is controlled.

[0043] FIG. 4 is a diagram illustrating reflected light for explaining how to calculate an FI value.

[0044] FIG. 5 is a graph showing an example angle dependence of Y(10?) with respect to a bright material-containing layer in a state without a colorant.

[0045] FIG. 6 is a diagram for explaining how to measure a Y value.

[0046] FIG. 7 is a graph showing suitable ranges of the Y(10?) and a colorant concentration when a coefficient k is equal to 0.4.

[0047] FIG. 8 is a graph showing suitable ranges of the Y(10?) and the colorant concentration when the coefficient k is equal to 0.2.

[0048] FIG. 9 is a graph showing suitable ranges of the Y(10?) and the colorant concentration when the coefficient k is equal to 0.6.

[0049] FIG. 10 is a graph showing a relationship between the Y(10?) and the coefficient k.

[0050] FIG. 11 is a graph showing a relationship between the coefficient k and the colorant concentration C.

[0051] FIG. 12 is a graph showing ranges of the Y(10?), the coefficient k, and the colorant concentration C when an FI value is 30 or more.

[0052] FIG. 13 is a graph showing ranges of the Y(10?), the coefficient k, and the colorant concentration C when the FI value is 35 or more.

DESCRIPTION OF EMBODIMENTS

[0053] Embodiments of the present invention will now be described with reference to the drawings. The following description of preferred embodiments is only an example in nature, and is not intended to limit the scope, applications or use of the present invention.

[0054] <Example Configuration of Multilayer Coating Film>

[0055] As illustrated in FIG. 1, a multilayer coating film 12 provided on a surface of an automobile body (steel plate) 11 according to the present embodiment contains a colored base layer 14, a bright material-containing layer 15, and a transparent clear layer 16 which are sequentially stacked one upon the other. An electrodeposition coating film (undercoat) 13 is formed on the surface of the automobile body 11 by cationic electrodeposition. The multilayer coating film 12 is provided on top of the electrodeposition coating film 13. In the multilayer coating film 12, the colored base layer 14 corresponds to an intermediate coat, and the bright material-containing layer 15 and the transparent clear layer 16 correspond to a topcoat.

[0056] A deep color pigment 21 is dispersed in the colored base layer 14. Flaked bright materials 22 and a deep color pigment 23 in a color similar to that of a pigment 21 of the colored base layer 14 are dispersed in the bright material-containing layer 15. Pigments of various hues including, for example, a black pigment (e.g., carbon black, perylene black, and aniline black) or a red pigment (e.g., perylene red) may be employed as the pigments 21 and 23. It is particularly preferable to employ as the pigment 21 carbon black having a particle size distribution with a peak at a particle size of 300 nm or more and 500 nm or less, and employ as pigment 23 carbon black having a particle size distribution with a peak at a particle size of 200 nm or less.

[0057] The surface smoothness of the colored base layer 14 is 8 or less in a measurement value Wd (wavelength of 3 to 10 mm) measured by WaveScan DOI (trade name) manufactured by BYK-Gardner, and the thickness of the bright material-containing layer 15 is 1.5 ?m or more and 6 ?m or less.

[0058] The bright material 22 of the bright material-containing layer 15 has a thickness of 25 nm or more and 200 nm or less, and is oriented approximately parallel to the surface of the bright material-containing layer 15. Specifically, the bright material 22 is oriented at an angle of 3 degrees or less with respect to the surface of the bright material-containing layer 15. After having applied a coating, which includes the bright material 22 and the pigment 23, on top of the colored base layer 14, a solvent included in the coating film is vaporized by stoving. As a result, the coating film shrinks in volume and becomes thin, and the bright material 22 is arranged at the orientation angle of 3 degrees or less (preferably 2 degree or less).

[0059] The colored base layer 14 contains a resin component which may be, e.g., a polyester-based resin. The bright material-containing layer 15 contains a resin component which may be, e.g., an acrylic-based resin. The colored base layer 16 contains a resin component which may be, e.g., an acid/epoxy-based cured acrylic resin.

[0060] <Control of Scattered Light, Etc.>

[0061] As illustrated in FIG. 2, if a large number of bright materials 22 are dispersed in the bright material-containing layer 30, light is reflected multiple times by the plurality of bright materials 22. The FI value is low if a large portion of the light undergoes multiple reflections and comes out of the bright material-containing layer 30 as scattered light at angles diverging from the specular reflection angle. That is, reducing the scattered light is important to increase the FI value. In addition, the light reaching a base layer 31 after the multiple reflections is diffused by the base layer 31 (i.e., diffuse reflection). The FI value is low if the diffuse reflection is strong. Thus, reducing the diffuse reflection by the base layer 31 is important to increase the FI value.

[0062] As illustrated in FIG. 3, the pigments 23 contained in the bright material-containing layer 15 contribute to increasing the FI value by absorbing the scattered light. The multiple reflections increase the optical path length. Due to the increased optical path length, light is more likely to be absorbed by the pigments 23. A greater FI value is obtained as a result. The broken-line arrows show that the pigments 23 reduce the intensity of the scattered light. Further, the scattered light which has reached the colored base layer 14 is absorbed by the colored base layer 14. That means the diffuse reflection is reduced. A greater FI value is obtained as a result.

[0063] A small area occupancy of the bright materials 22 reduces specular reflection of light by the bright materials 22, which affects adversely in increasing the FI value. On the other hand, a large area occupancy of the bight materials 22 increases the number of multiple reflections by the bight materials 22, which results in an increase in the scattered light and affects adversely in increasing the FI value.

[0064] As illustrated in FIG. 4, the FI value is obtained from the equation shown below, wherein L*45? is a lightness index of reflected light (45? reflected light) that is angled 45 degrees from a specular reflection angle toward an angle of incident light, which is incident on a surface of the multilayer coating film 12 at a 45-degree angle from a normal to the surface, L*15? is a lightness index of reflected light (15? reflected light) that is angled 15 degrees from the specular reflection angle toward the angle of incident light, and L*110? is a lightness index of reflected light (110? reflected light) that is angled 110 degrees from the specular reflection angle toward the angle of incident light.

FI=2.69?(L*15??L*110?).sup.1.11/L*45?.sup.0.86

[0065] <Bright Material-Containing Layer>

[0066] FIG. 5 illustrates example angle dependence of a Y value according to the XYZ color system, which is calibrated by a standard white plate, of the bright material-containing layer in a state without a colorant. FIG. 6 illustrates how to measure Y values. Light from a light source 41 is incident on the bright material-containing layer 15 at an angle of 45?. The receiving angle of a sensor 42 is defined such that the specular reflection angle is 0?. A three-dimensional gonio-spectrophotometric color measurement system GCMS-4 from Murakami Color Research Laboratory was used to measure the values. In the example illustrated in FIG. 5, Y(10?) is equal to 510 and Y(20?) is equal to 200, wherein Y(10?) represents a Y value of reflected light measured at a receiving angle (i.e., an angle toward the light source from the specular reflection angle) of 10?, and Y(20?) represents a Y value of the reflected light measured at a receiving angle of 20?.

[0067] According to the present invention, the following expressions are used in order that the coated object has a surface shining effect in a relatively wide area of its surface and significant FF properties: 50?Y(10?)?850 and Y(20?)=k?Y(10?), wherein Y(10?), k, and a colorant concentration C (% by mass) of the bright material-containing layer satisfy a predetermined condition. Herein, k is a coefficient and satisfies 0.2?k?0.6. Details will be described below.

[0068] As illustrated in FIG. 7, an experiment on a test product shows that if k is 0.4, the FI value is 30 or more when Y(10?) and C satisfy 100?Y(10?)?700 and 10?C?35. The FI value is 35 or more when Y(10?) and C satisfy 200?Y(10?)?600 and 15?C?30. In FIG. 7, the coordinates (x, y, z) given to the vertexes a to h of figures showing suitable ranges indicate the coordinates of a three-dimensional orthogonal coordinate space whose x-, y- and z-coordinate axes represent three variables Y(10?), k and C, respectively. The same explanation regarding the coordinates applies to FIGS. 8 and 9.

[0069] Similarly, as illustrated in FIG. 8, if k is 0.2, the H value is 30 or more when Y(10?) and C satisfy 50?Y(10?)?650 and 5?C?30. The H value is 35 or more when Y(10?) and C satisfy 150?Y(10?)?550 and 10?C?25.

[0070] Similarly, as illustrated in FIG. 9, if k is 0.6, the H value is 30 or more when Y(10?) and C satisfy 250?Y(10?)?850 and 15?C?40. The FI value is 35 or more when Y(10?) and C satisfy 350?Y(10?)?750 and 20?C?35.

[0071] FIG. 10 illustrates a two-dimensional orthogonal coordinate system whose coordinate axes represent two variables, i.e., Y(10?) and the coefficient k. The vertexes a to h, a to h, and a to h shown in FIGS. 7 to 9 are plotted in FIG. 10 to see the relationship between Y(10?) and the coefficient k. A suitable range of the coefficient k differs depending on Y(10?) as shown in the figure.

[0072] FIG. 11 illustrates a two-dimensional orthogonal coordinate system whose coordinate axes represent two variables, i.e., the coefficient k and the colorant concentration C. The vertexes a to h, a to h, and a to h are plotted in FIG. 11 to see the relationship between the coefficient k and the colorant concentration C. A suitable range of the colorant concentration C differs depending on the coefficient k as shown in the figure.

[0073] Thus, as illustrated in FIG. 12, ranges of Y(10?), the coefficient k, and the colorant concentration C at which the FI value is 30 or more can be expressed by the three-dimensional orthogonal coordinate space whose x-, y-, and z-coordinate axes represent the three variables Y(10?), k and C.

[0074] Specifically, the polyhedron shown in FIG. 12 is formed by the vertexes a to d, a to d, and a to d plotted in the three-dimensional orthogonal coordinate space. The polyhedron consists of ten planes A to J in total, each including four vertexes shown in Table 1.

[0075] A plane expressed by the coordinates (x, y, z) of the three-dimensional orthogonal coordinate space can be expressed by the equation ?x+?y+?z+?=0. The ten planes are expressed by the equations shown in Table 1.

TABLE-US-00001 TABLE 1 Plane Vertexes Equation for Plane A (a, c, a, c) A: 3000y ? 120z + 3000 = 0 B (b, d, b, d) B: 3000y ? 120z = 0 C (c, d, c, d) C: 5x ? 3750y ? 2000 = 0 D (a, b, a, b) D: 5x ? 3750y + 1000 = 0 E (a, c, b, d) E: 15000y ? 9000 = 0 F (c, d, c, d) F: 5x ? 1250y ? 3000 = 0 G (a, b, a, b) G: 5x ? 1250y = 0 H (a, c, b, d) H: 15000y ? 3000 = 0 I (a, c, a, c) A: 3000y ? 120z + 3000 = 0 J (b, d, b, d) B: 3000y ? 120z = 0

[0076] The planes A and I are expressed by the same equation, which means that these planes are the same plane. The planes B and J are expressed by the same equation, which means that these planes are the same plane. Thus, the polyhedron shown in FIG. 12 can be said to be an octahedron consisting of the eight planes A to H. The C and F planes of this octahedron form an inwardly protruding ridge, and the D and G planes form an outwardly protruding ridge.

[0077] Specifically, the polyhedron shown in FIG. 12 is an octahedron which consists of the eight planes expressed by the equations A to H listed in Table 1, wherein the planes expressed by the equations C and F form an inwardly protruding ridge, and the planes expressed by the equations D and G form an outwardly protruding ridge. The FI value is 30 or more if Y(10?), the coefficient k, and the colorant concentration C satisfy that the coordinates) (Y(10?, k, C) are in the range defined by the octahedron.

[0078] Similarly, as illustrated in FIG. 13, ranges of Y(10?), the coefficient k, and the colorant concentration C at which the FI value is 35 or more can be expressed by the three-dimensional orthogonal coordinate space whose x-, y-, and z-coordinate axes represent the three variables Y(10?), k and C. Specifically, this polyhedron is formed by the vertexes e to h, e to h, and e to h plotted in the three-dimensional orthogonal coordinate space, and consists of ten planes A to J in total, each including four vertexes shown in Table 2. The ten planes are expressed by the equations shown in Table 2.

TABLE-US-00002 TABLE 2 Plane Vertexes Equation for Plane A (e, g, e, g) A: 2000y ? 80z + 1600 = 0 B (f, h, f , h) B: 2000y ? 80z + 400 = 0 C (g, h, g, h) C: 3x ? 2250y ? 900 = 0 D (e, f, e, f) D: 3x ? 2250y + 300 = 0 E (e, g, f, h) E: 6000y ? 3600 = 0 F (g, h, g, h) F: 3x ? 750y ? 1500 = 0 G (e, f, e, f) G: 3x ? 750y ? 300 = 0 H (e, g, f, h) H: 6000y ? 1200 = 0 I (e, g, e, g) A: 2000y ? 80z + 1600 = 0 J (f, h, f, h) B: 2000y ? 80z + 400 = 0

[0079] The planes A and I are expressed by the same equation, which means that these planes are the same plane. The planes B and J are expressed by the same equation, which means that these planes are the same plane. Thus, the polyhedron shown in FIG. 13 can be said to be an octahedron consisting of the eight planes A to H. The C and F planes of this octahedron form an inwardly protruding ridge, and the D and G planes form an outwardly protruding ridge.

[0080] Specifically, the polyhedron shown in FIG. 13 is an octahedron which consists of the eight planes expressed by the equations A to H listed in Table 2, wherein the planes expressed by the equations C and F form an inwardly protruding ridge, and the planes expressed by the equations D and G form an outwardly protruding ridge. The FI value is 35 or more if Y(10?), the coefficient k, and the colorant concentration C satisfy that the coordinates (Y(10?), k, C) are in the range defined by the octahedron.

[0081] If the Y(10?), the coefficient k, and the colorant concentration C are determined such that the FI value is 30 or more, the bright material-containing layer containing a colorant has the Y(10?) of about 50 to 200, both inclusive, and the coefficient k (=Y(20?)/Y(10?)) of about 0.1 to 0.4, both inclusive.

Preferred Examples

[0082] First Example of Multilayer Coating Film (Gray Color Development)

[0083] Table 3 shows the constituents of a coating film according to the present example.

TABLE-US-00003 TABLE 3 First Example of Multilayer Coating Film (Gray Color Development) Mass % Coating Film of Solid Thickness Layer Kinds of Resin, etc. Content (?m) Transparent Resin: Acid/Epoxy-Based 100 30 Clear Layer Cured Acrylic Resin Bright Resin: Acrylic-Based 58.9 3 Material- Resin Containing Pigment: Fine Powder 21.5 Layer Carbon Black Y(10?) = 519 Bright Material: 19.6 Y(20?) = 198 Aluminum Flakes Colored Base Resin: Polyester-Based 65.7 10 Layer Resin Pigment: Commercially 7.1 Available Carbon Black Extender Pigment: 27.2 Barium Sulfate

[0084] After having employed the wet-on-wet method to apply coatings for the colored base layer, the bright material-containing layer, and the transparent clear layer, onto a steel product, the layers are stoved (heated at 140? C. for 20 minutes). Commercially available carbon black was employed as a pigment for the colored base layer. Fine powder carbon black is employed as a pigment for the bright material-containing layer. Aluminum flakes (having the average particle size of 12 ?m, a thickness of 110 nm, and the surface roughness of Ra?100 nm) are employed as a bright material, and arranged at the orientation angle of 2 degrees or less. The bright material-containing layer in a state without the pigment has the Y(10?) of 519 and the Y(20?) of 198.

[0085] Second Example of Multilayer Coating Film (Red Color Development)

[0086] Table 4 shows the constituents of a coating film according to the present example. The present example differs from the first example of the multilayer coating film in that perylene red is employed as a pigment for the bright material-containing layer, instead of the carbon black. The other constituents or preparation method are the same as those of the first example. The bright material-containing layer in a state without the pigment has the Y(10?) of 519 and the Y(20?) of 198.

TABLE-US-00004 TABLE 4 Second Example of Multilayer Coating Film (Red Color Development) Coating Film Mass % of Thickness Layer Kinds of Resin, etc. Solid Content (?m) Transparent Resin: Acid/Epoxy-Based 100 30 Clear Layer Cured Acrylic Resin Bright Resin: Acrylic-Based 61.5 3 Material- Resin Containing Pigment: Perylene Red 20.0 Layer Bright Material: 18.5 Y(10?) = 519 Aluminum Flakes Y(20?) = 198 Colored Base Resin: Polyester-Based 65.7 10 Layer Resin Pigment: Commercially 7.1 Available Carbon Black Extender Pigment: 27.2 Barium Sulfate

[0087] Third Example of Multilayer Coating Film (Red Color Development)

[0088] Table 5 shows the constituents of a coating film according to the present example. The present example differs from the first example of the multilayer coating film in that perylene red is employed as pigments for the bright material-containing layer and the colored base layer, instead of the carbon black. The other constituents or preparation method are the same as those of the first example. The bright material-containing layer in a state without the pigment has the Y(10?) of 519 and the Y(20?) of 198.

TABLE-US-00005 TABLE 5 Third Example of Multilayer Coating Film (Red Color Development) Coating Film Mass % of Thickness Layer Kinds of Resin, etc. Solid Content (?m) Transparent Resin: Acid/Epoxy-Based 100 30 Clear Layer Cured Acrylic Resin Bright Resin: Acrylic-Based 61.5 3 Material- Resin Containing Pigment: Perylene Red 20.0 Layer Bright Material: 18.5 Y(10?) = 519 Aluminum Flakes Y(20?) = 198 Colored Base Resin: Polyester-Based 60.9 12 Layer Resin Pigment: Perylene Red 13.9 Extender Pigment: 25.2 Barium Sulfate

[0089] Evaluation of Multilayer Coating Films

[0090] The FI vales of the first to third examples of the multilayer coating film were measured. Table 6 shows the results.

TABLE-US-00006 TABLE 6 First Example of Multilayer Coating Film FI = 35 (Gray Color Development) Second Example of Multilayer Coating Film FI = 30 (Red Color Development) Third Example of Multilayer Coating Film FI = 25 (Red Color Development)

[0091] The FI value of the second example of the multilayer coating film (red color development) is smaller than that of the first example of the multilayer coating film (gray color development). This may be because unlike a black pigment, the red pigment (i.e., perylene red) contained in the bright material-containing layer of the second example of the multilayer coating film strongly reflects visible light in a long wavelength range. That is, the FI value is small maybe because the light is diffused by the red pigment and because the red pigment absorbs less scattered light, scattered by the bright material, than the black pigment.

[0092] The FI value of the third example of the multilayer coating film is even smaller than that of the second example of the multilayer coating film. This may be because the red pigment is used in the colored base layer, that is, the colored base layer absorbs less light than the colored base layer containing a black pigment, in the third example of the multilayer coating film.

DESCRIPTION OF REFERENCE CHARACTERS

[0093] 11 Automobile Body (Steel Plate) [0094] 12 Multilayer Coating Film [0095] 13 Electrodeposition Coating Film [0096] 14 Colored Base Layer [0097] 15 Bright Material-Containing Layer [0098] 16 Transparent Clear Layer [0099] 21 Pigment (Colorant) [0100] 22 Bright Material [0101] 23 Pigment (Colorant)